CN109593085A - 吡啶-酰胺-噁唑啉配体、其合成方法及其金属配合物和用途 - Google Patents
吡啶-酰胺-噁唑啉配体、其合成方法及其金属配合物和用途 Download PDFInfo
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- CN109593085A CN109593085A CN201811512968.7A CN201811512968A CN109593085A CN 109593085 A CN109593085 A CN 109593085A CN 201811512968 A CN201811512968 A CN 201811512968A CN 109593085 A CN109593085 A CN 109593085A
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- Prior art keywords
- oxazoline
- amide
- pyridine
- ligand
- phosphine
- Prior art date
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- -1 Pyridine-amide-oxazoline Chemical compound 0.000 title claims abstract description 46
- 239000003446 ligand Substances 0.000 title claims abstract description 39
- 238000010189 synthetic method Methods 0.000 title claims description 7
- 150000004696 coordination complex Chemical class 0.000 title abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 19
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 11
- 230000003197 catalytic effect Effects 0.000 claims abstract description 10
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 8
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 6
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 6
- 150000003624 transition metals Chemical class 0.000 claims abstract description 6
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 229910052737 gold Inorganic materials 0.000 claims abstract description 4
- 125000001072 heteroaryl group Chemical group 0.000 claims abstract description 4
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 4
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- 229910052762 osmium Inorganic materials 0.000 claims abstract description 4
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 4
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 4
- 229910052709 silver Inorganic materials 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 35
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 32
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 11
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 claims description 10
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 125000001424 substituent group Chemical group 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 5
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 230000007704 transition Effects 0.000 claims description 5
- QFMZQPDHXULLKC-UHFFFAOYSA-N 1,2-bis(diphenylphosphino)ethane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 QFMZQPDHXULLKC-UHFFFAOYSA-N 0.000 claims description 4
