CN112645971A - Method for directly preparing alkyl borate compound from alkyl halide - Google Patents
Method for directly preparing alkyl borate compound from alkyl halide Download PDFInfo
- Publication number
- CN112645971A CN112645971A CN202110073552.5A CN202110073552A CN112645971A CN 112645971 A CN112645971 A CN 112645971A CN 202110073552 A CN202110073552 A CN 202110073552A CN 112645971 A CN112645971 A CN 112645971A
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- CN
- China
- Prior art keywords
- noted
- alkyl
- compound
- stirred
- chloroform
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- -1 alkyl borate compound Chemical class 0.000 title claims abstract description 82
- 150000001350 alkyl halides Chemical class 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 29
- 150000001875 compounds Chemical class 0.000 claims abstract description 107
- 239000012298 atmosphere Substances 0.000 claims abstract description 70
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 15
- 239000010936 titanium Substances 0.000 claims abstract description 15
- 239000003513 alkali Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 230000001681 protective effect Effects 0.000 claims abstract description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 171
- LZPWAYBEOJRFAX-UHFFFAOYSA-N 4,4,5,5-tetramethyl-1,3,2$l^{2}-dioxaborolane Chemical compound CC1(C)O[B]OC1(C)C LZPWAYBEOJRFAX-UHFFFAOYSA-N 0.000 claims description 160
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 143
- 238000002360 preparation method Methods 0.000 claims description 104
- JAGHDVYKBYUAFD-UHFFFAOYSA-L cyclopenta-1,3-diene;titanium(4+);dichloride Chemical compound [Cl-].[Cl-].[Ti+4].C1C=CC=[C-]1.C1C=CC=[C-]1 JAGHDVYKBYUAFD-UHFFFAOYSA-L 0.000 claims description 93
- JILPJDVXYVTZDQ-UHFFFAOYSA-N lithium methoxide Chemical compound [Li+].[O-]C JILPJDVXYVTZDQ-UHFFFAOYSA-N 0.000 claims description 68
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 57
- PKLFICDRWXSEJK-UHFFFAOYSA-N B.C1(=CC=CC2=CC=CC=C12)O Chemical compound B.C1(=CC=CC2=CC=CC=C12)O PKLFICDRWXSEJK-UHFFFAOYSA-N 0.000 claims description 15
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 15
- 125000000623 heterocyclic group Chemical group 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 7
- 125000003342 alkenyl group Chemical group 0.000 claims description 6
- 229910000103 lithium hydride Inorganic materials 0.000 claims description 5
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 claims description 5
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 5
- QCEOZLISXJGWSW-UHFFFAOYSA-K 1,2,3,4,5-pentamethylcyclopentane;trichlorotitanium Chemical compound [Cl-].[Cl-].[Cl-].CC1=C(C)C(C)([Ti+3])C(C)=C1C QCEOZLISXJGWSW-UHFFFAOYSA-K 0.000 claims description 4
- ZBFBXTFQCKIUHU-UHFFFAOYSA-L 1,2,3,5,5-pentamethylcyclopenta-1,3-diene;titanium(4+);dichloride Chemical compound [Cl-].[Cl-].[Ti+4].CC1=[C-]C(C)(C)C(C)=C1C.CC1=[C-]C(C)(C)C(C)=C1C ZBFBXTFQCKIUHU-UHFFFAOYSA-L 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 4
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 4
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- LZWQNOHZMQIFBX-UHFFFAOYSA-N lithium;2-methylpropan-2-olate Chemical compound [Li+].CC(C)(C)[O-] LZWQNOHZMQIFBX-UHFFFAOYSA-N 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 4
- 229940071536 silver acetate Drugs 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- VUWPOFFYSGYZQR-UHFFFAOYSA-L tert-butylcyclopentane;dichlorotitanium Chemical compound Cl[Ti]Cl.CC(C)(C)[C]1[CH][CH][CH][CH]1.CC(C)(C)[C]1[CH][CH][CH][CH]1 VUWPOFFYSGYZQR-UHFFFAOYSA-L 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- QOXHZZQZTIGPEV-UHFFFAOYSA-K cyclopenta-1,3-diene;titanium(4+);trichloride Chemical compound Cl[Ti+](Cl)Cl.C=1C=C[CH-]C=1 QOXHZZQZTIGPEV-UHFFFAOYSA-K 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 3
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- SIAPCJWMELPYOE-UHFFFAOYSA-N lithium hydride Chemical compound [LiH] SIAPCJWMELPYOE-UHFFFAOYSA-N 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 4
- 125000000524 functional group Chemical group 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 188
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 166
- 238000006243 chemical reaction Methods 0.000 description 121
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 110
- 229910052757 nitrogen Inorganic materials 0.000 description 94
- 229910010068 TiCl2 Inorganic materials 0.000 description 89
- 238000004607 11B NMR spectroscopy Methods 0.000 description 55
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 55
- 238000005160 1H NMR spectroscopy Methods 0.000 description 55
- 238000012512 characterization method Methods 0.000 description 55
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 54
- 239000003480 eluent Substances 0.000 description 54
- 239000003208 petroleum Substances 0.000 description 54
- 239000007788 liquid Substances 0.000 description 47
- 238000004440 column chromatography Methods 0.000 description 42
- 238000004817 gas chromatography Methods 0.000 description 42
- VMKOFRJSULQZRM-UHFFFAOYSA-N 1-bromooctane Chemical compound CCCCCCCCBr VMKOFRJSULQZRM-UHFFFAOYSA-N 0.000 description 40
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 description 36
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 34
- 238000000746 purification Methods 0.000 description 34
- 229910000027 potassium carbonate Inorganic materials 0.000 description 17
- 239000000203 mixture Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 12
- 239000011734 sodium Substances 0.000 description 12
- 229910000085 borane Inorganic materials 0.000 description 6
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
- IHLVCKWPAMTVTG-UHFFFAOYSA-N lithium;carbanide Chemical compound [Li+].[CH3-] IHLVCKWPAMTVTG-UHFFFAOYSA-N 0.000 description 4
- WMDHQEHPOVOEOG-UHFFFAOYSA-N 2-(2-bromoethyl)-1,3-dioxane Chemical compound BrCCC1OCCCO1 WMDHQEHPOVOEOG-UHFFFAOYSA-N 0.000 description 3
- LDPMCSWZEGKWLC-UHFFFAOYSA-N 2-hexyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Chemical compound CCCCCCB1OC(C)(C)C(C)(C)O1 LDPMCSWZEGKWLC-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- MPVONIMKFUZRQI-OPRDCNLKSA-N (1r,2r,4r)-2-bromo-4-methyl-1-propan-2-ylcyclohexane Chemical compound CC(C)[C@H]1CC[C@@H](C)C[C@H]1Br MPVONIMKFUZRQI-OPRDCNLKSA-N 0.000 description 2
- QXYOAWHKJRWNID-RRKCRQDMSA-N (1s,3r,4r)-3-bromobicyclo[2.2.1]heptane Chemical compound C1C[C@H]2[C@H](Br)C[C@@H]1C2 QXYOAWHKJRWNID-RRKCRQDMSA-N 0.000 description 2
- WGEHWCGDFFFRKA-UTLNTRLCSA-N (3S,8S,9S,10R,13S,14S,17R)-16-bromo-10,13-dimethyl-17-[(2R)-6-methylheptan-2-yl]-2,3,4,7,8,9,11,12,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthren-3-ol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC(Br)[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 WGEHWCGDFFFRKA-UTLNTRLCSA-N 0.000 description 2
- WTCVMJLGKMOROW-UHFFFAOYSA-N 1-(2-bromoethyl)-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(CCBr)C=C1 WTCVMJLGKMOROW-UHFFFAOYSA-N 0.000 description 2
- KWQRRNDZNAXRGO-UHFFFAOYSA-N 1-bromo-2-methylcyclohexane Chemical compound CC1CCCCC1Br KWQRRNDZNAXRGO-UHFFFAOYSA-N 0.000 description 2
- VGSUDZKDSKCYJP-UHFFFAOYSA-N 1-bromo-3,7-dimethyloctane Chemical compound CC(C)CCCC(C)CCBr VGSUDZKDSKCYJP-UHFFFAOYSA-N 0.000 description 2
- CEVMYGZHEJSOHZ-UHFFFAOYSA-N 1-bromo-3-methoxypropane Chemical compound COCCCBr CEVMYGZHEJSOHZ-UHFFFAOYSA-N 0.000 description 2
- YXZFFTJAHVMMLF-UHFFFAOYSA-N 1-bromo-3-methylbutane Chemical compound CC(C)CCBr YXZFFTJAHVMMLF-UHFFFAOYSA-N 0.000 description 2
- YWTSERISEGNNBO-UHFFFAOYSA-N 1-bromo-4-(4-bromobutyl)benzene Chemical compound BrCCCCC1=CC=C(Br)C=C1 YWTSERISEGNNBO-UHFFFAOYSA-N 0.000 description 2
- VQHPRVYDKRESCL-UHFFFAOYSA-N 1-bromoadamantane Chemical compound C1C(C2)CC3CC2CC1(Br)C3 VQHPRVYDKRESCL-UHFFFAOYSA-N 0.000 description 2
- LSXKDWGTSHCFPP-UHFFFAOYSA-N 1-bromoheptane Chemical compound CCCCCCCBr LSXKDWGTSHCFPP-UHFFFAOYSA-N 0.000 description 2
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical compound CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 description 2
- DZMDPHNGKBEVRE-UHFFFAOYSA-N 1-chloroheptane Chemical compound CCCCCCCCl DZMDPHNGKBEVRE-UHFFFAOYSA-N 0.000 description 2
- CNDHHGUSRIZDSL-UHFFFAOYSA-N 1-chlorooctane Chemical compound CCCCCCCCCl CNDHHGUSRIZDSL-UHFFFAOYSA-N 0.000 description 2
- ANOOTOPTCJRUPK-UHFFFAOYSA-N 1-iodohexane Chemical compound CCCCCCI ANOOTOPTCJRUPK-UHFFFAOYSA-N 0.000 description 2
- VOHRIBRQYLSFCF-UHFFFAOYSA-N 2-(3-bromopropoxy)naphthalene Chemical compound C1=CC=CC2=CC(OCCCBr)=CC=C21 VOHRIBRQYLSFCF-UHFFFAOYSA-N 0.000 description 2
- HJNHUFQGDJLQRS-UHFFFAOYSA-N 2-(3-bromopropoxy)oxane Chemical compound BrCCCOC1CCCCO1 HJNHUFQGDJLQRS-UHFFFAOYSA-N 0.000 description 2
- RCXJARRRXOPXBC-UHFFFAOYSA-N 2-bromoadamantane Chemical compound C1C(C2)CC3CC1C(Br)C2C3 RCXJARRRXOPXBC-UHFFFAOYSA-N 0.000 description 2
- JRQAAYVLPPGEHT-UHFFFAOYSA-N 2-bromoethylcyclohexane Chemical compound BrCCC1CCCCC1 JRQAAYVLPPGEHT-UHFFFAOYSA-N 0.000 description 2
- FTJHYGJLHCGQHQ-UHFFFAOYSA-N 2-bromooctane Chemical compound CCCCCCC(C)Br FTJHYGJLHCGQHQ-UHFFFAOYSA-N 0.000 description 2
- XQZUHTDYDIRXPP-UHFFFAOYSA-N 3-(2-bromoethyl)thiophene Chemical compound BrCCC=1C=CSC=1 XQZUHTDYDIRXPP-UHFFFAOYSA-N 0.000 description 2
- NIDWUZTTXGJFNN-UHFFFAOYSA-N 3-bromopropoxybenzene Chemical compound BrCCCOC1=CC=CC=C1 NIDWUZTTXGJFNN-UHFFFAOYSA-N 0.000 description 2
- PSUXTZLDBVEZTD-UHFFFAOYSA-N 3-bromopropoxymethylbenzene Chemical compound BrCCCOCC1=CC=CC=C1 PSUXTZLDBVEZTD-UHFFFAOYSA-N 0.000 description 2
- AZXLOLRTEJEZHJ-UHFFFAOYSA-N 3-chloropropoxybenzene Chemical compound ClCCCOC1=CC=CC=C1 AZXLOLRTEJEZHJ-UHFFFAOYSA-N 0.000 description 2
- QCKVUTCVXGLZQC-UHFFFAOYSA-N 3-hydroxy-1,2-dimethyl-1,2,3,9-tetrahydrocarbazol-4-one Chemical compound N1C2=CC=CC=C2C2=C1C(C)C(C)C(O)C2=O QCKVUTCVXGLZQC-UHFFFAOYSA-N 0.000 description 2
- IVBVKTPDEWDNRW-UHFFFAOYSA-N 4-bromooxane Chemical compound BrC1CCOCC1 IVBVKTPDEWDNRW-UHFFFAOYSA-N 0.000 description 2
- DHRSKOBIDIDMJZ-UHFFFAOYSA-N 4-chlorooxane Chemical compound ClC1CCOCC1 DHRSKOBIDIDMJZ-UHFFFAOYSA-N 0.000 description 2
- JRKZQRRYNCMSCB-UHFFFAOYSA-N 5-(2-bromoethyl)-2,3-dihydro-1-benzofuran Chemical compound BrCCC1=CC=C2OCCC2=C1 JRKZQRRYNCMSCB-UHFFFAOYSA-N 0.000 description 2
- UNXURIHDFUQNOC-UHFFFAOYSA-N 5-bromo-2-methylpent-2-ene Chemical compound CC(C)=CCCBr UNXURIHDFUQNOC-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LEAYTROYTDCWDN-UHFFFAOYSA-N C1CCCC1.O(C1=CC=CC=C1)CCCB1OC(C(O1)(C)C)(C)C Chemical compound C1CCCC1.O(C1=CC=CC=C1)CCCB1OC(C(O1)(C)C)(C)C LEAYTROYTDCWDN-UHFFFAOYSA-N 0.000 description 2
- YITQVQAZYWMOFE-UHFFFAOYSA-N CC1(C)OB(C2=CC=C(CCCCBr)C=C2)OC1(C)C Chemical compound CC1(C)OB(C2=CC=C(CCCCBr)C=C2)OC1(C)C YITQVQAZYWMOFE-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- BFWKSPOSMPKTSV-UHFFFAOYSA-N benzyl 4-bromopiperidine-1-carboxylate Chemical compound C1CC(Br)CCN1C(=O)OCC1=CC=CC=C1 BFWKSPOSMPKTSV-UHFFFAOYSA-N 0.000 description 2
- LOXORFRCPXUORP-UHFFFAOYSA-N bromo-Cycloheptane Chemical compound BrC1CCCCCC1 LOXORFRCPXUORP-UHFFFAOYSA-N 0.000 description 2
- KXVUSQIDCZRUKF-UHFFFAOYSA-N bromocyclobutane Chemical compound BrC1CCC1 KXVUSQIDCZRUKF-UHFFFAOYSA-N 0.000 description 2
- AQNQQHJNRPDOQV-UHFFFAOYSA-N bromocyclohexane Chemical compound BrC1CCCCC1 AQNQQHJNRPDOQV-UHFFFAOYSA-N 0.000 description 2
- BRTFVKHPEHKBQF-UHFFFAOYSA-N bromocyclopentane Chemical compound BrC1CCCC1 BRTFVKHPEHKBQF-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- STJYMUBZVMSMBP-UHFFFAOYSA-N chlorocyclobutane Chemical compound ClC1CCC1 STJYMUBZVMSMBP-UHFFFAOYSA-N 0.000 description 2
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- OOBFNDGMAGSNKA-UHFFFAOYSA-N ethyl 7-bromoheptanoate Chemical compound CCOC(=O)CCCCCCBr OOBFNDGMAGSNKA-UHFFFAOYSA-N 0.000 description 2
- URIRDRHUUFRHAS-UHFFFAOYSA-N hexyl methanesulfonate Chemical compound CCCCCCOS(C)(=O)=O URIRDRHUUFRHAS-UHFFFAOYSA-N 0.000 description 2
- 238000006197 hydroboration reaction Methods 0.000 description 2
- ULYZAYCEDJDHCC-UHFFFAOYSA-N isopropyl chloride Chemical compound CC(C)Cl ULYZAYCEDJDHCC-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- KZBWIYHDNQHMET-UHFFFAOYSA-N tert-butyl 4-bromopiperidine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCC(Br)CC1 KZBWIYHDNQHMET-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- OWXJKYNZGFSVRC-IHWYPQMZSA-N (z)-1-chloroprop-1-ene Chemical group C\C=C/Cl OWXJKYNZGFSVRC-IHWYPQMZSA-N 0.000 description 1
- CRRUGYDDEMGVDY-UHFFFAOYSA-N 1-bromoethylbenzene Chemical compound CC(Br)C1=CC=CC=C1 CRRUGYDDEMGVDY-UHFFFAOYSA-N 0.000 description 1
- AYMUQTNXKPEMLM-UHFFFAOYSA-N 1-bromononane Chemical compound CCCCCCCCCBr AYMUQTNXKPEMLM-UHFFFAOYSA-N 0.000 description 1
- 238000004293 19F NMR spectroscopy Methods 0.000 description 1
- LKWTXDMOVNQZQJ-UHFFFAOYSA-N 2-(2-adamantyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Chemical compound C12C(C3CC(CC(C1)C3)C2)B1OC(C(O1)(C)C)(C)C LKWTXDMOVNQZQJ-UHFFFAOYSA-N 0.000 description 1
- SZLPRRVCSGZARF-UHFFFAOYSA-N 2-(2-bromoethyl)-2-methyl-1,3-dioxolane Chemical compound BrCCC1(C)OCCO1 SZLPRRVCSGZARF-UHFFFAOYSA-N 0.000 description 1
- QESAOLFAFYVLJP-UHFFFAOYSA-N 2-(3-bromopropylsulfanyl)-2-methylpropane Chemical compound CC(C)(C)SCCCBr QESAOLFAFYVLJP-UHFFFAOYSA-N 0.000 description 1
- VNYAVQWHXWIAQD-UHFFFAOYSA-N 2-(4,4-dimethylpentyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Chemical compound CC(C)(C)CCCB1OC(C)(C)C(C)(C)O1 VNYAVQWHXWIAQD-UHFFFAOYSA-N 0.000 description 1