- BKLJUYPLUWUEOQ-UHFFFAOYSA-N 6-bromopyridin-2-amine Chemical compound NC1=CC=CC(Br)=N1 BKLJUYPLUWUEOQ-UHFFFAOYSA-N 0.000 claims description 4
- UBJUDOWYGUICSE-UHFFFAOYSA-N 6-bromopyridine-2-carbonyl chloride Chemical compound ClC(=O)C1=CC=CC(Br)=N1 UBJUDOWYGUICSE-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- XURXQNUIGWHWHU-UHFFFAOYSA-N 6-bromopyridine-2-carboxylic acid Chemical compound OC(=O)C1=CC=CC(Br)=N1 XURXQNUIGWHWHU-UHFFFAOYSA-N 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 230000008901 benefit Effects 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- 230000003287 optical effect Effects 0.000 claims description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 claims description 2
- 125000002577 pseudohalo group Chemical group 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- 239000003795 chemical substances by application Substances 0.000 claims 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims 2
- 125000003118 aryl group Chemical group 0.000 claims 1
- 150000001555 benzenes Chemical group 0.000 claims 1
- 125000000532 dioxanyl group Chemical group 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 abstract description 14
- 238000006197 hydroboration reaction Methods 0.000 abstract description 10
- 238000002360 preparation method Methods 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 44
- 239000007787 solid Substances 0.000 description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000012299 nitrogen atmosphere Substances 0.000 description 11
- 238000005160 1H NMR spectroscopy Methods 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- 239000012065 filter cake Substances 0.000 description 10
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000001345 alkine derivatives Chemical class 0.000 description 6
- 229910052796 boron Inorganic materials 0.000 description 5
- 238000005660 chlorination reaction Methods 0.000 description 5
- 239000012467 final product Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- 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 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 229910000085 borane Inorganic materials 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 4
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 4