- LTOCOTGOQPVJGL-UHFFFAOYSA-N 2-[4-(4-bromophenyl)butyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Chemical compound CC1(C)OB(CCCCc2ccc(Br)cc2)OC1(C)C LTOCOTGOQPVJGL-UHFFFAOYSA-N 0.000 description 1
- APYDCTAPNKFTRB-UHFFFAOYSA-N 2-bromo-2,3-dihydro-1h-indene Chemical compound C1=CC=C2CC(Br)CC2=C1 APYDCTAPNKFTRB-UHFFFAOYSA-N 0.000 description 1
- CJHFLFQCUUOKEK-UHFFFAOYSA-N 2-cyclobutyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Chemical compound O1C(C)(C)C(C)(C)OB1C1CCC1 CJHFLFQCUUOKEK-UHFFFAOYSA-N 0.000 description 1
- SXXIRRKFRJTGRV-UHFFFAOYSA-N 2-cycloheptyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Chemical compound O1C(C)(C)C(C)(C)OB1C1CCCCCC1 SXXIRRKFRJTGRV-UHFFFAOYSA-N 0.000 description 1
- OUEVCDGYTKLNMJ-UHFFFAOYSA-N 2-cyclohexyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Chemical compound O1C(C)(C)C(C)(C)OB1C1CCCCC1 OUEVCDGYTKLNMJ-UHFFFAOYSA-N 0.000 description 1
- BLLUYOVVBCMKHV-UHFFFAOYSA-N 2-cyclopentyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Chemical compound O1C(C)(C)C(C)(C)OB1C1CCCC1 BLLUYOVVBCMKHV-UHFFFAOYSA-N 0.000 description 1
- NMNNFIWUPMSIOH-UHFFFAOYSA-N 2-heptyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Chemical compound CCCCCCCB1OC(C)(C)C(C)(C)O1 NMNNFIWUPMSIOH-UHFFFAOYSA-N 0.000 description 1
- UCFSYHMCKWNKAH-UHFFFAOYSA-N 4,4,5,5-tetramethyl-1,3,2-dioxaborolane Chemical compound CC1(C)OBOC1(C)C UCFSYHMCKWNKAH-UHFFFAOYSA-N 0.000 description 1
- VCDOIGFHIYDCOV-UHFFFAOYSA-N 4,4,5,5-tetramethyl-2-(1-methylcyclohexyl)-1,3,2-dioxaborolane Chemical compound O1C(C)(C)C(C)(C)OB1C1(C)CCCCC1 VCDOIGFHIYDCOV-UHFFFAOYSA-N 0.000 description 1
- CQDNCEVDFBTLSJ-UHFFFAOYSA-N 4,4,5,5-tetramethyl-2-(2-thiophen-3-ylethyl)-1,3,2-dioxaborolane Chemical compound O1C(C)(C)C(C)(C)OB1CCC1=CSC=C1 CQDNCEVDFBTLSJ-UHFFFAOYSA-N 0.000 description 1
- SXRUVAWZZHDPCJ-UHFFFAOYSA-N 4,4,5,5-tetramethyl-2-(3-phenylmethoxypropyl)-1,3,2-dioxaborolane Chemical compound CC1(C)OB(CCCOCc2ccccc2)OC1(C)C SXRUVAWZZHDPCJ-UHFFFAOYSA-N 0.000 description 1
- WHSCXARPDWZZRD-UHFFFAOYSA-N 4,4,5,5-tetramethyl-2-(4-methylpent-3-enyl)-1,3,2-dioxaborolane Chemical compound CC(C)=CCCB1OC(C)(C)C(C)(C)O1 WHSCXARPDWZZRD-UHFFFAOYSA-N 0.000 description 1
- HYBBUOVFAUSTSO-UHFFFAOYSA-N 4,4,5,5-tetramethyl-2-[2-[4-(trifluoromethyl)phenyl]ethyl]-1,3,2-dioxaborolane Chemical compound O1C(C)(C)C(C)(C)OB1CCC1=CC=C(C(F)(F)F)C=C1 HYBBUOVFAUSTSO-UHFFFAOYSA-N 0.000 description 1
- LVDYSUBEFHXDRW-UHFFFAOYSA-N 4,4,5,5-tetramethyl-2-nonyl-1,3,2-dioxaborolane Chemical compound CCCCCCCCCB1OC(C)(C)C(C)(C)O1 LVDYSUBEFHXDRW-UHFFFAOYSA-N 0.000 description 1
- JYYHTFAJEPMWME-UHFFFAOYSA-N 4,4,5,5-tetramethyl-2-octyl-1,3,2-dioxaborolane Chemical compound CCCCCCCCB1OC(C)(C)C(C)(C)O1 JYYHTFAJEPMWME-UHFFFAOYSA-N 0.000 description 1
- KYWQKZZFEDWVJW-UHFFFAOYSA-N 5-bromo-5-propylcyclohexa-1,3-diene Chemical compound CCCC1(Br)CC=CC=C1 KYWQKZZFEDWVJW-UHFFFAOYSA-N 0.000 description 1
- 241000349731 Afzelia bipindensis Species 0.000 description 1
- FVTCETUZWPRVHN-UHFFFAOYSA-N B(O)(O)O.CC(C(C)C)CC(O)(C)C(C)(C)O Chemical compound B(O)(O)O.CC(C(C)C)CC(O)(C)C(C)(C)O FVTCETUZWPRVHN-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- FFLUWRSGIQQKPK-UHFFFAOYSA-N BrCCCCC(C)(C)SC(CCCCBr)(C)C Chemical compound BrCCCCC(C)(C)SC(CCCCBr)(C)C FFLUWRSGIQQKPK-UHFFFAOYSA-N 0.000 description 1
- GXENTCUOLKUXOV-UHFFFAOYSA-N C(C)(C)C1C(CC(CC1)C)B1OC(C(O1)(C)C)(C)C Chemical compound C(C)(C)C1C(CC(CC1)C)B1OC(C(O1)(C)C)(C)C GXENTCUOLKUXOV-UHFFFAOYSA-N 0.000 description 1
- IDNXNEHEXZQMSR-UHFFFAOYSA-N C(C)C1C(CCCC1)B1OC(C)(C)C(C)(C)O1 Chemical compound C(C)C1C(CCCC1)B1OC(C)(C)C(C)(C)O1 IDNXNEHEXZQMSR-UHFFFAOYSA-N 0.000 description 1
- SNWQIZUNQXKCHW-UHFFFAOYSA-N C1CCCC1.C1(CCC1)B1OC(C(O1)(C)C)(C)C Chemical compound C1CCCC1.C1(CCC1)B1OC(C(O1)(C)C)(C)C SNWQIZUNQXKCHW-UHFFFAOYSA-N 0.000 description 1
- FNOAMAFRNTVRTQ-UHFFFAOYSA-N C1CCCC1.CC1(OBOC1(C)C)C Chemical compound C1CCCC1.CC1(OBOC1(C)C)C FNOAMAFRNTVRTQ-UHFFFAOYSA-N 0.000 description 1
- NTJMNICMMYRFCE-UHFFFAOYSA-N C1CCCC1.COCCCB1OC(C(O1)(C)C)(C)C Chemical compound C1CCCC1.COCCCB1OC(C(O1)(C)C)(C)C NTJMNICMMYRFCE-UHFFFAOYSA-N 0.000 description 1
- FCJNKEZRAAAPFR-UHFFFAOYSA-N CC(CB1OC(C(O1)(C)C)(C)C)CCCCC(C)C Chemical compound CC(CB1OC(C(O1)(C)C)(C)C)CCCCC(C)C FCJNKEZRAAAPFR-UHFFFAOYSA-N 0.000 description 1
- PTGXRVIDOHHRTJ-UHFFFAOYSA-N CC1(C)OB(CCCOC2CCCCO2)OC1(C)C Chemical compound CC1(C)OB(CCCOC2CCCCO2)OC1(C)C PTGXRVIDOHHRTJ-UHFFFAOYSA-N 0.000 description 1
- ZWYJHHZYIYZENQ-UHFFFAOYSA-N CC1(OBOC1(C)C)C.C(C)C1OC2=C(C1)C=CC=C2 Chemical compound CC1(OBOC1(C)C)C.C(C)C1OC2=C(C1)C=CC=C2 ZWYJHHZYIYZENQ-UHFFFAOYSA-N 0.000 description 1
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- 229910010062 TiCl3 Inorganic materials 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- TUWZZXGAUMSUOB-UHFFFAOYSA-N benzyl piperidine-1-carboxylate Chemical compound C1CCCCN1C(=O)OCC1=CC=CC=C1 TUWZZXGAUMSUOB-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- DAJLHNABGVYSOO-UHFFFAOYSA-N boric acid;2,3-dimethylbutane-2,3-diol Chemical compound OB(O)O.CC(C)(O)C(C)(C)O DAJLHNABGVYSOO-UHFFFAOYSA-N 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 238000005271 boronizing Methods 0.000 description 1
- DVEXRVSMBASKIW-UHFFFAOYSA-N bromobenzene;propane Chemical compound CCC.BrC1=CC=CC=C1 DVEXRVSMBASKIW-UHFFFAOYSA-N 0.000 description 1
- IADKAKQBSKWITE-UHFFFAOYSA-N bromocyclododecane Chemical compound BrC1CCCCCCCCCCC1 IADKAKQBSKWITE-UHFFFAOYSA-N 0.000 description 1
- UUWSLBWDFJMSFP-UHFFFAOYSA-N bromomethylcyclohexane Chemical compound BrCC1CCCCC1 UUWSLBWDFJMSFP-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- ZCSQKFUQLUJERT-UHFFFAOYSA-K cyclopenta-1,3-diene titanium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Ti+3].C1C=CC=C1 ZCSQKFUQLUJERT-UHFFFAOYSA-K 0.000 description 1
- 238000005695 dehalogenation reaction Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N methyl heptene Natural products CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/025—Boronic and borinic acid compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J51/00—Normal steroids with unmodified cyclopenta(a)hydrophenanthrene skeleton not provided for in groups C07J1/00 - C07J43/00
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
Abstract
The invention relates to a method for directly preparing alkyl borate compounds from alkyl halides, which comprises the following steps: in a protective atmosphere, mixing a titanium metal catalyst, an alkali compound, a borate compound and an alkyl halide or sulfonate compound, and reacting at 35-100 ℃ for 8-24 hours, namely directly converting the alkyl halide or sulfonate compound into an alkyl boronic acid pinacol ester compound. The method has the advantages of simple operation, low cost, good functional group tolerance and wide substrate application range.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a method for directly preparing alkyl borate compounds from alkyl halides.
Background
The alkyl borate compounds are important organic synthesis intermediates, can be cross-coupled with an electrophilic reagent to prepare drug molecules, and play an important role in pharmaceutical chemistry application. Alkyl borate compounds are traditionally prepared by using metal reagents such as alkyl lithium, alkyl magnesium and the like through transmetallization reaction, but the application range of substrates is narrow. In addition, olefin hydroboration reaction can also be used for preparing alkyl borate compounds, but due to multiple reaction sites of olefin and occurrence of olefin isomerization, selectivity of the olefin is very challenging.
In recent years, scientists have focused on the use of boronation of alkyl halides as an alternative method for preparing alkyl borate esters, which has the advantages of using abundant or readily available alkyl halides as starting materials, reducing synthesis costs, and avoiding regioselectivity problems in the olefin hydroboration reaction. Scientists have developed processes for the conversion of alkyl halides to alkyl borate compounds based on transition metal catalysts such as Cu, Ni, Pd, Rh, Zn, Fe, Mn, etc. However, B is used in all of these known methods2pin2Or B2cat2As a boronizing agent, no report has been found on the study of HBpin or HBcat as a boron source.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for directly preparing alkyl borate compounds from alkyl halides, which has the advantages of simple operation, low cost, good functional group tolerance and wide substrate application range.
In order to solve the problems, the method for directly preparing the alkyl borate compound by using the alkyl halide is characterized by comprising the following steps of: in a protective atmosphere, mixing a titanium metal catalyst, an alkali compound, a borate compound and an alkyl halide or sulfonate compound, and reacting at 35-100 ℃ for 8-24 hours, namely directly converting the alkyl halide or sulfonate compound into an alkyl boronic acid pinacol ester compound; the molar ratio of the alkyl halide or sulfonate compound, the titanium metal catalyst, the alkali compound and the borate compound is 1: 0.05-0.1: 0.25-1: 2 to 3.
The reaction equation is as follows:
an organic solvent is also added in the mixing process of the titanium metal catalyst, the alkali compound, the borate compound and the alkyl halide or sulfonate compound; the molar ratio of the alkyl halide or sulfonate compound to the organic solvent is 0.2 mmol: 1 mL.
The structural formula of the alkyl halide or sulfonate compound is as follows:(ii) a In the formula: r1Is one of benzyl, substituted benzyl, heterocycle, substituted heterocycle, alkyl or alkenyl; r2And R3Are both alkyl or hydrogen.
The R is1Is one of benzyl, substituted benzyl, heterocycle, substituted heterocycle, alkyl or alkenyl.
And the substituent in the substituted benzyl is one of methyl, methoxy, ester, fluorine, chlorine, bromine, phenyl or trifluoromethyl.
The titanium metal catalyst is one of bis (cyclopentadienyl) titanium dichloride, (cyclopentadienyl) titanium trichloride, bis (tert-butylcyclopentadienyl) titanium dichloride, pentamethylcyclopentadienyl titanium trichloride and bis (pentamethylcyclopentadienyl) titanium dichloride.
The borate compound is pinacol borane or naphthol borane.
The alkali compound is one of potassium methoxide, sodium methoxide, lithium methoxide, potassium tert-butoxide, sodium tert-butoxide, lithium tert-butoxide, cesium carbonate, cesium fluoride, silver acetate, lithium carbonate, lithium hydride and methyllithium.
The organic solvent is one of N-hexane, dioxane, chloroform, N-dimethylformamide, ethyl acetate, diethylene glycol dimethyl ether, methyl tert-butyl ether, tetrahydrofuran, dichloromethane, acetonitrile and toluene.
The protective atmosphere refers to nitrogen atmosphere or argon atmosphere, and the pressure is 1 atm.
Compared with the prior art, the invention has the following advantages:
1. the method uses the titanium metal which is relatively cheap and widely exists in the nature, and reduces the reaction cost.
2. The method takes titanium metal as a catalyst, takes HBpin or HBcat as a boron source, can directly convert alkyl halide or sulfonate compound into the alkyl boronic acid pinacol ester compound, and has the advantages of simple operation, low cost, good functional group tolerance and wide substrate application range. Meanwhile, the reaction that the alkyl halide reacts with the borane to generate saturated alkane through hydrogenation dehalogenation reaction, which is often generated by using other transition metal catalysts, is avoided.
3. The synthesized borate compound has high yield and good selectivity, and is beneficial to separation and purification of products.
Detailed Description
A method for directly preparing alkyl borate compounds from alkyl halides comprises the following steps: in a nitrogen or argon protective atmosphere with the pressure of 1atm, mixing a titanium metal catalyst, an alkaline compound, a borate compound and an alkyl halide or sulfonate compound, and reacting for 8-24 hours at 35-100 ℃, namely directly converting the alkyl halide or sulfonate compound into an alkyl boronic acid pinacol ester compound.
Wherein: the molar ratio of the alkyl halide or sulfonate compound to the titanium metal catalyst to the alkali compound to the borate compound is 1: 0.05-0.1: 0.25-1: 2 to 3.
An organic solvent is also added in the mixing process of the titanium metal catalyst, the alkali compound, the borate compound and the alkyl halide or sulfonate compound; the volume ratio of the molar weight of the alkyl halide or sulfonate compound to the organic solvent is 0.2 mmol: 1 mL.
The structural formula of the alkyl halide or sulfonate compound is as follows:(ii) a In the formula: r1Is one of benzyl, substituted benzyl, heterocycle, substituted heterocycle, alkyl or alkenyl; r2And R3Are both alkyl or hydrogen. R1Is one of benzyl, substituted benzyl, heterocycle, substituted heterocycle, alkyl or alkenyl. The substituent in the substituted benzyl is one of methyl, methoxy, ester, fluorine, chlorine, bromine, phenyl or trifluoromethyl。
The titanium metal catalyst is one of bis (cyclopentadienyl) titanium dichloride, (cyclopentadienyl) titanium trichloride, bis (tert-butylcyclopentadienyl) titanium dichloride, pentamethylcyclopentadienyl titanium trichloride and bis (pentamethylcyclopentadienyl) titanium dichloride.
The borate compound is pinacol borane or naphthol borane.
The alkali compound is one of potassium methoxide, sodium methoxide, lithium methoxide, potassium tert-butoxide, sodium tert-butoxide, lithium tert-butoxide, cesium carbonate, cesium fluoride, silver acetate, lithium carbonate, lithium hydride and methyllithium.
The organic solvent is one of N-hexane, dioxane, chloroform, N-dimethylformamide, ethyl acetate, diethylene glycol dimethyl ether, methyl tert-butyl ether, tetrahydrofuran, dichloromethane, acetonitrile and toluene.
In the present invention, all the raw materials are commercially available products well known to those skilled in the art unless otherwise specified. The present invention is not limited to any particular substitution site for the substituent.
In a specific embodiment of the invention, the alkyl halide or sulfonate compound is 1-bromooctane, 1-bromohexane, 1-bromoheptane, 1-bromononane bromomethylcyclohexane, 2-cyclohexylbromoethane, 1-bromo-3-methylbutane, 1-bromo-3, 7-dimethyloctane, 1-bromophenyl propane, ethyl 7-bromoheptanoate, ethyl 2- (4- (4-bromobutyl) phenyl) acetate, 5-bromo-2-methyl-2-pentene, 1-bromoethyl benzene, p-trifluoromethylbromoethyl benzene, 3- (2-bromoethyl) thiophene, 5- (2-bromoethyl) -2, 3-dihydrobenzofuran, 2- (2-bromoethyl) -1, 3-dioxane, 2- (2-bromoethyl) -1, 3-dioxane, 3-bromopropyl methyl ether, 3-phenoxybromopropane, 3-benzyloxybromopropane, 2- (3-bromopropoxy) naphthalene, 2- (3-bromopropoxy) tetrahydro-2 h-pyran, 3-bromopropyl-1, 1-dimethylethyl sulfide, 2- (4- (4-bromobutyl) phenyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborole, 1-bromo-4- (4-bromobutyl) benzene, 1- (5-bromopentyl) -1 hydroindole, 9- (5-bromopentyl) -9 hydrocarbazole, bromocyclobutane, bromocyclododecane, and the like, Bromocyclopentane, bromocyclohexane, bromocycloheptane, 4-bromotetrahydropyran, 1-bromo-2-methylcyclohexane, (1R, 2R, 4R) -2-bromo-1-isopropyl-4-methylcyclohexane, 2-bromoindane, exo-2-bromonorbornane, 2-bromooctane, 2-bromoadamantane, 1-Cbz-4-bromopiperidine, 1-Boc-4-bromopiperidine, 1-bromoadamantane, 1-bromocedryl, bromocholesterol, 1-chloroheptane, 1-chlorooctane, 1-chloroethane, 1-chloropropylene, 3-phenoxychloropropane, 2-chloropropane, 4-chlorotetrahydropyran, chlorocyclobutane, 1-iodohexane, hexyl methanesulfonate, (5S, 8S, 9S, 10S, 13S, 14S) -3-bromo-10, 13-dimethylhexadecahydro-17 hydro-cyclopenta [ a ] phenanthren-17-one.
In the present invention, the reaction is preferably carried out under stirring, and the stirring conditions in the present invention are not particularly limited, and may be carried out by a procedure well known to those skilled in the art.
After the reduction reaction is finished, the method also preferably comprises separation, the method does not have any special limitation on the separation, column chromatography is adopted to purify the product, if naphthol borane is used as a boron source in the reaction, pinacol and triethylamine are added to carry out conversion after the reaction is finished, and then column chromatography purification is carried out. In the embodiment of the invention, the separation is not performed in the embodiments 1 to 40, an alkyl boronic acid pinacol ester product system is directly obtained, and the yield of the alkyl boronic acid pinacol ester compound in the product system is analyzed through gas chromatography. If the product system needs to be separated and purified, the separation method is referred to.
The following examples are provided to illustrate the preparation of the borate compounds of the present invention in detail, but they should not be construed as limiting the scope of the present invention.
Example 1 bis (cyclopentadienyl) titanium dichloride (noted Cp)2TiCl20.01mmol, 2.5 mg), lithium methoxide (noted as MeOLi,0.2mmol,7.6 mg), methyl tert-butyl ether (noted as MTBE, 1 mL), and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-bromooctane (noted as 1a, 0.2mmol, 34. mu.L), and stirred at 60 ℃ for 24h under nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure represented by formula 2 a. The yield of the gas chromatography was 81%.
The chemical reaction formula of the preparation process is as follows:
example 2 bis (cyclopentadienyl) titanium dichloride (noted Cp)2TiCl20.02mmol, 5 mg), potassium methoxide (noted as MeOK, 0.2mmol, 14.0 mg), toluene (1 mL) and pinacolborane (noted as HBpin, 0.4mmol, 58 μ L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-bromooctane (noted as 1a, 0.2mmol, 34 μ L), and stirred at 100 ℃ for 8h under nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure shown in formula 2 a. The yield of the gas chromatography was 6%.
The chemical reaction formula of the preparation process is as follows:
example 3 bis (cyclopentadienyl) titanium dichloride (noted Cp)2TiCl20.02mmol, 5 mg), sodium methoxide (MeONa, 0.2mmol, 11 mg), toluene (1 mL) and pinacolborane (HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-bromooctane (1 a, 0.2mmol, 34. mu.L), and stirred at 100 ℃ for 8h under a nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure represented by formula 2 a. The yield of the gas chromatography was 33%.
The chemical reaction formula of the preparation process is as follows:
example 4 bis (cyclopentadienyl) titanium dichloride (noted Cp)2TiCl20.02mmol, 5 mg), lithium methoxide (MeOLi, 0.2mmol,7.6 mg), toluene (1 mL) and pinacolborane (HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, added with 1-bromooctane (1 a, 0.2mmol, 34. mu.L), and the mixture was stirred in a vacuum flaskStirring at 100 deg.C for 8h under nitrogen (1 atm) atmosphere to obtain product system containing compound with structure shown in formula 2 a. The yield of the gas chromatography was 65%.
The chemical reaction formula of the preparation process is as follows:
example 5 bis (cyclopentadienyl) titanium dichloride (noted Cp)2TiCl20.02mmol, 5 mg), potassium tert-butoxide (notedtBuOK, 0.2mmol, 22.4 mg), toluene (1 mL) and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added into a 38mL pressure resistant tube, stirred for 30min, added with 1-bromooctane (noted as 1a, 0.2mmol, 34. mu.L), and stirred at 100 ℃ for 8h under nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure shown in formula 2 a. The yield of the gas chromatography was 26%.
The chemical reaction formula of the preparation process is as follows:
example 6 bis (cyclopentadienyl) titanium dichloride (noted Cp)2TiCl20.02mmol, 5 mg), sodium tert-butoxide (notedtBuONa, 0.2mmol, 19 mg), toluene (1 mL) and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, added with 1-bromooctane (noted as 1a, 0.2mmol, 34. mu.L), and stirred at 100 ℃ for 8h under nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure shown in formula 2 a. The yield of the gas chromatography was 32%.
The chemical reaction formula of the preparation process is as follows:
example 7 bis (cyclopentadienyl) titanium dichloride (noted Cp)2TiCl20.02mmol, 5 mg) of lithium tert-butoxide (Is marked astBuOLi, 0.2mmol, 16 mg), toluene (1 mL) and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, added with 1-bromooctane (noted as 1a, 0.2mmol, 34. mu.L), and stirred at 100 ℃ for 8h under nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure shown in formula 2 a. The yield of the gas chromatography was 20%.
The chemical reaction formula of the preparation process is as follows:
example 8 bis (cyclopentadienyl) titanium dichloride (noted Cp)2TiCl20.02mmol, 5 mg), cesium carbonate (noted as Cs)2CO30.2mmol, 55 mg), toluene (1 mL) and pinacolborane (HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, added with 1-bromooctane (1 a, 0.2mmol, 34. mu.L), and stirred at 100 ℃ for 8h under nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure represented by formula 2 a. The yield of the gas chromatography was 1%.
The chemical reaction formula of the preparation process is as follows:
example 9 bis (cyclopentadienyl) titanium dichloride (noted Cp)2TiCl20.02mmol, 5 mg), cesium fluoride (CsF, 0.2mmol, 30.4 mg), toluene (1 mL) and pinacolborane (HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-bromooctane (1 a, 0.2mmol, 34. mu.L), and stirred at 100 ℃ for 8h under a nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure shown in formula 2 a. The yield of the gas chromatography was 5%.
The chemical reaction formula of the preparation process is as follows:
example 10 bis (cyclopentadienyl) titanium dichloride (noted Cp)2TiCl20.02mmol, 5 mg), silver acetate (shown as AgOAc, 0.2mmol, 33.4 mg), toluene (1 mL) and pinacolborane (shown as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, added with 1-bromooctane (shown as 1a, 0.2mmol, 34. mu.L), and stirred at 100 ℃ for 8h under nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure shown in formula 2 a. The yield of the gas chromatography was 29%.
The chemical reaction formula of the preparation process is as follows:
example 11 bis (cyclopentadienyl) titanium dichloride (noted Cp)2TiCl20.02mmol, 5 mg), lithium carbonate (noted as Li)2CO30.2mmol, 15 mg), toluene (1 mL) and pinacolborane (HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, added with 1-bromooctane (1 a, 0.2mmol, 34. mu.L), and stirred at 100 ℃ for 8h under nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure represented by formula 2 a. The yield of the gas chromatography was 6%.
The chemical reaction formula of the preparation process is as follows:
example 12 bis (cyclopentadienyl) titanium dichloride (noted Cp)2TiCl20.02mmol, 5 mg), lithium hydride (denoted as LiH, 0.2mmol, 1.6 mg), toluene (1 mL) and pinacolborane (denoted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, added with 1-bromooctane (denoted as 1a, 0.2mmol, 34. mu.L), and stirred at 100 ℃ for 8h under a nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure represented by formula 2 a. The yield of the gas chromatography was 3%.
The chemical reaction formula of the preparation process is as follows:
example 13 bis (cyclopentadienyl) titanium dichloride (noted Cp)2TiCl20.02mmol, 5 mg), methyllithium (noted as MeLi, 0.2mmol, 4.4 mg), toluene (1 mL) and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, added with 1-bromooctane (noted as 1a, 0.2mmol, 34. mu.L), and stirred at 100 ℃ for 8h under nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure shown in formula 2 a. The yield of the gas chromatography was 3%.
The chemical reaction formula of the preparation process is as follows:
example 14 (cyclopentadiene) titanium trichloride (denoted as CpTiCl)30.02mmol, 4.4 mg), lithium methoxide (noted as MeOLI,0.2mmol,7.6 mg), toluene (1 mL), and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-bromooctane (noted as 1a, 0.2mmol, 34. mu.L), and stirred at 100 ℃ for 8h under nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure represented by formula 2 a. The yield of the gas chromatography was 21%.
The chemical reaction formula of the preparation process is as follows:
example 15 bis (t-butylcyclopentadienyl) titanium dichloride (notedtBuCp2TiCl20.02mmol, 7.2 mg), lithium methoxide (noted as MeOLi,0.2mmol,7.6 mg), toluene (1 mL) and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min and then added with 1-bromooctane (noted as HBpin)1a, 0.2mmol, 34 μ L) and stirred at 100 ℃ for 8h under nitrogen (1 atm) atmosphere to give a product system containing the compound of formula 2 a. The yield of the gas chromatography was 3%.
The chemical reaction formula of the preparation process is as follows:
example 16 pentamethylcyclopentadienyltitanium trichloride (denoted Cp TiCl)30.02mmol, 5.8 mg), lithium methoxide (noted as MeOLI,0.2mmol,7.6 mg), toluene (1 mL), and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-bromooctane (noted as 1a, 0.2mmol, 34. mu.L), and stirred at 100 ℃ for 8h under nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure represented by formula 2 a. The yield of the gas chromatography was 1%.
The chemical reaction formula of the preparation process is as follows:
example 17 bis (pentamethylcyclopentadienyl) titanium dichloride (noted Cp;)2TiCl30.02mmol, 7.8 mg), lithium methoxide (noted as MeOLI,0.2mmol,7.6 mg), toluene (1 mL), and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-bromooctane (noted as 1a, 0.2mmol, 34. mu.L), and stirred at 100 ℃ for 8h under nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure represented by formula 2 a. The yield of the gas chromatography was 1%.
The chemical reaction formula of the preparation process is as follows:
example 18 bis (cyclopentadienyl) titanium dichloride (noted Cp)2TiCl2,0.02mmol,5mg)、Lithium methoxide (noted as MeOLi,0.2mmol,7.6 mg), tetrahydrofuran (1 mL) and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, added with 1-bromooctane (noted as 1a, 0.2mmol, 34. mu.L), and stirred at 100 ℃ for 8h under a nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure represented by formula 2 a. The yield of the gas chromatography was 27%.
The chemical reaction formula of the preparation process is as follows:
example 19 bis (cyclopentadienyl) titanium dichloride (noted Cp)2TiCl20.02mmol, 5 mg), lithium methoxide (noted as MeOLI,0.2mmol,7.6 mg), dioxane (1 mL) and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-bromooctane (noted as 1a, 0.2mmol, 34. mu.L), and stirred at 100 ℃ for 8h under nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure represented by formula 2 a. The yield of the gas chromatography was 81%.
The chemical reaction formula of the preparation process is as follows:
example 20 bis (cyclopentadienyl) titanium dichloride (noted Cp)2TiCl20.02mmol, 5 mg), lithium methoxide (noted as MeOLI,0.2mmol,7.6 mg), dichloromethane (1 mL) and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-bromooctane (noted as 1a, 0.2mmol, 34. mu.L), and stirred at 100 ℃ for 8h under nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure represented by formula 2 a. The yield of the gas chromatography was 1%.
The chemical reaction formula of the preparation process is as follows:
example 21 bis (cyclopentadienyl) titanium dichloride (noted Cp2TiCl20.02mmol, 5 mg), lithium methoxide (noted as MeOLI,0.2mmol,7.6 mg), N-dimethylformamide (1 mL) and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-bromooctane (noted as 1a, 0.2mmol, 34. mu.L), and stirred at 100 ℃ for 8h under nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure represented by formula 2 a. The yield of the gas chromatography was 1%.
The chemical reaction formula of the preparation process is as follows:
example 22 bis (cyclopentadienyl) titanium dichloride (noted Cp2TiCl20.02mmol, 5 mg), lithium methoxide (noted as MeOLI,0.2mmol,7.6 mg), n-hexane (1 mL), and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, added with 1-bromooctane (noted as 1a, 0.2mmol, 34. mu.L), and stirred at 100 ℃ for 8h under a nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure represented by formula 2 a. The yield of the gas chromatography was 46%.
The chemical reaction formula of the preparation process is as follows:
example 23 bis (cyclopentadienyl) titanium dichloride (noted Cp2TiCl20.02mmol, 5 mg), lithium methoxide (noted as MeOLI,0.2mmol,7.6 mg), acetonitrile (1 mL) and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-bromooctane (noted as 1a, 0.2mmol, 34. mu.L), and stirred at 100 ℃ for 8h under nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure represented by formula 2 a. The yield of the gas chromatography was 3%.
The chemical reaction formula of the preparation process is as follows:
example 24 bis (cyclopentadienyl) titanium dichloride (noted Cp)2TiCl20.02mmol, 5 mg), lithium methoxide (noted as MeOLI,0.2mmol,7.6 mg), n-hexane (1 mL), and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, added with 1-bromooctane (noted as 1a, 0.2mmol, 34. mu.L), and stirred at 100 ℃ for 8h under a nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure represented by formula 2 a. The yield of the gas chromatography was 46%.
The chemical reaction formula of the preparation process is as follows:
example 25 bis (cyclopentadienyl) titanium dichloride (noted Cp)2TiCl20.02mmol, 5 mg), lithium methoxide (noted as MeOLI,0.2mmol,7.6 mg), diethylene glycol dimethyl ether (1 mL) and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, added with 1-bromooctane (noted as 1a, 0.2mmol, 34. mu.L), and stirred at 100 ℃ for 8h under nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure represented by formula 2 a. The yield of the gas chromatography was 14%.
The chemical reaction formula of the preparation process is as follows:
example 26 bis (cyclopentadienyl) titanium dichloride (noted Cp)2TiCl20.02mmol, 5 mg), lithium methoxide (as MeOLi,0.2mmol,7.6 mg), chloroform (1 mL) and pinacolborane (as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min and then added with 1-bromooctane (C/O)Noted as 1a, 0.2mmol, 34. mu.L) and stirred at 100 ℃ for 8h under nitrogen (1 atm) atmosphere to give a product system containing the compound of formula 2 a. The yield of the gas chromatography was 1%.