- 238000004607 11B NMR spectroscopy Methods 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229940125904 compound 1 Drugs 0.000 description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- FPIBKDDEZCKPGT-ZCFIWIBFSA-N (4s)-4-propan-2-yl-4,5-dihydro-1,3-oxazole Chemical compound CC(C)[C@H]1COC=N1 FPIBKDDEZCKPGT-ZCFIWIBFSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- ZZPNDIHOQDQVNU-UHFFFAOYSA-N 2-hydroxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Chemical compound CC1(C)OB(O)OC1(C)C ZZPNDIHOQDQVNU-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- IPWKHHSGDUIRAH-UHFFFAOYSA-N bis(pinacolato)diboron Chemical compound O1C(C)(C)C(C)(C)OB1B1OC(C)(C)C(C)(C)O1 IPWKHHSGDUIRAH-UHFFFAOYSA-N 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-N cyanic acid Chemical compound OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000011565 manganese chloride Substances 0.000 description 2
- 239000003863 metallic catalyst Substances 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 230000000707 stereoselective effect Effects 0.000 description 2
- IFIUFEBEPGGBIJ-BYPYZUCNSA-N (4S)-4-methyl-4,5-dihydro-1,3-oxazole Chemical compound C[C@H]1COC=N1 IFIUFEBEPGGBIJ-BYPYZUCNSA-N 0.000 description 1
- RWGLROKEYRSHME-JTQLQIEISA-N (4s)-4-benzyl-4,5-dihydro-1,3-oxazole Chemical compound C=1C=CC=CC=1C[C@H]1COC=N1 RWGLROKEYRSHME-JTQLQIEISA-N 0.000 description 1
- QEMGMKHRBKOVHA-ZCFIWIBFSA-N (4s)-4-tert-butyl-4,5-dihydro-1,3-oxazole Chemical compound CC(C)(C)[C@H]1COC=N1 QEMGMKHRBKOVHA-ZCFIWIBFSA-N 0.000 description 1
- YOCRKHKJFCWTHG-UHFFFAOYSA-N 2-[6-(4,5-dihydro-1,3-oxazol-2-yl)pyridin-2-yl]-4,5-dihydro-1,3-oxazole Chemical compound O1CCN=C1C1=CC=CC(C=2OCCN=2)=N1 YOCRKHKJFCWTHG-UHFFFAOYSA-N 0.000 description 1
- KOAMXHRRVFDWRQ-UHFFFAOYSA-N 4,4-dimethyl-5h-1,3-oxazole Chemical compound CC1(C)COC=N1 KOAMXHRRVFDWRQ-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- RWMKXFCUXJWKBU-RXMQYKEDSA-N CC[C@@H]1COC=N1 Chemical compound CC[C@@H]1COC=N1 RWMKXFCUXJWKBU-RXMQYKEDSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- LXNAVEXFUKBNMK-UHFFFAOYSA-N acetic acid;palladium Chemical compound [Pd].CC(O)=O.CC(O)=O LXNAVEXFUKBNMK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- UVCJGUGAGLDPAA-UHFFFAOYSA-N ensulizole Chemical compound N1C2=CC(S(=O)(=O)O)=CC=C2N=C1C1=CC=CC=C1 UVCJGUGAGLDPAA-UHFFFAOYSA-N 0.000 description 1
- 229960000655 ensulizole Drugs 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- LZWQNOHZMQIFBX-UHFFFAOYSA-N lithium;2-methylpropan-2-olate Chemical compound [Li+].CC(C)(C)[O-] LZWQNOHZMQIFBX-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B53/00—Asymmetric syntheses
-
- 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
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic Table without C-Metal linkages
-