The chemical reaction formula of the preparation process is as follows:
example 27 bis (cyclopentadienyl) titanium dichloride (noted Cp2TiCl20.02mmol, 5 mg), lithium methoxide (noted as MeOLI,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL), and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-bromooctane (noted as 1a, 0.2mmol, 34. mu.L), and stirred at 100 ℃ for 8h under nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure represented by formula 2 a. The yield of the gas chromatography was 91%.
The chemical reaction formula of the preparation process is as follows:
example 28 bis (cyclopentadienyl) titanium dichloride (noted Cp2TiCl20.02mmol, 5 mg), lithium methoxide (noted as MeOLI,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL), and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-bromooctane (noted as 1a, 0.2mmol, 34. mu.L), and stirred at 90 ℃ for 8h under nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure represented by formula 2 a. The yield of the gas chromatography was 93%.
The chemical reaction formula of the preparation process is as follows:
example 29 bis (cyclopentadienyl) titanium dichloride (noted Cp)2TiCl2,0.02mmol, 5 mg), lithium methoxide (noted as MeOLI,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL), and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, added with 1-bromooctane (noted as 1a, 0.2mmol, 34. mu.L), and stirred at 80 ℃ for 8h under a nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure represented by formula 2 a. The yield of the gas chromatography was 85%.
The chemical reaction formula of the preparation process is as follows:
example 30 bis (cyclopentadienyl) titanium dichloride (noted Cp2TiCl20.02mmol, 5 mg), lithium methoxide (noted as MeOLI, 0.15mmol, 5.7 mg), methyl tert-butyl ether (1 mL), and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-bromooctane (noted as 1a, 0.2mmol, 34. mu.L), and stirred at 80 ℃ for 8h under nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure represented by formula 2 a. The yield of the gas chromatography was 57%.
The chemical reaction formula of the preparation process is as follows:
example 31 bis (cyclopentadienyl) titanium dichloride (noted Cp2TiCl20.02mmol, 5 mg), lithium methoxide (noted as MeOLI,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL), and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-bromooctane (noted as 1a, 0.2mmol, 34. mu.L), and stirred at 60 ℃ for 8h under nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure represented by formula 2 a. The yield of the gas chromatography was 72%.
The chemical reaction formula of the preparation process is as follows:
example 32 bis (cyclopentadienyl) titanium dichloride (noted Cp2TiCl20.02mmol, 5 mg), lithium methoxide (noted as MeOLI,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL), and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-bromooctane (noted as 1a, 0.2mmol, 34. mu.L), and stirred at 35 ℃ for 8h under nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure represented by formula 2 a. The yield of the gas chromatography was 32%.
The chemical reaction formula of the preparation process is as follows:
example 33 bis (cyclopentadienyl) titanium dichloride (noted Cp2TiCl20.02mmol, 5 mg), lithium methoxide (noted as MeOLI, 0.1mmol, 3.8 mg), methyl tert-butyl ether (1 mL), and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-bromooctane (noted as 1a, 0.2mmol, 34. mu.L), and stirred at 80 ℃ for 8h under nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure represented by formula 2 a. The yield of the gas chromatography was 38%.
The chemical reaction formula of the preparation process is as follows:
example 34 bis (cyclopentadienyl) titanium dichloride (noted Cp2TiCl20.02mmol, 5 mg), lithium methoxide (noted as MeOLI, 0.05mmol, 1.9 mg), methyl tert-butyl ether (1 mL) and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, added with 1-bromooctane (noted as 1a, 0.2mmol, 34. mu.L), and stirred at 80 ℃ for 8h under nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure represented by formula 2a. The yield of the gas chromatography was 4%.
The chemical reaction formula of the preparation process is as follows:
example 35 bis (cyclopentadienyl) titanium dichloride (noted Cp)2TiCl20.02mmol, 5 mg), lithium methoxide (noted as MeOLI, 0.02mmol, 0.76 mg), methyl tert-butyl ether (1 mL), and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-bromooctane (noted as 1a, 0.2mmol, 34. mu.L), and stirred at 80 ℃ for 8h under nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure represented by formula 2 a. The yield of the gas chromatography was 3%.
The chemical reaction formula of the preparation process is as follows:
example 36 bis (cyclopentadienyl) titanium dichloride (noted Cp2TiCl20.01mmol, 2.5 mg), lithium methoxide (noted as MeOLI,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL), and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-bromooctane (noted as 1a, 0.2mmol, 34. mu.L), and stirred at 80 ℃ for 8h under nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure represented by formula 2 a. The yield of the gas chromatography was 89%.
The chemical reaction formula of the preparation process is as follows:
example 37 bis (cyclopentadienyl) titanium dichloride (noted Cp2TiCl20.005mmol, 1.3 mg), lithium methoxide (noted as MeOLi,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL) and pinacolborane (noted as HBpin, 0.4mmol, 5 mg)8 mu L) are sequentially added into a 38mL pressure resistant tube, stirred for 30min, added with 1-bromooctane (1 a, 0.2mmol, 34 mu L) and stirred for 8h at 80 ℃ under the atmosphere of nitrogen (1 atm), and a product system containing the compound with the structure shown in the formula 2a is obtained. The yield of the gas chromatography was 72%.
The chemical reaction formula of the preparation process is as follows:
example 38 bis (cyclopentadienyl) titanium dichloride (noted Cp2TiCl20.002mmol, 0.63 mg), lithium methoxide (noted as MeOLi,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL), and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-bromooctane (noted as 1a, 0.2mmol, 34. mu.L), and stirred at 80 ℃ for 8h under nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure represented by formula 2 a. The yield of the gas chromatography was 65%.
The chemical reaction formula of the preparation process is as follows:
example 39 bis (cyclopentadienyl) titanium dichloride (noted Cp2TiCl20.01mmol, 2.5 mg), lithium methoxide (noted as MeOLI,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL), and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-bromooctane (noted as 1a, 0.2mmol, 34. mu.L), and stirred at 80 ℃ for 12h under a nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure represented by formula 2 a. The yield of the gas chromatography was 76%.
The chemical reaction formula of the preparation process is as follows:
example 40 bis (cyclopentadienyl) titanium dichloride (denoted Cp)2TiCl20.01mmol, 2.5 mg), lithium methoxide (noted as MeOLI,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL), and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, added (noted as 1a, 0.2mmol, 34. mu.L), and stirred at 60 ℃ for 24h under a nitrogen (1 atm) atmosphere to obtain a product system containing the compound having the structure represented by formula 2 a. The yield of the gas chromatography was 81%.
The chemical reaction formula of the preparation process is as follows:
the borate ester compounds with the structure shown in the formula 2a prepared in the embodiments 1-40 are all colorless transparent liquid 1-octane borate pinacol ester, and the characterization data are as follows:1H NMR (400 MHz, Chloroform-d) δ 1.49 – 1.33 (m, 3H), 1.25 (s, 9H), 1.23 (s, 12H), 0.86 (t, J = 6.7 Hz, 3H), 0.75 (t, J = 7.7 Hz, 2H). 13C NMR (101 MHz, Chloroform-d) δ 82.8, 32.4, 31.9, 29.4, 29.2, 24.8, 24.0, 22.7, 14.1. 11B NMR (128 MHz, Chloroform-d) δ 34.35。
example 41 bis (cyclopentadienyl) titanium dichloride (noted Cp2TiCl20.01mmol, 2.5 mg), lithium methoxide (noted as MeOLI,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL), and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-bromohexane (noted as 1b, 0.2mmol, 28.2. mu.L), stirred at 60 ℃ for 24h under nitrogen (1 atm) atmosphere, and column chromatography was performed using petroleum ether/ethyl acetate (40: 1, v/v) as an eluent to obtain a compound of the structure represented by formula 2b (colorless transparent liquid, 1-hexanylboronic acid pinacol ester). The isolated yield was 83%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are:1H NMR (400 MHz, Chloroform-d) δ 1.47 – 1.35 (m, 2H), 1.27 (ddd, J = 6.5, 3.7, 2.2 Hz, 6H), 1.24 (s, 12H), 0.93 – 0.84 (m, 3H), 0.76 (t, J = 7.7 Hz, 2H). 13C NMR (101 MHz, Chloroform-d) δ 82.8, 32.1, 31.6, 29.7, 24.8, 24.0, 22.6, 14.1. 11B NMR (128 MHz, Chloroform-d) δ 34.31。
example 42 bis (cyclopentadienyl) titanium dichloride (noted Cp2TiCl20.01mmol, 2.5 mg), lithium methoxide (noted as MeOLI,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL), and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then 1-bromoheptane (noted as 1c, 0.2mmol, 31.5. mu.L) was added, stirred at 60 ℃ for 24h under nitrogen (1 atm) atmosphere, and column chromatography purification was performed using petroleum ether/ethyl acetate (40: 1, v/v) as an eluent to obtain a compound of the structure represented by formula 2c (colorless transparent liquid, 1-heptanylpinacolato borate). The isolated yield was 83%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are:1H NMR (400 MHz, Chloroform-d) δ 1.49 – 1.33 (m, 3H), 1.25 (s, 9H), 1.23 (s, 12H), 0.86 (t, J = 6.7 Hz, 3H), 0.75 (t, J = 7.7 Hz, 2H). 13C NMR (101 MHz, Chloroform-d) δ 82.8, 32.4, 31.9, 29.4, 29.2, 24.8, 24.0, 22.7, 14.1. 11B NMR (128 MHz, Chloroform-d) δ 34.35。
example 43 bis (cyclopentadienyl) titanium dichloride (noted Cp)2TiCl20.01mmol, 2.5 mg), lithium methoxide (as MeOLi,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL), and pinacolborane (as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, added with 1-bromononane (as 1d, 0.2mmol, 31.5. mu.L), and placed under nitrogen (1 atm) at 6 deg.CStirring at 0 deg.C for 24h, and purifying by column chromatography with petroleum ether/ethyl acetate (40: 1, v/v) as eluent to obtain compound (colorless transparent liquid, 1-nonanylboronic acid pinacol ester) with structure shown in formula 2 d. The isolated yield was 89%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are:1H NMR (400 MHz, Chloroform-d) δ 1.51 – 1.33 (m, 2H), 1.25 (s, 12H), 1.24 (s, 12H), 0.87 (t, J = 6.8 Hz, 3H), 0.76 (t, J = 7.8 Hz, 2H).13C NMR (101 MHz, Chloroform-d) δ 82.8, 32.4, 31.9, 29.6, 29.4, 29.3, 24.8, 24.0, 22.7, 14.1.11B NMR (128 MHz, Chloroform-d) δ 34.24。
example 44 bis (cyclopentadienyl) titanium dichloride (noted Cp)2TiCl20.02mmol, 2.5 mg), lithium methoxide (noted as MeOLI,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL), and pinacolborane (noted as Hbpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, bromomethylcyclohexane (noted as 1e, 0.2mmol, 29. mu.L) was added, stirred at 60 ℃ for 24h under nitrogen (1 atm) atmosphere, and column chromatography purification was performed using petroleum ether/ethyl acetate (40: 1, v/v) as an eluent to obtain a compound of the structure shown in formula 2e (colorless transparent liquid, 2-methylcyclohexyl boronic acid pinacol ester). The isolated yield was 57%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are:1H NMR (400 MHz, Chloroform-d) δ 1.81 – 1.57 (m, 5H), 1.53 – 1.39 (m, 1H), 1.24 (s, 15H), 1.03 – 0.84 (m, 2H), 0.71 (d, J = 7.1 Hz, 2H).13C NMR (101 MHz, Chloroform-d) δ 82.8, 35.9, 34.2, 26.6, 26.3, 24.9.11B NMR (128 MHz, Chloroform-d) δ 34.07。
example 45 bis (cyclopentadienyl) titanium dichloride (noted Cp)2TiCl20.01mmol, 2.5 mg), lithium methoxide (noted as MeOLI,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL), and pinacolborane (noted as Hbpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then 2-cyclohexylbromoethane (noted as 1f, 0.2mmol, 31.4. mu.L) was added, stirred at 60 ℃ for 24h under nitrogen (1 atm) atmosphere, and column chromatography purification was performed with petroleum ether/ethyl acetate (40: 1, v/v) as an eluent to obtain a compound of the structure represented by formula 2f (colorless transparent liquid, 2-ethylcyclohexylboronic acid pinacol ester). The isolated yield was 70%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are:1H NMR (400 MHz, Chloroform-d) δ 1.79 – 1.52 (m, 6H), 1.25 – 1.21 (m, 2H), 1.17 (s, 12H), 1.13 – 1.03 (m, 3H), 0.78 (td, J = 11.6, 2.9 Hz, 2H), 0.69 (dd, J = 9.3, 7.3 Hz, 2H). 13C NMR (101 MHz, Chloroform-d) δ 82.8, 40.0, 33.0, 31.4, 26.8, 26.4, 24.8. 11B NMR (128 MHz, Chloroform-d) δ 34.22。
example 46 bis (cyclopentadienyl) titanium dichloride (noted Cp)2TiCl20.01mmol, 2.5 mg), lithium methoxide (noted as MeOLI,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL), and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-bromo-3-methylbutane (noted as 1g, 0.2mmol, 25. mu.L), stirred at 60 ℃ for 24h under nitrogen (1 atm) atmosphere, and column chromatography purification was performed with petroleum ether/ethyl acetate (40: 1, v/v) as an eluent to obtain the structural compound represented by formula 2g (colorless transparent liquid, 2-isopentyl pinacol borate). The isolated yield was 74%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are:1H NMR (400 MHz, Chloroform-d) δ 1.50 – 1.41 (m, 1H), 1.34 – 1.26 (m, 2H), 1.24 (s, 12H), 0.86 (d, J = 6.6 Hz, 6H), 0.79 – 0.70 (m, 2H).13C NMR (101 MHz, Chloroform-d) δ 82.8, 32.9, 30.2, 24.8, 22.2.11B NMR (128 MHz, Chloroform-d) δ 34.30。
example 47 bis (cyclopentadienyl) titanium dichloride (noted Cp2TiCl20.01mmol, 2.5 mg), lithium methoxide (described as MeOLi,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL) and pinacolborane (described as HBpin, 0.4mmol, 58 μ L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-bromo-3, 7-dimethyloctane (described as 1h, 0.2mmol, 42 μ L), stirred at 60 ℃ for 24h under nitrogen (1 atm) atmosphere, and mixed with petroleum ether/ethyl acetate (40: 1, v/v) as eluent to obtain a compound (2 h) shown in the formula (2- (2, 7-dimethyl octyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborole) by column chromatography purification. The isolated yield was 74%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are:1H NMR (400 MHz, Chloroform-d) δ 1.71 – 1.44 (m, 1H), 1.41 – 1.27 (m, 6H), 1.24 (s, 12H), 1.18 – 0.98 (m, 3H), 0.85 (dd, J = 7.7, 6.5 Hz, 9H), 0.80 – 0.59 (m, 2H). 13C NMR (101 MHz, Chloroform-d) δ 82.8, 39.4, 36.9, 35.0, 31.0, 28.0, 24.8, 24.8, 22.7, 22.6, 19.2.11B NMR (128 MHz, Chloroform-d) δ 34.35. HRMS (ESI) m/z: [M+Na]+ calcd for C16H33BNaO2 +: 291.2466; found: 291.2468。
practice ofEXAMPLE 48 bis (cyclopentadienyl) titanium dichloride (denoted as Cp)2TiCl20.01mmol, 2.5 mg), lithium methoxide (described as MeOLi,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL) and pinacolborane (described as HBpin, 0.4mmol, 58 μ L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-bromobenzene propane (described as 1h, 0.2mmol, 30.4 μ L), stirred at 60 ℃ for 24h under nitrogen (1 atm) atmosphere, and mixed with petroleum ether/ethyl acetate (40: 1, v/v) as an eluent to obtain a compound (colorless transparent liquid, 2- (3-phenylpropyl) boronic acid pinacol ester) with a structure shown in formula 2h by column chromatography purification. The isolated yield was 86%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are:1H NMR (400 MHz, Chloroform-d) δ 7.24 – 7.12 (m, 2H), 7.11 – 7.04 (m, 3H), 2.59 – 2.46 (m, 2H), 1.76 – 1.57 (m, 2H), 1.16 (s, 12H), 0.84 – 0.68 (m, 2H).13C NMR (101 MHz, Chloroform-d) δ 142.7, 128.5, 128.1, 125.5, 82.9, 38.6, 26.1, 24.8.11B NMR (128 MHz, Chloroform-d) δ 34.13。
example 49 bis (cyclopentadienyl) titanium dichloride (noted Cp)2TiCl20.01mmol, 2.5 mg), lithium methoxide (note as MeOLi,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL) and pinacolborane (note as HBpin, 0.4mmol, 58 μ L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then ethyl 7-bromoheptanoate (note as 1k, 0.2mmol, 38.8 μ L) was added, stirred under nitrogen (1 atm) at 100 ℃ for 24h, and the mixture was cooled to room temperature using petroleum ether/ethyl acetate (40: 1, v/v) as eluent to obtain a compound (2 h) shown in the formula (colorless transparent liquid, 2- (7-ethyl heptanoate) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan). The isolated yield was 47%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are:1H NMR (400 MHz, Chloroform-d) δ 4.11 (q, J = 7.1 Hz, 2H), 2.26 (t, J = 7.6 Hz, 2H), 1.65 – 1.56 (m, 3H), 1.39 (td, J = 6.0, 4.8, 2.7 Hz, 3H), 1.30 (q, J = 3.7 Hz, 5H), 1.23 (s, 12H), 0.75 (t, J = 7.7 Hz, 2H).13C NMR (101 MHz, Chloroform-d) δ 173.9, 82.9, 60.1, 34.4, 31.9, 28.9, 24.8, 23.8, 14.2. 11B NMR (128 MHz, Chloroform-d) δ 34.22. HRMS (ESI) m/z: [M+Na]+calcd for C15H29BNaO4 +: 307.2051; found: 307.2054。
example 50 bis (cyclopentadienyl) titanium dichloride (noted Cp)2TiCl20.01mmol, 2.5 mg), lithium methoxide (described as MeOLi,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL), and pinacolborane (described as HBpin, 0.4mmol, 58 μ L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, added with ethyl 2- (4- (4-bromobutyl) phenyl) acetate (described as 1j, 0.2mmol, 63 mg), and stirred at 100 ℃ for 24h under a nitrogen (1 atm) atmosphere to obtain a solution of petroleum ether/ethyl acetate (5: 1, v/v) as an eluent to obtain a compound (4- ((5- (4, 4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) pentyl) oxy) phenyl propionate) with a structure shown in a formula 2j by column chromatography purification. The isolated yield was 61%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are:1H NMR (400 MHz, Chloroform-d) δ 7.98 (d, J = 8.8 Hz, 2H), 6.89 (d, J = 8.9 Hz, 2H), 4.34 (q, J = 7.1 Hz, 2H), 4.00 (t, J = 6.6 Hz, 2H), 1.80 (dd, J = 8.6, 5.0 Hz, 2H), 1.55 – 1.45 (m, 4H), 1.38 (t, J = 7.1 Hz, 3H), 1.24 (s, 12H), 0.92 – 0.73 (m, 2H).13C NMR (101 MHz, Chloroform-d) δ 166.5, 162.9, 131.5, 122.7, 114.2, 82.9, 68.1, 60.5, 28.9, 28.6, 24.8, 23.7, 14.4.11B NMR (128 MHz, Chloroform-d) δ 34.50。
example 51 bis (cyclopentadienyl) titanium dichloride (noted Cp2TiCl20.01mmol, 2.5 mg), lithium methoxide (described as MeOLi,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL) and pinacolborane (described as HBpin, 0.4mmol, 58 μ L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 5-bromo-2-methyl-2-pentene (described as 1L, 0.2mmol, 26.8 μ L), stirred under nitrogen (1 atm) at 60 ℃ for 24h, and mixed with petroleum ether/ethyl acetate (40: 1, v/v) as eluent to obtain a compound (4, 4,5, 5-tetramethyl-2- (4-methylpent-3-en-1-yl) -1,3, 2-dioxaborolan) with a structure shown in a formula 2l by column chromatography purification. The isolated yield was 47%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are:1H NMR (400 MHz, Chloroform-d) δ 5.11 (tt, J = 7.2, 1.5 Hz, 1H), 2.08 (q, J = 7.3 Hz, 2H), 1.66 (s, 3H), 1.60 (s, 3H), 1.24 (s, 12H), 0.82 (t, J = 7.8 Hz, 2H).13C NMR (101 MHz, Chloroform-d) δ 130.4, 126.8, 82.9, 25.7, 24.8, 22.5, 17.6. 11B NMR (128 MHz, Chloroform-d) δ 34.02. HRMS (ESI) m/z: [M+Na]+ calcd for C13H27BNaO2 +: 233.1683; found: 233.1680。
example 52 bis (cyclopentadienyl) titanium dichloride (noted Cp)2TiCl20.01mmol, 2.5 mg), lithium methoxide (as MeOLi,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL), and pinacolborane (as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, added with 1-bromobenzenethane (as 1m, 0.2mmol, 27.3. mu.L), and placed under nitrogen (1 atm) atmosphereStirring at 60 deg.C for 24h, and purifying by column chromatography with petroleum ether/ethyl acetate (40: 1, v/v) as eluent to obtain compound (colorless transparent liquid, 2- (2-phenylethyl) boronic acid pinacol ester) with structure shown in formula 2 m. The isolated yield was 80%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are:1H NMR (400 MHz, Chloroform-d) δ 7.33 – 7.19 (m, 4H), 7.20 – 7.12 (m, 1H), 2.91 – 2.59 (m, 2H), 1.22 (s, 12H), 1.14 (dd, J = 9.0, 7.4 Hz, 2H). 13C NMR (101 MHz, Chloroform-d) δ 144.4, 128.2, 128.0, 125.5, 83.1, 30.0, 24.8. 11B NMR (128 MHz, Chloroform-d) δ 33.98。
example 53 bis (cyclopentadienyl) titanium dichloride (noted Cp2TiCl20.01mmol, 2.5 mg), lithium methoxide (note as MeOLi,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL), and pinacolborane (note as HBpin, 0.4mmol, 58 μ L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, added with p-trifluoromethylbromoethylbenzene (note as 1n, 0.2mmol, 27.3 μ L), stirred at 60 ℃ for 24h under nitrogen (1 atm) atmosphere, and replaced with petroleum ether/ethyl acetate (40: 1, v/v) as eluent to obtain a compound (2 n) shown in the formula (2- (4- (trifluoromethyl) phenethyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan) by column chromatography purification. The isolated yield was 60%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are:1H NMR (400 MHz, Chloroform-d) δ 7.51 (d, J = 7.7 Hz, 2H), 7.32 (d, J = 8.0 Hz, 2H), 2.80 (t, J = 8.1 Hz, 2H), 1.22 (s, 12H), 1.19 – 1.11 (m, 2H).13C NMR (101 MHz, Chloroform-d) δ 147.51, 127.31, 126.9 (d, J = 32.1 Hz), 124.8, 124.1 (q, J = 3.8 Hz), 122.10, 82.24, 28.83, 23.78.11B NMR (128 MHz, Chloroform-d) δ 33.84.19F NMR (376 MHz, Chloroform-d) δ -62.26。
example 54 bis (cyclopentadienyl) titanium dichloride (noted Cp2TiCl20.01mmol, 2.5 mg), lithium methoxide (note as MeOLi,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL) and pinacolborane (note as HBpin, 0.4mmol, 58 μ L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 3- (2-bromoethyl) thiophene (note as 1o, 0.2mmol, 38 mg), stirred at 60 ℃ under nitrogen (1 atm) for 24h, and mixed with petroleum ether/ethyl acetate (40: 1, v/v) as eluent to obtain a compound (colorless transparent liquid, 2- (thiophene-3-yl) ethyl-4, 4,5, 5-tetramethyl-1, 3, 2-dioxaborole) with a structure shown in a formula 2 o. The isolated yield was 74%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are:1H NMR (400 MHz, Chloroform-d) δ 7.07 (dd, J = 5.1, 1.3 Hz, 1H), 6.89 (dd, J = 5.1, 3.4 Hz, 1H), 6.79 (dt, J = 3.4, 1.1 Hz, 1H), 2.96 (td, J = 8.0, 1.0 Hz, 2H), 1.23 (s, 14H). 13C NMR (101 MHz, Chloroform-d) δ 147.8, 126.5, 123.4, 122.6, 83.2, 24.8, 24.3.11B NMR (128 MHz, Chloroform-d) δ 33.77。
example 55 bis (cyclopentadienyl) titanium dichloride (noted Cp)2TiCl20.01mmol, 2.5 mg), lithium methoxide (as MeOLi,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL), and pinacolborane (as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, added with 5- (2-bromoethyl) -2, 3-dihydrobenzofuran (as 1p, 0.2mmol, 45.4 mg), stirred at 60 ℃ for 24h under nitrogen (1 atm),purifying by column chromatography with petroleum ether/ethyl acetate (40: 1, v/v) as eluent to obtain compound (colorless transparent liquid, 2-ethyl (2, 3-dihydrobenzofuran) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan) with structure shown in formula 2 p. The isolated yield was 89%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are:1H NMR (400 MHz, Chloroform-d) δ 7.05 (d, J = 1.9 Hz, 1H), 6.94 (ddd, J = 8.1, 1.8, 0.8 Hz, 1H), 6.67 (d, J = 8.1 Hz, 1H), 4.52 (t, J = 8.7 Hz, 2H), 3.16 (t, J = 8.6 Hz, 2H), 2.86 – 2.56 (m, 2H), 1.22 (s, 12H), 1.08 (s, 2H).13C NMR (101 MHz, Chloroform-d) δ 158.0, 136.5, 127.3, 126.7, 124.5, 108.7, 83.0, 71.0, 29.8, 29.4, 24.8. 11B NMR (128 MHz, Chloroform-d) δ 33.92. HRMS (ESI) m/z: [M+Na]+ calcd for C16H23BNaO4 +: 297.1632; found: 297.1635。
example 56 bis (cyclopentadienyl) titanium dichloride (noted Cp)2TiCl20.01mmol, 2.5 mg), lithium methoxide (note as MeOLi,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL) and pinacolborane (note as HBpin, 0.4mmol, 58 μ L) were added in sequence to a 38mL pressure resistant tube, stirred for 30min, then 2- (2-bromoethyl) -1, 3-dioxane (note as 1q, 0.2mmol, 27.5 μ L) was added, stirred under nitrogen (1 atm) at 60 ℃ for 24h, and the mixture was cooled to room temperature in petroleum ether/ethyl acetate (40: 1, v/v) as an eluent to obtain a compound having a structure represented by formula 2q (colorless transparent liquid, 2- (2-ethyl (1, 3-dioxane)) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan). The isolated yield was 79%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are:1H NMR (400 MHz, Chloroform-d) δ 4.46 (t, J = 5.1 Hz, 1H), 4.06 (dd, J = 11.9, 5.0, 1.4 Hz, 2H), 3.72 (dd, J = 11.9, 10.5, 2.6, 1.6 Hz, 2H), 2.04 (dt, J = 13.4, 12.4, 5.0 Hz, 1H), 1.70 (td, J = 7.8, 5.1 Hz, 2H), 1.35 – 1.26 (m, 1H), 1.22 (s, 12H), 0.81 (t, J = 7.7 Hz, 2H). 13C NMR (101 MHz, Chloroform-d) δ 103.2, 82.9, 29.5, 25.9, 24.8.11B NMR (128 MHz, Chloroform-d) δ 33.77。
example 57 bis (cyclopentadienyl) titanium dichloride (noted Cp2TiCl20.01mmol, 2.5 mg), lithium methoxide (note as MeOLi,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL), and pinacolborane (note as HBpin, 0.4mmol, 58 μ L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then 2- (2-bromoethyl) -2-methyl-1, 3-dioxolane (note as 1r, 0.2mmol, 28 μ L) was added, and stirred under nitrogen (1 atm) atmosphere at 60 ℃ for 24h to obtain a solution of petroleum ether/ethyl acetate (40: 1, v/v) as eluent to obtain a compound (colorless transparent liquid, 2- (2-methyl-1, 3-dioxygen heterocycle) ethyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxy boron heterocyclic cyclopentane) with a structure shown in a formula 2 r. The isolated yield was 83%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are:1H NMR (400 MHz, Chloroform-d) δ 3.92 (s, 3H), 1.78 (t, J= 7.9 Hz, 2H), 1.29 (d, J = 8.0 Hz, 4H), 1.24 (s, 12H), 0.81 (t, J = 7.9 Hz, 2H).13C NMR (101 MHz, Chloroform-d) δ 110.5, 82.9, 64.8, 33.4, 24.8, 23.7.11B NMR (128 MHz, Chloroform-d) δ 34.00. HRMS (ESI) m/z: [M+Na]+ calcd for C12H23BNaO4 +: 265.1582; found: 265.1584。
example 58 bis (cyclopentadienyl) titanium dichloride (noted Cp2TiCl20.01mmol, 2.5 mg), lithium methoxide (note as MeOLi,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL) and pinacolborane (note as HBpin, 0.4mmol, 58 μ L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 3-bromopropylmethyl ether (note as 1s, 0.2mmol, 23 μ L), stirred under nitrogen (1 atm) at 60 ℃ for 24h, and replaced with petroleum ether/ethyl acetate (40: 1, v/v) as eluent to obtain a compound (colorless transparent liquid, 2- (3-methoxy propyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborole cyclopentane) with a structure shown in a formula 2 s. The isolated yield was 90%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are:1H NMR (400 MHz, Chloroform-d) δ 3.34 (t, J = 6.6 Hz, 1H), 3.31 (s, 1H), 1.68 (p, J = 7.2 Hz, 2H), 1.24 (d, J = 1.1 Hz, 12H), 0.79 (t, J= 7.7 Hz, 2H).13C NMR (101 MHz, Chloroform-d) δ 82.9, 74.6, 58.4, 29.7, 24.8, 24.0. 11B NMR (128 MHz, Chloroform-d) δ 34.07。
example 59 bis (cyclopentadienyl) titanium dichloride (noted Cp)2TiCl20.01mmol, 2.5 mg), lithium methoxide (note as MeOLi,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL), and pinacolborane (note as HBpin, 0.4mmol, 58 μ L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then 3-phenoxybromopropane (note as 1t, 0.2mmol, 32 μ L) was added, stirred under nitrogen (1 atm) at 60 ℃ for 24h, and the mixture was cooled to room temperature using petroleum ether/ethyl acetate (10: 1, v/v) as eluent to obtain a compound (colorless transparent liquid, 2- (3-phenoxypropyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborole cyclopentane) with a structure shown in formula 2t by column chromatography purification. The isolated yield was 78%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are:1H NMR (400 MHz, Chloroform-d) δ 7.31 – 7.22 (m, 4H), 7.22 – 7.16 (m, 1H), 4.43 (s, 2H), 3.37 (t, J = 6.7 Hz, 2H), 1.67 (p, J = 7.0 Hz, 2H), 1.15 (s, 12H), 0.76 (t, J = 7.8 Hz, 2H). 13C NMR (101 MHz, Chloroform-d) δ 138.9, 128.3, 127.6, 127.4, 82.9, 72.7, 72.4, 24.8, 24.2. 11B NMR (128 MHz, Chloroform-d) δ 34.18。
example 60 bis (cyclopentadienyl) titanium dichloride (noted Cp)2TiCl20.01mmol, 2.5 mg), lithium methoxide (described as MeOLi,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL) and pinacolborane (described as HBpin, 0.4mmol, 58 μ L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then 3-benzyloxy bromopropane (described as 1u, 0.2mmol, 35 μ L) was added, stirred under nitrogen (1 atm) at 60 ℃ for 24h, and the mixture was cooled to room temperature using petroleum ether/ethyl acetate (30: 1, v/v) as eluent to obtain a compound (colorless transparent liquid, 2- (3- (benzyloxy) propyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan) with a structure shown in a formula 2u by column chromatography purification. The isolated yield was 78%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are:1H NMR (400 MHz, Chloroform-d) δ 7.31 – 7.22 (m, 4H), 7.22 – 7.16 (m, 1H), 4.43 (s, 2H), 3.37 (t, J = 6.7 Hz, 2H), 1.67 (p, J = 7.0 Hz, 2H), 1.15 (s, 12H), 0.76 (t, J = 7.8 Hz, 2H). 13C NMR (101 MHz, Chloroform-d) δ 138.9, 128.3, 127.6, 127.4, 82.9, 72.7, 72.4, 24.8, 24.2. 11B NMR (128 MHz, Chloroform-d) δ 34.18。