- 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
- C07F13/00—Compounds containing elements of Groups 7 or 17 of the Periodic Table
- C07F13/005—Compounds without a metal-carbon linkage
-
- 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/02—Iron compounds
- C07F15/025—Iron compounds without a metal-carbon linkage
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Abstract
本发明公开了一种吡啶‑酰胺‑噁唑啉配体,其为式(1)所述的化合物或者为式(1)所述化合物的对映体或消旋体,其中,R1和R2分别独立为C1~C10的烃基、苄基、苯基或取代的苯基、杂芳基中的一种。吡啶‑酰胺‑噁唑啉配体可以独立用于制备手性或非手性有机化合物,也可以与过渡金属Fe、Co、Ni、Cu、Ag、Au、Ru、Rh、Pd、Os、Ir形成稳定的金属配合物,该金属配合物能够应用于不对称催化反应,特别是对烯烃的不对称硼氢化反应具有非常高的催化活性。本发明还提供了高效的合成路线,两步总产率80%以上。
Description
技术领域
本发明涉及催化剂技术领域,尤其涉及吡啶-酰胺-噁唑啉配体、其合成方法及其金属配合物和用途。
背景技术
过渡金属催化的不对称合成反应是制备手性化合物最为高效的方式之一,也是工业和学术界共同关注的热门领域。自从化学家们发现可以通过手性配体的结合来调节过渡金属在不对称催化反应中的活性和选择性之后,手性配体的设计就成为了过渡金属催化不对称合成领域的核心内容之一。至今已有数以千计的手性配体被发展出来应用于不对称合成反应,其中也涌现了一些具有广泛催化活性的优势手性配体[(a)Q.Zhou,PrivilegedChiral Ligands and Catalysts,Wiley-VCH,Weinheim,2011;b)T.P.Yoon,E.N.Jacobsen,Science 2003,299,1691;c)A.faltz,W.J.Drury III,PNAS2004,101,5723.]。手性噁唑啉可以由自然界常见的氨基酸来制备,是一类常见的手性配体砌块,如优势手性配体PyBox、BOX、PHOX等,可以和很多金属形成络合物催化许多类型的反应[(a)D.Rechavi,M.Lemaire,Chem.Rev.2002,102,346;(b)G.Desimoni,G.Faita,P.Quadrelli,Chem.Rev.2003,103,3119.]。因此,基于噁唑啉砌块构建不同的手性配体骨架引起了化学工作者的广泛兴趣,也由此实现了一系列高效的不对称催化转化,推动了不对称催化领域的发展[(a)S.Zhu,X.Song,Y.Li,Y.Cai,Q.Zhou,J.Am.Chem.Soc.2010,132,16374;(b)Y.Zhang,F.Wang,W.Zhang,J.Org.Chem.2007,72,9208;(c)B.Cheng,W.Liu,Z.Lu,J.Am.Chem.Soc.2018,140,501;(d)J.Guo,B.Cheng,X.Shen,Z.Lu,J.Am.Chem.Soc.2017,139,15316.]。
有机硼化合物是合成化学中最重要的中间体之一,可以转化为几乎所有类型的官能团化合物[(a)Eur.J.Org.Chem.2008,2013;(b)Chem.Rev.2011,111,1417;(c)Chem.Eur.J.2011,17,13124.]。烯烃不对称硼氢化反应是最为常见和高效的制备手性硼化合物的方法,通过进一步的衍生化反应能够转化为几乎所有类型的手性官能团化合物。
因此,提供一种能够催化简单烯烃的不对称硼氢化反应和炔烃的立体选择性硼氢化反应的催化剂具有重要的意义和巨大的应用价值。
发明内容
为了克服上述所指出的现有技术的缺陷,本发明人对此进行了深入研究,在付出了大量创造性劳动后,从而完成了本发明。
具体而言,本发明所要解决的技术问题是:提供吡啶-酰胺-噁唑啉配体、其合成方法及其金属配合物和用途,以提供能够通过简单的合成线路实现高合成产率的催化剂,并确保其对烯烃不对称硼氢化反应中具有非常高的催化活性。
为解决上述技术问题,本发明的技术方案是:
第一方面,本发明提供了吡啶-酰胺-噁唑啉配体,其为式(1)所述的化合物
或者为式(1)所述化合物的对映体或消旋体,其中,
R1和R2分别独立为C1~C10的烃基、苄基、苯基或取代的苯基、杂芳基中的一种。
其中,所述的烃基为甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、环戊基、正己基、环己基等。
本发明中,作为一种优选的技术方案,R1优选为甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、苯基或苄基中的一种。
本发明中,作为一种优选的技术方案,R2优选为取代的苯基,取代的苯基中取代基为C1~C6的烃基、烃氧基以及卤素,取代基数量为1-5。
第二方面,本发明提供了上述吡啶-酰胺-噁唑啉配体的合成方法,包括如下步骤:
第一步:惰性气氛下,6-溴-2-吡啶甲酸(A)和草酰氯在催化量的N,N-二甲基甲酰胺作用下在溶剂中反应一段时间后生成相应的6-溴-2-吡啶甲酰氯;随后,6-溴-2-吡啶甲酰氯和胺(B)在四氢呋喃溶剂中回流反应一段时间后得到中间体6-溴-2-吡啶酰胺(C);
第二步:惰性气氛下,在溶剂中,中间体6-溴-2-吡啶酰胺(C)和手性噁唑啉(D)在叔丁醇锂、催化量的醋酸钯和1,2-双(二苯膦)乙烷的作用下,经过偶联反应一定时间得到吡啶-酰胺-噁唑啉配体(1)。
本发明中,作为作为一种优选的技术方案,第一步中的溶剂为二氯甲烷。