example 61 bis (cyclopentadienyl) titanium dichloride (noted Cp2TiCl20.01mmol, 2.5 mg), lithium methoxide (note as MeOLi,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL) and pinacolborane (note as HBpin, 0.4mmol, 58 μ L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 2- (3-bromopropoxy) naphthalene (note as 1v, 0.2mmol, 53 mg), stirred at 60 ℃ under nitrogen (1 atm) for 24h, and mixed with petroleum ether/ethyl acetate (40: 1, v/v) as eluent to obtain a compound (2 v) shown in the formula (2- (3- (naphthalene-2-acyloxy) propyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborole) by column chromatography purification. The isolated yield was 79%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are:1H NMR (400 MHz, Chloroform-d) δ 7.83 – 7.67 (m, 3H), 7.42 (ddd, J = 8.2, 6.9, 1.4 Hz, 1H), 7.37 – 7.28 (m, 1H), 7.21 – 7.09 (m, 2H), 4.07 (t, J = 6.7 Hz, 2H), 1.98 (dq, J = 8.0, 6.7 Hz, 2H), 1.27 (s, 12H), 0.98 (t, J = 7.8 Hz, 2H). 13C NMR (101 MHz, Chloroform-d) δ 157.2, 134.7, 129.2, 127.6, 126.7, 126.2, 123.4, 119.1, 106.8, 83.1, 69.7, 24.9, 23.7.11B NMR (128 MHz, Chloroform-d) δ 34.48。
example 62 bis (cyclopentadienyl) titanium dichloride (noted Cp)2TiCl20.01mmol, 2.5 mg), lithium methoxide (noted as MeOLi,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL) and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirring for 30min, adding 2- (3-bromopropoxy) tetrahydro-2H-pyran (1 w, 0.2mmol, 34 μ L), stirring at 60 deg.C for 24H under nitrogen (1 atm), and purifying by column chromatography with petroleum ether/ethyl acetate (40: 1, v/v) as eluent to obtain compound (colorless transparent liquid, 2- (3- ((tetrahydro-2H-pyran-2-yl) oxy) propyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan) with structure shown in formula 2 w. Separated productThe ratio was 78%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are:1H NMR (400 MHz, Chloroform-d) δ 4.58 (dd, J = 4.2, 2.9 Hz, 1H), 3.85 (dd, J = 11.2, 8.0, 3.2 Hz, 1H), 3.67 (dt, J = 9.6, 7.0 Hz, 1H), 3.56 – 3.40 (m, 1H), 3.35 (dt, J = 9.6, 6.7 Hz, 1H), 1.77 – 1.45 (m, 8H), 1.23 (s, 12H), 0.81 (td, J = 7.7, 2.5 Hz, 2H).13C NMR (101 MHz, Chloroform-d) δ 98.5, 82.9, 69.2, 62.0, 30.7, 25.5, 24.8, 24.2, 19.5.11B NMR (128 MHz, Chloroform-d) δ 34.26。
example 63 bis (cyclopentadienyl) titanium dichloride (noted Cp)2TiCl20.01mmol, 2.5 mg), lithium methoxide (noted as MeOLi,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL) and pinacolborane (noted as HBpin, 0.4mmol, 58 μ L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 3-bromopropyl 1, 1-dimethylethyl sulfide (noted as 1x, 0.2mmol, 42 mg), stirred under nitrogen (1 atm) atmosphere at 60 ℃ for 24h, and mixed with petroleum ether/ethyl acetate (40: 1, v/v) as eluent to obtain a compound (2 x) shown in the formula (colorless transparent liquid, 2- (3- (tert-butyl) propyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan). The isolated yield was 70%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are:1H NMR (400 MHz, Chloroform-d) δ 2.67 – 2.46 (m, 2H), 1.69 (p, J = 7.6 Hz, 2H), 1.31 (s, 9H), 1.24 (s, 12H), 0.89 (t, J = 7.7 Hz, 2H). 13C NMR (101 MHz, Chloroform-d) δ 83.0, 41.8, 31.1, 30.8, 24.8. 11B NMR (128 MHz, Chloroform-d) δ 33.98. HRMS (ESI) m/z: [M+Na]+ calcd for C13H27BNaO2S+: 281.1717; found: 281.1716。
example 64 bis (cyclopentadienyl) titanium dichloride (noted Cp2TiCl20.01mmol, 2.5 mg), lithium methoxide (described as MeOLi,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL) and pinacolborane (described as HBpin, 0.4mmol, 58 μ L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then 2- (4- (4-bromobutyl) phenyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan (described as 1y, 0.2mmol, 65 mg) was added, stirred under nitrogen (1 atm) at 60 ℃ for 24h, and the mixture was stirred with petroleum ether/ethyl acetate (40: 1, v/v) as eluent to obtain a compound with a structure shown in a formula 2y (colorless transparent liquid, 2- (4- (4, 4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) butyl) phenyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan). The isolated yield was 20%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are:1H NMR (400 MHz, Chloroform-d) δ 7.83 – 7.60 (m, 2H), 7.19 (d, J = 7.9 Hz, 2H), 2.62 (dd, J = 8.8, 6.8 Hz, 2H), 1.80 – 1.66 (m, 2H), 1.33 (s, 14H), 1.24 (s, 12H), 0.82 (d, J = 8.0 Hz, 2H).13C NMR (101 MHz, Chloroform-d) δ 146.2, 134.8, 128.0, 83.6, 82.9, 38.8, 25.9, 24.86, 24.83.11B NMR (128 MHz, Chloroform-d) δ 34.47, 31.66. HRMS (ESI) m/z: [M+Na]+ calcd for C21H34B2NaO4 +: 409.2692; found: 409.2689。
example 65 bis (cyclopentadienyl) titanium dichloride (noted Cp)2TiCl20.01mmol, 2.5 mg), lithium methoxide (noted as MeOLi,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL) and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L)Adding into 38mL pressure resistant tube, stirring for 30min, adding 1-bromo-4- (4-bromobutyl) benzene (1 z, 0.2mmol, 58 mg), stirring at 60 deg.C under nitrogen (1 atm) for 24h, and purifying by column chromatography with petroleum ether/ethyl acetate (40: 1, v/v) as eluent to obtain the compound (colorless transparent liquid, 2- (4- (4-bromophenyl) butyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan) with structure shown in formula 2 z. The isolated yield was 66%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are:1H NMR (400 MHz, Chloroform-d) δ 7.44 – 7.20 (m, 2H), 7.18 – 6.99 (m, 2H), 2.57 (dt, J = 21.1, 7.7 Hz, 2H), 1.72 – 1.54 (m, 2H), 1.45 (ddd, J = 11.2, 7.6, 5.7 Hz, 2H), 1.23 (s, 12H), 0.92 – 0.71 (m, 2H). 13C NMR (101 MHz, Chloroform-d) δ 142.9, 141.8, 131.2, 130.1, 128.4, 128.2, 125.5, 119.2, 82.90, 82.86, 35.8, 35.1, 34.1, 33.9, 24.8, 23.8, 23.6. 11B NMR (128 MHz, Chloroform-d) δ 34.09. HRMS (ESI) m/z: [M+Na]+ calcd for C16H24BBrNaO2 +: 361.0945; found: 361.0945。
example 66 bis (cyclopentadienyl) titanium dichloride (noted Cp)2TiCl20.01mmol, 2.5 mg), lithium methoxide (note as MeOLi,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL) and pinacolborane (note as HBpin, 0.4mmol, 58 μ L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1- (5-bromopentyl) -1 hydroindole (note as 1aa, 0.2mmol, 53 mg), stirred under nitrogen (1 atm) atmosphere at 60 ℃ for 24h, and the mixture was cooled to room temperature in petroleum ether/ethyl acetate (40: 1, v/v) as an eluent to obtain a compound having a structure represented by formula 2aa (colorless transparent liquid, 1- (5- (4, 4,5, 5-tetramethyl-1, 3, 2-dioxaborole cyclopentane) pentyl)). The isolated yield was 66%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are:1H NMR (400 MHz, Chloroform-d) δ 7.63 (dt, J = 7.9, 1.0 Hz, 1H), 7.35 (dd, J = 8.3, 1.0 Hz, 1H), 7.20 (ddd, J = 8.3, 7.0, 1.2 Hz, 1H), 7.16 – 7.05 (m, 2H), 6.48 (dd, J = 3.1, 0.9 Hz, 1H), 4.12 (t, J = 7.1 Hz, 2H), 1.86 (p, J = 7.3 Hz, 2H), 1.47 (q, J = 7.9 Hz, 2H), 1.36 – 1.30 (m, 2H), 1.23 (s, 12H), 0.79 (t, J = 7.7 Hz, 2H). 13C NMR (101 MHz, Chloroform-d) δ 136.0, 128.6, 127.7, 121.2, 120.9, 119.1, 109.4, 100.8, 82.9, 46.3, 30.0, 29.6, 24.8, 23.6. 11B NMR (128 MHz, Chloroform-d) δ 34.19. HRMS (ESI) m/z: [M+H]+ calcd for C19H29BNO2 +: 314.2286; found: 314.2291。
example 67 bis (cyclopentadienyl) titanium dichloride (noted Cp)2TiCl20.01mmol, 2.5 mg), lithium methoxide (note as MeOLi,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL) and pinacolborane (note as HBpin, 0.4mmol, 58 μ L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then 9- (5-bromopentyl) -9 hydrocarbazole (note as 1ab, 0.2mmol, 63 mg) was added, stirred under nitrogen (1 atm) at 60 ℃ for 24h, and the mixture was cooled to room temperature using petroleum ether/ethyl acetate (40: 1, v/v) as eluent to obtain a compound (colorless transparent liquid, 9- (5- (4, 4,5, 5-tetramethyl-1, 3, 2-dioxaborole) pentyl) -9H carbazole) with a structure shown in a formula 2 ab) through column chromatography purification. The isolated yield was 71%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are:1H NMR (400 MHz, Chloroform-d) δ 8.01 (d, J = 7.7 Hz, 1H), 7.43 – 7.26 (m, 4H), 7.13 (ddd, J = 8.0, 6.9, 1.2 Hz, 2H), 4.21 (t, J = 7.3 Hz, 2H), 1.80 (p, J = 7.3 Hz, 2H), 1.46 – 1.27 (m, 2H), 1.10 (s, 12H), 0.68 (t, J = 7.5 Hz, 2H).13C NMR (101 MHz, Chloroform-d) δ 140.5, 125.5, 122.8, 120.3, 118.6, 108.7, 82.9, 43.1, 29.9, 28.8, 24.8, 23.8. 11B NMR (128 MHz, Chloroform-d) δ 33.82. HRMS (ESI) m/z: [M+Na]+ calcd for C23H30BNNaO2 +: 386.2262; found: 386.2266。
example 68 bis (cyclopentadienyl) titanium dichloride (noted Cp)2TiCl20.01mmol, 2.5 mg), potassium carbonate (noted as K)2CO30.2mmol, 26.7 mg), methyl tert-butyl ether (1 mL) and naphthol borane (noted HBcat, 0.6mmol, 63. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then bromocyclobutane (noted 1ac, 0.2mmol, 17. mu.L) was added, stirred under nitrogen (1 atm) atmosphere at 80 ℃ for 24h, after the reaction was complete triethylamine (0.6 mmol, 84. mu.L) and pinacol (0.6 mmol, 70.8 mg) were added, and stirred at room temperature for 1 h. Then, the compound with the structure shown in the formula 2ac (colorless transparent liquid, 2-cyclobutyl-4, 4,5, 5-tetramethyl-1, 3, 2-dioxaborole) is obtained by column chromatography purification with petroleum ether/ethyl acetate (40: 1, v/v) as an eluent. The isolated yield was 95%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are:1H NMR (400 MHz, Chloroform-d) δ 2.24 – 1.92 (m, 6H), 1.25 (s, 12H).13C NMR (101 MHz, Chloroform-d) δ 82.9, 24.8, 23.9, 22.7.11B NMR (128 MHz, Chloroform-d) δ 33.91。
example 69 bis (cyclopentadienyl) titanium dichloride (noted Cp2TiCl20.01mmol, 2.5 mg), potassium carbonate (noted as K)2CO30.2mmol, 26.7 mg), methyl tert-butyl ether (1 mL) andnaphtholborane (noted as HBcat, 0.6mmol, 63. mu.L) was sequentially added to 38mL of pressure resistant tube, and after stirring for 30min, bromocyclopentane (noted as 1ab, 0.2mmol, 21. mu.L) was added, and after the reaction was completed, triethylamine (0.6 mmol, 84. mu.L) and pinacol (0.6 mmol, 70.8 mg) were added, and the mixture was stirred at room temperature for 1 h. Then using petroleum ether/ethyl acetate (40: 1, v/v) as eluent to carry out column chromatography purification to obtain a compound (colorless transparent liquid, 2-cyclopentyl-4, 4,5, 5-tetramethyl-1, 3, 2-dioxaborolan) with a structure shown in a formula 2 ab. The isolated yield was 92%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are:1H NMR (400 MHz, Chloroform-d) δ 1.80 – 1.70 (m, 2H), 1.58 (dd, J = 5.3, 1.2 Hz, 2H), 1.53 – 1.40 (m, 4H), 1.24 (s, 12H), 1.16 (d, J = 8.7 Hz, 1H).13C NMR (101 MHz, Chloroform-d) δ 82.8, 28.5, 26.8, 24.7.11B NMR (128 MHz, Chloroform-d) δ 34.73。
example 70 bis (cyclopentadienyl) titanium dichloride (noted Cp2TiCl20.01mmol, 2.5 mg), potassium carbonate (noted as K)2CO30.2mmol, 26.7 mg), methyl tert-butyl ether (1 mL) and naphthol borane (denoted as HBcat, 0.6mmol, 63. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then bromocyclohexane (denoted as 1ae, 0.2mmol, 24. mu.L) was added, stirred under nitrogen (1 atm) atmosphere at 80 ℃ for 24h, after the reaction was complete triethylamine (0.6 mmol, 84. mu.L) and pinacol (0.6 mmol, 70.8 mg) were added, and stirred at room temperature for 1 h. Then, the compound with the structure shown in the formula 2ae (colorless transparent liquid, 2-cyclohexyl-4, 4,5, 5-tetramethyl-1, 3, 2-dioxaborole) is obtained by column chromatography purification with petroleum ether/ethyl acetate (40: 1, v/v) as an eluent. The isolated yield was 57%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are:1H NMR (400 MHz, Chloroform-d) δ 1.45 – 1.34 (m, 2H), 1.29 – 1.25 (m, 4H), 1.24 (s, 12H), 0.92 – 0.83 (m, 3H), 0.76 (t, J = 7.7 Hz, 2H).13C NMR (101 MHz, Chloroform-d) δ 82.8, 32.1, 31.6, 24.8, 24.0, 22.6, 14.1.11B NMR (128 MHz, Chloroform-d) δ 34.27。
example 71 bis (cyclopentadienyl) titanium dichloride (noted Cp2TiCl20.01mmol, 2.5 mg), potassium carbonate (noted as K)2CO30.2mmol, 26.7 mg), methyl tert-butyl ether (1 mL) and naphthol borane (noted HBcat, 0.6mmol, 63. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, bromocycloheptane (noted 1af, 0.2mmol, 28. mu.L) was added, stirred under nitrogen (1 atm) atmosphere at 80 ℃ for 24h, triethylamine (0.6 mmol, 84. mu.L) and pinacol (0.6 mmol, 70.8 mg) were added after the reaction was complete, and stirred at room temperature for 1 h. Then using petroleum ether/ethyl acetate (40: 1, v/v) as eluent to carry out column chromatography purification to obtain the compound with the structure shown in the formula 2af (colorless transparent liquid, 2-cycloheptyl-4, 4,5, 5-tetramethyl-1, 3, 2-dioxaborolan). The isolated yield was 78%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are:1H NMR (400 MHz, Chloroform-d) δ 1.97 – 1.61 (m, 4H), 1.57 – 1.40 (m, 8H), 1.23 (s, 12H), 1.08 (q, J = 4.8 Hz, 1H).13C NMR (101 MHz, Chloroform-d) δ 82.8, 29.6, 29.0, 28.4, 24.7.11B NMR (128 MHz, Chloroform-d) δ 34.55。
example 72 bis (cyclopentadienyl) titanium dichloride (noted Cp2TiCl20.01mmol, 2.5 mg), potassium carbonate (noted as K)2CO30.2mmol, 26.7 mg), methyl tert-butyl ether (1 mL) and naphthol borane (HBcat, 0.6mmol, 63. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 4-bromotetrahydropyran (1 ag, 0.2mmol, 23. mu.L), stirred under nitrogen (1 atm) at 80 ℃ for 24h, after the reaction was complete, added with triethylamine (0.6 mmol, 84. mu.L) and pinacol (0.6 mmol, 70.8 mg), and stirred at room temperature for 1 h. Then, the compound with the structure shown in the formula 2ag (colorless transparent liquid, 2- (tetrahydro-2H-pyran) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborocycloborolane) is obtained by column chromatography purification with petroleum ether/ethyl acetate (40: 1, v/v) as an eluent. The isolated yield was 79%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are:1H NMR (400 MHz, Chloroform-d) δ 3.81 (d, J = 11.2 Hz, 2H), 3.45 (dd, J = 12.7, 6.4, 4.8 Hz, 2H), 1.61 (td, J = 7.5, 6.8, 3.8 Hz, 4H), 1.23 (s, 12H), 1.18 (m, 1H). 13C NMR (101 MHz, Chloroform-d) δ 83.1, 68.8, 27.6, 24.7. 11B NMR (128 MHz, Chloroform-d) δ 33.75。
example 73 bis (cyclopentadienyl) titanium dichloride (noted Cp2TiCl20.01mmol, 2.5 mg), potassium carbonate (noted as K)2CO30.2mmol, 26.7 mg), methyl tert-butyl ether (1 mL) and naphthol borane (denoted as HBcat, 0.6mmol, 63. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-bromo-2-methylcyclohexane (denoted as 1ah, 0.2mmol, 28. mu.L), stirred under nitrogen (1 atm) at 80 ℃ for 24h, after the reaction was complete, added with triethylamine (0.6 mmol, 84. mu.L) and pinacol (0.6 mmol, 70.8 mg), and stirred at room temperature for 1 h. Then, the compound of formula 2ah (colorless transparent liquid, 2- (1-methylcyclohexyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan) was purified by column chromatography using petroleum ether/ethyl acetate (40: 1, v/v) as an eluent. The isolated yield was 68%。
The chemical reaction formula of the preparation process is as follows:
the characterization data are:1H NMR (400 MHz, Chloroform-d) δ 1.77 – 1.59 (m, 4H), 1.48 – 1.38 (m, 2H), 1.24 (d, J = 3.0 Hz, 12H), 0.87 (d, J = 6.5 Hz, 3H), 0.64 – 0.55 (m, 1H).13C NMR (101 MHz, Chloroform-d) δ 82.7, 36.1, 33.3, 28.0, 26.8, 26.5, 24.8, 24.6, 22.9.11B NMR (128 MHz, Chloroform-d) δ 34.23. HRMS (ESI) m/z: [M+Na]+ calcd for C13H25BNaO2 +: 247.1840; found: 247.1844。
example 74 bis (cyclopentadienyl) titanium dichloride (noted Cp2TiCl20.01mmol, 2.5 mg), potassium carbonate (noted as K)2CO30.2mmol, 26.7 mg), methyl tert-butyl ether (1 mL) and borane naphthol (HBcat, 0.6mmol, 63. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then (1R, 2R, 4R) -2-bromo-1-isopropyl-4-methylcyclohexane (1 ai, 0.2mmol, 44 mg) was added, stirred under nitrogen (1 atm) at 80 ℃ for 24h, after the reaction was complete triethylamine (0.6 mmol, 84. mu.L) and pinacol (0.6 mmol, 70.8 mg) were added, and stirred at room temperature for 1 h. Then, the compound with the structure shown in the formula 2ai (colorless transparent liquid, 2- (2-isopropyl-5-methylcyclohexyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan) is obtained by column chromatography purification with petroleum ether/ethyl acetate (40: 1, v/v) as an eluent. The isolated yield was 77%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are:1H NMR (400 MHz, Chloroform-d) δ 1.79 – 1.67 (m, 1H), 1.68 – 1.57 (m, 3H), 1.23 (s, 15H), 0.90 (d, J = 6.9 Hz, 4H), 0.84 (d, J = 6.5 Hz, 4H), 0.77 (d, J = 6.9 Hz, 3H). 13C NMR (101 MHz, Chloroform-d) δ 82.7, 43.8, 37.2, 35.4, 33.5, 32.0, 26.0, 24.8, 24.7, 22.7, 21.7, 16.5.11B NMR (128 MHz, Chloroform-d) δ 33.76。
example 75 bis (cyclopentadienyl) titanium dichloride (noted Cp)2TiCl20.01mmol, 2.5 mg), potassium carbonate (noted as K)2CO30.2mmol, 26.7 mg), methyl tert-butyl ether (1 mL) and naphthol borane (denoted as HBcat, 0.6mmol, 63. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 2-bromohydrindene (denoted as 1aj, 0.2mmol, 39 mg), stirred under nitrogen (1 atm) at 80 ℃ for 24h, after the reaction was complete, added with triethylamine (0.6 mmol, 84. mu.L) and pinacol (0.6 mmol, 70.8 mg), and stirred at room temperature for 1 h. Then, the compound with the structure shown in the formula 2aj (colorless transparent liquid, 2- (2, 3-dihydro-1-hydro-indene) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan) is obtained by column chromatography purification with petroleum ether/ethyl acetate (40: 1, v/v) as an eluent. The isolated yield was 59%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are:1H NMR (400 MHz, Chloroform-d) δ 7.21 (dd, J = 5.3, 3.3 Hz, 2H), 7.12 (dd, J = 5.5, 3.2 Hz, 2H), 3.18 – 2.82 (m, 4H), 1.89 (t, J = 9.8 Hz, 1H), 1.27 (s, 12H).13C NMR (101 MHz, Chloroform-d) δ 144.4, 125.9, 124.2, 83.2, 35.1, 24.8.11B NMR (128 MHz, Chloroform-d) δ 34.59。
example 76 bis (cyclopentadienyl) titanium dichloride (noted Cp2TiCl20.01mmol, 2.5 mg), potassium carbonate (noted as K)2CO30.2mmol, 26.7 mg), methyl tert-butyl ether (1 mL) and borane naphthol (noted as HBcat, 0.6mmol, 63. mu.L) were added sequentially to a 38mL pressure resistant tube,after stirring for 30min, the mixture was added with exo-2-bromonorbornane (1 ak, 0.2mmol, 24. mu.L), stirred at 80 ℃ for 24h under nitrogen (1 atm), and after the reaction was completed, triethylamine (0.6 mmol, 84. mu.L) and pinacol (0.6 mmol, 70.8 mg) were added, and stirred at room temperature for 1 h. Then using petroleum ether/ethyl acetate (40: 1, v/v) as eluent to carry out column chromatography purification to obtain a compound (colorless transparent liquid, 2- ((1S, 4S) -bicyclo [ 2.2.1) with a structure shown in a formula 2ak]Heptan-2-yl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan). The isolated yield was 80%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1H NMR (400 MHz, Chloroform-d) δ 2.35 – 2.13 (m, 2H), 1.58 – 1.44 (m, 3H), 1.38 – 1.28 (m, 1H), 1.24 (s, 4H), 1.22 (s, 12H), 1.16 – 1.15 (m, 1H). 13C NMR (101 MHz, Chloroform-d) δ 82.9, 82.8, 39.0, 38.7, 38.1, 37.1, 36.7, 32.2, 29.9, 29.3, 24.7.11B NMR (128 MHz, Chloroform-d) δ 34.14。
example 77 bis (cyclopentadienyl) titanium dichloride (noted Cp)2TiCl20.01mmol, 2.5 mg), potassium carbonate (noted as K)2CO30.2mmol, 26.7 mg), methyl tert-butyl ether (1 mL) and naphthol borane (HBcat, 0.6mmol, 63. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 2-bromooctane (1 al, 0.2mmol, 34. mu.L), stirred at 80 ℃ for 24h under nitrogen (1 atm) atmosphere, after the reaction was complete, added with triethylamine (0.6 mmol, 84. mu.L) and pinacol (0.6 mmol, 70.8 mg), and stirred at room temperature for 1 h. Then using petroleum ether/ethyl acetate (40: 1, v/v) as eluent to carry out column chromatography purification to obtain a compound with a structure shown in a formula 2al (colorless transparent liquid, 2-octyl-4, 4,5, 5-tetramethyl-1, 3, 2-dioxaborolan). The isolated yield was 58%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1H NMR (400 MHz, Chloroform-d) δ 1.48 – 1.37 (m, 1H), 1.31 – 1.25 (m, 9H), 1.23 (s, 12H), 0.96 (s, 3H), 0.90 – 0.83 (m, 3H).13C NMR (101 MHz, Chloroform-d) δ 82.7, 33.3, 31.9, 29.5, 24.8, 24.8, 24.7, 22.6, 15.5, 14.1.11B NMR (128 MHz, Chloroform-d) δ 34.59。
example 78 bis (cyclopentadienyl) titanium dichloride (noted Cp)2TiCl20.01mmol, 2.5 mg), potassium carbonate (noted as K)2CO30.2mmol, 26.7 mg), methyl tert-butyl ether (1 mL) and naphthol borane (denoted as HBcat, 0.6mmol, 63. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 2-bromoadamantane (denoted as 1am, 0.2mmol, 44 mg), stirred under nitrogen (1 atm) atmosphere at 80 ℃ for 24h, after the reaction was complete, added with triethylamine (0.6 mmol, 84. mu.L) and pinacol (0.6 mmol, 70.8 mg), and stirred at room temperature for 1 h. Then, the compound with the structure shown in the formula 2am (colorless transparent liquid, 2-adamantyl-4, 4,5, 5-tetramethyl-1, 3, 2-dioxaborolan) is obtained by column chromatography purification with petroleum ether/ethyl acetate (40: 1, v/v) as an eluent. The isolated yield was 90%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are:1H NMR (400 MHz, Chloroform-d) δ 2.08 – 2.00 (m, 2H), 1.92 – 1.58 (m, 12H), 1.40 – 1.31 (m, 1H), 1.24 (s, 12H).13C NMR (101 MHz, Chloroform-d) δ 82.7, 39.4, 37.8, 36.3, 29.3, 28.3, 28.1, 24.8.11B NMR (128 MHz, Chloroform-d) δ 34.17。
example 79 bis (cyclopentadienyl) titanium dichloride (noted Cp2TiCl20.01mmol, 2.5 mg), potassium carbonate (noted as K)2CO30.2mmol, 26.7 mg), methyl tert-butyl ether (1 mL) and borane naphthol (noted as HBcat, 0.6mmol, 63. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-Cbz-4-bromopiperidine (noted as 1an, 0.2mmol, 44. mu.L), stirred under nitrogen (1 atm) atmosphere at 80 ℃ for 24h, after the reaction was complete, added with triethylamine (0.6 mmol, 84. mu.L) and pinacol (0.6 mmol, 70.8 mg), and stirred at room temperature for 1 h. Then, the compound represented by the formula 2an (4- (2-4, 4,5, 5-tetramethyl-1, 3, 2-dioxaborole cyclopentyl) piperidine-1-carboxylic acid benzyl ester) is obtained by column chromatography purification with petroleum ether/ethyl acetate (20: 1, v/v) as an eluent. The isolated yield was 78%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are:1H NMR (400 MHz, Chloroform-d) δ 7.46 – 7.28 (m, 5H), 5.11 (s, 2H), 3.87 (d, J = 13.2 Hz, 2H), 3.17 – 2.94 (m, 2H), 1.65 (s, 2H), 1.61 – 1.46 (m, 2H), 1.23 (s, 12H), 1.13 (td, J = 10.3, 5.1 Hz, 1H).13C NMR (101 MHz, Chloroform-d) δ 155.3, 128.4, 127.8, 127.8, 83.2, 66.8, 45.1, 24.8.11B NMR (128 MHz, Chloroform-d) δ 33.65。
example 80 bis (cyclopentadienyl) titanium dichloride (noted Cp2TiCl20.01mmol, 2.5 mg), potassium carbonate (noted as K)2CO30.2mmol, 26.7 mg), methyl tert-butyl ether (1 mL) and borane naphthol (noted HBcat, 0.6mmol, 63. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-Boc-4-bromopiperidine (noted 1ao, 0.2mmol, 53 mg), stirred under nitrogen (1 atm) atmosphere at 80 ℃ for 24h, after the reaction was complete triethylamine (0.6 mmol, 84. mu.L) and pinacol (0.6 mmol, 70.8 mg), and stirred at room temperature for 1 h. Then using petroleum ether/ethyl acetate (20: 1, v/v) as eluent to carry out column chromatography purification to obtain a compound (colorless transparent liquid, 1-carboxylic acid tert-butyl ester-2- (4, 4,5, 5-tetramethyl) with a structure shown in formula 2ao-1,3, 2-dioxaborohetero) piperidine). The isolated yield was 36%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are:1H NMR (400 MHz, Chloroform-d) δ 3.90 – 3.67 (m, 2H), 2.92 (ddd, J = 13.4, 10.2, 3.2 Hz, 2H), 1.63 (ddt, J = 12.4, 8.4, 3.6 Hz, 9H), 1.44 (s, 12H), 1.23 (s, 6H), 1.17 – 1.03 (m, 1H).13C NMR (101 MHz, Chloroform-d) δ 154.9, 83.1, 79.0, 28.5, 27.0, 24.8. 11B NMR (128 MHz, Chloroform-d) δ 34. 04。
example 81 bis (cyclopentadienyl) titanium dichloride (noted Cp2TiCl20.01mmol, 2.5 mg), potassium carbonate (noted as K)2CO30.2mmol, 26.7 mg), methyl tert-butyl ether (1 mL) and naphthol borane (denoted as HBcat, 0.6mmol, 63. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-bromoadamantane (denoted as 1ap, 0.2mmol, 53 mg), stirred at 80 ℃ under nitrogen (1 atm) for 24h, after the reaction was complete, added with triethylamine (0.6 mmol, 84. mu.L) and pinacol (0.6 mmol, 70.8 mg), and stirred at room temperature for 1 h. Then, the compound with the structure shown in the formula 2ap (white solid, 2- ((3 r, 5r, 7 r) -adamantyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan) is obtained by column chromatography purification with petroleum ether/ethyl acetate (40: 1, v/v) as an eluent. The isolated yield was 63%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are:1H NMR (400 MHz, Chloroform-d) δ 1.84 (dd, J = 6.0, 3.0 Hz, 3H), 1.75 (d, J = 3.1 Hz, 12H), 1.20 (s, 12H). 13C NMR (101 MHz, Chloroform-d) δ 82.6, 38.0, 37.5, 27.6, 24.6.11B NMR (128 MHz, Chloroform-d) δ 33.60。
example 82 bis (cyclopentadienyl) titanium dichloride (noted Cp2TiCl20.01mmol, 2.5 mg), potassium carbonate (noted as K)2CO30.2mmol, 26.7 mg), methyl tert-butyl ether (1 mL) and borane naphthol (HBcat, 0.6mmol, 63. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-bromocedrol (1 aq, 0.2mmol, 56.8 mg), stirred under nitrogen (1 atm) at 80 ℃ for 24h, after the reaction was complete, added with triethylamine (0.6 mmol, 84. mu.L) and pinacol (0.6 mmol, 70.8 mg), and stirred at room temperature for 1 h. Then, the compound with the structure shown in the formula 2aq (colorless transparent liquid, 2- ((3R, 3aS, 6S, 7S, 8 aS) -3,6,8, 8-tetramethyl-1-hydro-3 a, 7-formyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan) is obtained by column chromatography purification with petroleum ether/ethyl acetate (40: 1, v/v) aS an eluent. The isolated yield was 66%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are:1H NMR (400 MHz, Chloroform-d) δ 1.88 – 1.69 (m, 5H), 1.61 (td, J = 7.4, 6.0 Hz, 2H), 1.53 – 1.29 (m, 7H), 1.24 (d, J = 5.3 Hz, 12H), 1.13 (s,3H), 1.02 (d, J = 7.3 Hz, 3H), 0.92 (s, 3H), 0.82 (d, J = 7.1 Hz, 3H).13C NMR (101 MHz, Chloroform-d) δ 82.8, 57.8, 56.3, 54.4, 47.3, 44.1, 42.5, 39.3, 37.1, 35.4, 29.0, 27.1, 25.5, 24.9, 24.5, 21.7, 15.4.11B NMR (128 MHz, Chloroform-d) δ 34.63. HRMS (ESI) m/z: [M+Na]+ calcd for C21H37BNaO2 +: 355.2779; found: 355.2777。
example 83 bis (cyclopentadienyl) titanium dichloride (noted Cp)2TiCl20.01mmol, 2.5 mg), potassium carbonate (noted as K)2CO30.2mmol, 26.7 mg) of methyl tert-butylSequentially adding the base ether (1 mL) and the naphthol borane (marked as HBcat, 0.6mmol, 63 mu L) into a 38mL pressure resistant tube, stirring for 30min, and adding the (5S, 8S, 9S, 10S, 13S, 14S) -3-bromo-10, 13-dimethylhexadecahydro-17 hydro-cyclopentyl [ a ] into the mixture]Phenanthren-17-one (denoted as 1ar, 0.2mmol, 70 mg) was stirred at 80 ℃ for 24h under nitrogen (1 atm), and after completion of the reaction, triethylamine (0.6 mmol, 84. mu.L) and pinacol (0.6 mmol, 70.8 mg) were added and stirred at room temperature for 1 h. Then using petroleum ether/ethyl acetate (40: 1, v/v) as eluent to carry out column chromatography purification to obtain a compound (colorless transparent liquid, 5S, 8S, 9S, 10S, 13S, 14S) -10, 13-dimethyl-3- (4, 4,5, 5-tetramethyl-1, 3, 2-dioxybenzofuran-2-yl) hexadecahydro-17H-cyclopentane [ a ] with a structure shown in formula 2ar]Phenanthren-17-one). The isolated yield was 66%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1H NMR (400 MHz, Chloroform-d) δ 3.61 (t, J = 8.5 Hz, 1H), 2.03 (ddd, J = 9.5, 5.8, 4.1 Hz, 1H), 1.82 – 1.50 (m, 8H), 1.45 – 1.32 (m, 5H), 1.22 (s, 12H), 1.09 – 0.98 (m, 2H), 0.97 – 0.81 (m, 5H), 0.78 (s, 3H), 0.72 (d, J = 3.0 Hz, 3H). 13C NMR (101 MHz, Chloroform-d) δ 125.8, 82.7, 82.0, 54.8, 51.2, 47.9, 43.0, 39.5, 36.8, 36.2, 35.6, 31.7, 30.5, 30.1, 28.8, 24.7, 23.4, 23.4, 20.4, 12.4, 11.1. 11B NMR (128 MHz, Chloroform-d) δ 35.42。
example 84 bis (cyclopentadienyl) titanium dichloride (noted Cp2TiCl20.01mmol, 2.5 mg), potassium carbonate (noted as K)2CO30.2mmol, 26.7 mg), methyl tert-butyl ether (1 mL) and naphthol borane (HBcat, 0.6mmol, 63. mu.L) were added in sequence to a 38mL pressure resistant tube, stirred for 30min, then bromocholesterol (1 as, 0.2mmol, 90 mg) was added, stirred under nitrogen (1 atm) atmosphere at 80 ℃ for 24h, and after the reaction was complete triethylamine (0.6 mmol, 84. mu.L) and pinacol (0.6 mmol, 84. mu.L) were added6mmol, 70.8 mg), stirred at room temperature for 1 h. Then using petroleum ether/ethyl acetate (40: 1, v/v) as eluent to carry out column chromatography purification to obtain the compound with the structure shown in the formula 2as (colorless transparent liquid, 2- (3 a, 6 a-dimethyl-3- (6-methylheptan-2-yl) -2,3,3a, 4,5,5a, 6,6a, 7,8,9,10,11a, 11 b-tetradecahydro-1H-cyclopentane [ a ] as]Anthracen-9-yl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan). The isolated yield was 66%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are: 1H NMR (400 MHz, Chloroform-d) δ 5.26 (d, J = 5.0 Hz, 1H), 2.20 (td, J = 13.8, 2.8 Hz, 1H), 2.10 – 1.89 (m, 6H), 1.83 (tq, J = 14.8, 5.7, 4.3 Hz, 13H), 1.70 – 1.31 (m, 12H), 1.23 (s, 7H), 1.15 – 1.03 (m, 7H), 0.99 (s, 3H), 0.91 (d, J = 6.5 Hz, 3H), 0.86 (d, J = 6.7 Hz, 6H), 0.67 (s, 3H).13C NMR (101 MHz, Chloroform-d) δ 143.7, 118.5, 82.7, 56.8, 56.2, 50.6, 42.3, 40.9, 39.9, 39.5, 37.3, 36.2, 35.8, 33.8, 31.9, 28.2, 28.0, 24.7, 24.3, 24.1, 23.9, 22.8, 22.6, 20.8, 19.5, 18.7, 11.9.11B NMR (128 MHz, Chloroform-d) δ 34.85. HRMS (ESI) m/z: [M+Na]+ calcd for C33H57BNaO2 +: 519.4344; found: 519.4353。
example 85 bis (cyclopentadienyl) titanium dichloride (noted Cp2TiCl20.01mmol, 2.5 mg), lithium methoxide (note as MeOLi,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL) and pinacolborane (note as HBpin, 0.4mmol, 58 μ L) were added in this order to a 38mL pressure resistant tube, stirred for 30min, then added with 1-chloroheptane (note as 1at, 0.2mmol, 31 μ L), stirred under nitrogen (1 atm) at 100 ℃ for 24h, and replaced with petroleum ether/ethyl acetate (40: 1, v/v) as an eluent to obtain a compound having a structure represented by formula 2at (a colorless transparent liquid, 1-heptanylboronic acid pinacol ester). Isolated yield 55%。
The chemical reaction formula of the preparation process is as follows:
the characterization data are:1H NMR (400 MHz, Chloroform-d) δ 1.49 – 1.33 (m, 3H), 1.25 (s, 9H), 1.23 (s, 12H), 0.86 (t, J = 6.7 Hz, 3H), 0.75 (t, J = 7.7 Hz, 2H). 13C NMR (101 MHz, Chloroform-d) δ 82.8, 32.4, 31.9, 29.4, 29.2, 24.8, 24.0, 22.7, 14.1. 11B NMR (128 MHz, Chloroform-d) δ 34.35。
example 86 bis (cyclopentadienyl) titanium dichloride (noted Cp2TiCl20.01mmol, 2.5 mg), lithium methoxide (MeOLi, 0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL), and pinacolborane (HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-chlorooctane (1 au, 0.2mmol, 34. mu.L), stirred at 100 ℃ for 24h under nitrogen (1 atm) atmosphere, and purified by column chromatography using petroleum ether/ethyl acetate (40: 1, v/v) as an eluent to obtain a compound of the structure shown in formula 2au (colorless transparent liquid, 1-heptanylpinacol borate). The isolated yield was 69%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are:1H NMR (400 MHz, Chloroform-d) δ 1.49 – 1.33 (m, 3H), 1.25 (s, 9H), 1.23 (s, 12H), 0.86 (t, J = 6.7 Hz, 3H), 0.75 (t, J = 7.7 Hz, 2H). 13C NMR (101 MHz, Chloroform-d) δ 82.8, 32.4, 31.9, 29.4, 29.2, 24.8, 24.0, 22.7, 14.1. 11B NMR (128 MHz, Chloroform-d) δ 34.35。
example 87 bis (cyclopentadienyl) titanium dichloride (noted Cp2TiCl20.01mmol, 2.5 mg) ofSequentially adding lithium alkoxide (marked as MeOLI,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL) and pinacolborane (marked as HBpin, 0.4mmol, 58 μ L) into a 38mL pressure resistant tube, stirring for 30min, adding 1-chloroethane (marked as 1av, 0.2mmol, 27 μ L), stirring at 100 ℃ for 24h under a nitrogen (1 atm) atmosphere, and performing column chromatography purification by using petroleum ether/ethyl acetate (40: 1, v/v) as an eluent to obtain a structural compound (colorless transparent liquid, 2- (2-phenylethyl) pinacol borate) shown in formula 2 av. The isolated yield was 84%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are:1H NMR (400 MHz, Chloroform-d) δ 7.33 – 7.19 (m, 4H), 7.20 – 7.12 (m, 1H), 2.91 – 2.59 (m, 2H), 1.22 (s, 12H), 1.14 (dd, J = 9.0, 7.4 Hz, 2H). 13C NMR (101 MHz, Chloroform-d) δ 144.4, 128.2, 128.0, 125.5, 83.1, 30.0, 24.8. 11B NMR (128 MHz, Chloroform-d) δ 33.98。
example 88 bis (cyclopentadienyl) titanium dichloride (noted Cp2TiCl20.01mmol, 2.5 mg), lithium methoxide (note as MeOLi,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL), and pinacolborane (note as HBpin, 0.4mmol, 58 μ L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-chloropropane (note as 1aw, 0.2mmol, 30 μ L), stirred under nitrogen (1 atm) at 100 ℃ for 24h, and mixed with petroleum ether/ethyl acetate (40: 1, v/v) as an eluent to obtain a compound (colorless transparent liquid, 2- (3-phenylpropyl) boronic acid pinacol ester) having a structure shown in formula 2 aw. The isolated yield was 86%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are:1H NMR (400 MHz, Chloroform-d) δ 7.24 – 7.12 (m, 2H), 7.11 – 7.04 (m, 3H), 2.59 – 2.46 (m, 2H), 1.76 – 1.57 (m, 2H), 1.16 (s, 12H), 0.84 – 0.68 (m, 2H).13C NMR (101 MHz, Chloroform-d) δ 142.7, 128.5, 128.1, 125.5, 82.9, 38.6, 26.1, 24.8.11B NMR (128 MHz, Chloroform-d) δ 34.13。
example 89 bis (cyclopentadienyl) titanium dichloride (noted Cp2TiCl20.01mmol, 2.5 mg), lithium methoxide (note as MeOLi,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL), and pinacolborane (note as HBpin, 0.4mmol, 58 μ L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 3-phenoxychloropropane (note as 1ax, 0.2mmol, 32 μ L), stirred at 100 ℃ for 24h under nitrogen (1 atm) atmosphere, and mixed with petroleum ether/ethyl acetate (10: 1, v/v) as eluent to obtain a compound (colorless transparent liquid, 2- (3-phenoxypropyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborole cyclopentane) with a structure shown in a formula 2ax by column chromatography purification. The isolated yield was 58%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are:1H NMR (400 MHz, Chloroform-d) δ 7.31 – 7.22 (m, 4H), 7.22 – 7.16 (m, 1H), 4.43 (s, 2H), 3.37 (t, J = 6.7 Hz, 2H), 1.67 (p, J = 7.0 Hz, 2H), 1.15 (s, 12H), 0.76 (t, J = 7.8 Hz, 2H). 13C NMR (101 MHz, Chloroform-d) δ 138.9, 128.3, 127.6, 127.4, 82.9, 72.7, 72.4, 24.8, 24.2. 11B NMR (128 MHz, Chloroform-d) δ 34.18。
example 90 bis (cyclopentadienyl) titanium dichloride (noted Cp2TiCl20.01mmol, 2.5 mg), lithium methoxide (noted as MeOLi,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL) and pinacolborane (noted as HBpin, 0.4mmol, 58. mu.L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min and then 2-chloropropane (noted as 1ay, 0.2 m)mol, 30 μ L), stirred at 100 ℃ for 24h under nitrogen (1 atm) atmosphere, and purified with petroleum ether/ethyl acetate (40: 1, v/v) as eluent to obtain a compound (colorless transparent liquid, 2-phenylpropyl-4, 4,5, 5-tetramethyl-1, 3, 2-dioxaborocyclopentane) with the structure shown in the formula 2ay by column chromatography purification. The isolated yield was 41%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are:1H NMR (400 MHz, Chloroform-d) δ 7.40 – 7.04 (m, 5H), 2.81 (dd, J = 13.6, 7.5 Hz, 1H), 2.56 (td, J = 14.4, 13.6, 8.2 Hz, 1H), 1.44 – 1.30 (m, 1H), 1.18 (d, J = 4.4 Hz, 12H), 0.96 (d, J = 7.4 Hz, 3H).13C NMR (101 MHz, Chloroform-d) δ 142.4, 128.9, 128.0, 125.5, 83.0, 39.0, 24.8, 24.7, 24.7, 15.2.11B NMR (128 MHz, Chloroform-d) δ 34.45。
example 91 bis (cyclopentadienyl) titanium dichloride (noted Cp2TiCl20.01mmol, 2.5 mg), lithium methoxide (note as MeOLi,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL), and pinacolborane (note as HBpin, 0.4mmol, 58 μ L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 4-chlorotetrahydropyran (note as 1az, 0.2mmol, 23 μ L), stirred under nitrogen (1 atm) at 100 ℃ for 24h, and replaced with petroleum ether/ethyl acetate (40: 1, v/v) as eluent to obtain a compound (2-tetrahydro-2-hydropyran) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborocycloborolane) with a structure shown in a formula 2 az. The isolated yield was 68%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are:1H NMR (400 MHz, Chloroform-d) δ 3.81 (d, J = 11.2 Hz, 2H), 3.45 (dd, J = 12.7, 6.4, 4.8 Hz, 2H), 1.61 (td, J = 7.5, 6.8, 3.8 Hz, 4H), 1.23 (s, 12H), 1.18 (m, 1H). 13C NMR (101 MHz, Chloroform-d) δ 83.1, 68.8, 27.6, 24.7. 11B NMR (128 MHz, Chloroform-d) δ 33.75。
example 92 bis (cyclopentadienyl) titanium dichloride (noted Cp)2TiCl20.01mmol, 2.5 mg), lithium methoxide (note as MeOLi,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL) and pinacolborane (note as HBpin, 0.4mmol, 58 μ L) were sequentially added to a 38mL pressure resistant tube, and after stirring for 30min, chlorocyclobutane (note as 1aba, 0.2mmol, 17 μ L) was added, and the mixture was stirred under nitrogen (1 atm) at 100 ℃ for 24h to obtain a solution of petroleum ether/ethyl acetate (40: 1, v/v) as eluent to obtain a compound (colorless transparent liquid, 2-cyclobutyl-4, 4,5, 5-tetramethyl-1, 3, 2-dioxaborole cyclopentane) with a structure shown in formula 2 aba. The isolated yield was 88%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are:1H NMR (400 MHz, Chloroform-d) δ 2.24 – 1.92 (m, 6H), 1.25 (s, 12H).13C NMR (101 MHz, Chloroform-d) δ 82.9, 24.8, 23.9, 22.7.11B NMR (128 MHz, Chloroform-d) δ 33.91。
example 93 bis (cyclopentadienyl) titanium dichloride (noted Cp2TiCl20.01mmol, 2.5 mg), lithium methoxide (note as MeOLi,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL), and pinacolborane (note as HBpin, 0.4mmol, 58 μ L) were sequentially added to a 38mL pressure resistant tube, stirred for 30min, then added with 1-iodohexane (note as 1abb, 0.2mmol, 30 μ L), stirred under nitrogen (1 atm) at 50 ℃ for 24h, and mixed with petroleum ether/ethyl acetate (40: 1, v/v) as an eluent to obtain a compound (colorless transparent liquid, 1-hexanylboronic acid pinacol ester) having a structure represented by formula 2 abb. Quality of qiThe analytical yield was 95%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are:1H NMR (400 MHz, Chloroform-d) δ 1.47 – 1.35 (m, 2H), 1.27 (ddd, J = 6.5, 3.7, 2.2 Hz, 6H), 1.24 (s, 12H), 0.93 – 0.84 (m, 3H), 0.76 (t, J = 7.7 Hz, 2H). 13C NMR (101 MHz, Chloroform-d) δ 82.8, 32.1, 31.6, 29.7, 24.8, 24.0, 22.6, 14.1. 11B NMR (128 MHz, Chloroform-d) δ 34.31。
example 94 bis (cyclopentadienyl) titanium dichloride (noted Cp2TiCl20.01mmol, 2.5 mg), lithium methoxide (described as MeOLi,0.2mmol,7.6 mg), methyl tert-butyl ether (1 mL) and pinacolborane (described as HBpin, 0.4mmol, 58 μ L) were added in this order to a 38mL pressure resistant tube, and after stirring for 30min, hexyl methanesulfonate (described as 1abc, 0.2mmol, 34 μ L) was added, and the mixture was stirred under nitrogen (1 atm) at 100 ℃ for 24h to obtain a solution of petroleum ether/ethyl acetate (40: 1, v/v) as an eluent to obtain a compound (colorless transparent liquid, 1-hexanylboronic acid pinacol ester) having a structure shown in formula 2 abc. The yield of the gas chromatography was 59%.
The chemical reaction formula of the preparation process is as follows:
the characterization data are:1H NMR (400 MHz, Chloroform-d) δ 1.47 – 1.35 (m, 2H), 1.27 (ddd, J = 6.5, 3.7, 2.2 Hz, 6H), 1.24 (s, 12H), 0.93 – 0.84 (m, 3H), 0.76 (t, J = 7.7 Hz, 2H). 13C NMR (101 MHz, Chloroform-d) δ 82.8, 32.1, 31.6, 29.7, 24.8, 24.0, 22.6, 14.1. 11B NMR (128 MHz, Chloroform-d) δ 34.31。
the foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A method for directly preparing alkyl borate compounds from alkyl halides is characterized by comprising the following steps: in a protective atmosphere, mixing a titanium metal catalyst, an alkali compound, a borate compound and an alkyl halide or sulfonate compound, and reacting at 35-100 ℃ for 8-24 hours, namely directly converting the alkyl halide or sulfonate compound into an alkyl boronic acid pinacol ester compound; the molar ratio of the alkyl halide or sulfonate compound, the titanium metal catalyst, the alkali compound and the borate compound is 1: 0.05-0.1: 0.25-1: 2 to 3.
2. The process for the direct preparation of alkyl borates from alkyl halides according to claim 1, wherein: an organic solvent is also added in the mixing process of the titanium metal catalyst, the alkali compound, the borate compound and the alkyl halide or sulfonate compound; the molar ratio of the alkyl halide or sulfonate compound to the organic solvent is 0.2 mmol: 1 mL.
3. The process for the direct preparation of alkyl borates from alkyl halides according to claim 1 or 2, wherein: the structural formula of the alkyl halide or sulfonate compound is as follows:(ii) a In the formula: r1Is one of benzyl, substituted benzyl, heterocycle, substituted heterocycle, alkyl or alkenyl; r2And R3Are both alkyl or hydrogen.
4. The process for the direct preparation of alkyl borates from alkyl halides according to claim 3, wherein: the R is1Is one of benzyl, substituted benzyl, heterocycle, substituted heterocycle, alkyl or alkenyl.
5. The process for the direct preparation of alkyl borates from alkyl halides according to claim 4, wherein: and the substituent in the substituted benzyl is one of methyl, methoxy, ester, fluorine, chlorine, bromine, phenyl or trifluoromethyl.
6. The process for the direct preparation of alkyl borates from alkyl halides according to claim 1 or 2, wherein: the titanium metal catalyst is one of bis (cyclopentadienyl) titanium dichloride, (cyclopentadienyl) titanium trichloride, bis (tert-butylcyclopentadienyl) titanium dichloride, pentamethylcyclopentadienyl titanium trichloride and bis (pentamethylcyclopentadienyl) titanium dichloride.
7. The process for the direct preparation of alkyl borates from alkyl halides according to claim 1 or 2, wherein: the borate compound is pinacol borane or naphthol borane.
8. The process for the direct preparation of alkyl borates from alkyl halides according to claim 1 or 2, wherein: the alkali compound is one of potassium methoxide, sodium methoxide, lithium methoxide, potassium tert-butoxide, sodium tert-butoxide, lithium tert-butoxide, cesium carbonate, cesium fluoride, silver acetate, lithium carbonate, lithium hydride and methyllithium.
9. The process for the direct preparation of alkyl borates from alkyl halides according to claim 1 or 2, wherein: the organic solvent is one of N-hexane, dioxane, chloroform, N-dimethylformamide, ethyl acetate, diethylene glycol dimethyl ether, methyl tert-butyl ether, tetrahydrofuran, dichloromethane, acetonitrile and toluene.
10. The process for the direct preparation of alkyl borates from alkyl halides according to claim 1, wherein: the protective atmosphere refers to nitrogen atmosphere or argon atmosphere, and the pressure is 1 atm.
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