本发明中,作为作为一种优选的技术方案,第二步中的溶剂为二氧六环。
其合成路线如下:
第三方面,本发明提供了二苯胺-膦-噁唑啉金属配合物,该配合物是由化合物1与元素周期表的过渡金属形成,且具有如式(2)所述的通式
其中,M为过渡金属Fe、Co、Ni、Cu、Ag、Au、Ru、Rh、Pd、Os、Ir中的一种;
X选自卤化物(F、Cl、Br、I)、拟卤化物(氰化物、氰酸、盐、异氰酸盐)、羧酸、磺酸、膦酸的阴离子(碳酸根、甲酸根、乙酸根、丙酸根、甲基磺酸根、三氯甲基磺酸根、苯基磺酸根、甲苯磺酸根)中的任意一种;
E为H或烃基;
n1为X的个数,为0、1、2、3;
n2为E的个数,为0或1。
如上所述的,R1和R2分别为C1~C10的烃基、苄基、苯基或取代的苯基(取代基为C1~C6的烃基、烃氧基以及卤代烃基,取代基数量为1-5)、杂芳基中的一种。
其中,所述的烃基为甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、环戊基、正己基、环己基等。
本发明中,作为一种优选的技术方案,R1优选为甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、苯基或苄基中的一种。
本发明中,作为一种优选的技术方案,R2优选为取代的苯基,取代的苯基中取代基为C1~C6的烃基、烃氧基以及卤素,取代基数量为1-5。
第四方面,本发明提供了二苯胺-膦-噁唑啉配体以及二苯胺-膦-噁唑啉金属配合物的用途,是指利用催化量的至少一种二苯胺-膦-噁唑啉配体或二苯胺-膦-噁唑啉金属配合物作为催化剂通过催化反应制备光学选择性有机化合物。
采用了上述技术方案后,本发明的有益效果是:
本发明提供了一种新型吡啶-酰胺-噁唑啉配体,吡啶-酰胺-噁唑啉配体可以独立用于制备手性或非手性有机化合物,也可以与过渡金属Fe、Co、Ni、Cu、Ag、Au、Ru、Rh、Pd、Os、Ir形成稳定的金属配合物,该金属配合物能够应用于不对称催化反应,特别是对烯烃不对称硼氢化反应中具有非常高的催化活性。本发明还提供了高效的合成路线,两步总产率均在80%以上。即:本发明涉及的吡啶-酰胺-噁唑啉配体,能够与铁、钴和铜等地球丰产过渡金属盐形成稳定的配合物,进而催化简单烯烃的不对称硼氢化反应和炔烃的立体选择性硼氢化反应,制备高附加值的手性硼酯和烯基硼酯等化合物,在天然产物全合成、药物化学和精细化工等领域具有巨大的应用价值。
本发明还提供了化合物1应用于金属催化不对称反应的用途,通过与金属预配位形成的金属催化剂或与金属盐现场生成金属催化剂,化合物1可以用于制备手性或非手性有机化合物。可根据本发明制备的手性或非手性有机化合物是活性物质或用于制备该物质的中间物,特别是在香料和增香剂、药物制剂、农用化学品的生产方面。
具体实施方式
下面结合具体的实施例对本发明进一步说明。但这些例举性实施方式的用途和目的仅用来例举本发明,并非对本发明的实际保护范围构成任何形式的任何限定,更非将本发明的保护范围局限于此。
吡啶-酰胺-噁唑啉配体,其为式(1)所述的化合物
或者为式(1)所述化合物的对映体或消旋体,其中,
R1和R2分别独立为C1~C10的烃基、苄基、苯基或取代的苯基、1-萘基、2-萘基中的一种。
实施例1
吡啶-酰胺-噁唑啉配体(1a),其结构式为:
该化合物采用如下方法制备得到:
第一步:室温,惰性气氛下,反应瓶中依次加入6-溴-2-吡啶甲酸(A)(20mmol),干燥二氯甲烷(DCM)(40mL),N,N-二甲基甲酰胺(DMF)(1mL),然后反应瓶转移至0℃反应浴中,滴加草酰氯[(COCl)2](40mmol),滴加完毕后转移至室温继续反应3小时,反应结束后减压旋干溶剂得到黄色固体(6-溴-2-吡啶甲酰氯)。随后,黄色固体溶解于150mL四氢呋喃中,加入2,6-二异丙基苯胺(B1)(22mmol),0℃下滴加三乙胺(50mmol),滴加完毕后继续0℃搅拌15分钟,恢复到室温后升温至回流,反应5小时后冷却到室温,硅胶过滤,减压旋转蒸发除去溶剂,柱层析分离得到中间体C1。
白色固体,产率为92%,检测结果如下:
1H NMR:(399.9MHz,CDCl3)δ9.15(br,1H),[8.27(d,J=7.6Hz,0.4H),8.24(d,J=7.6Hz,0.6H)],[7.89(dd,J=7.8,7.6Hz,0.6H),7.78(dd,J=7.8,7.6Hz,0.4H)],[7.70(d,J=7.8Hz,0.4H),7.55(d,J=7.8Hz,0.6H)],7.37-7.31(m,1H),7.25-7.20(m,2H),3.15-3.04(m,2H),1.22(d,J=6.8Hz,12H).
第二步:室温,惰性气氛下,反应瓶中加入C(10mmol),干燥二氧六环(50mL),醋酸钯[Pd(OAc)2](0.25mmol),1,2-双(二苯膦)乙烷(dppe)(0.30mmol),叔丁醇锂(LiOtBu)(30mmol),(S)-4-异丙基-噁唑啉(D1)(10mmol),然后升温回流反应12小时,冷却至室温,硅胶过滤,减压旋转蒸发除去溶剂,柱层析分离得到产物。
棕黄色固体,产率为95%,检测结果如下:
1H NMR:(399.9MHz,CDCl3)δ9.76(br,1H),8.41(dd,J=7.8,0.8Hz,1H),8.22(dd,J=8.0,0.8Hz,1H),8.00(dd,J=8.0,7.8Hz,1H),7.36-7.29(m,1H),7.25-7.19(m,2H),4.54(dd,J=9.2,8.0Hz,1H),4.25(dd,J=8.2,8.0Hz,1H),4.23-4.15(m,1H),3.20-3.08(m,2H),1.97-1.86(m,1H),1.22(d,J=3.2Hz,6H),1.21(d,J=3.2Hz,6H),1.07(d,J=6.8Hz,3H),0.98(d,J=6.8Hz,3H);13C NMR:(125.8MHz,CDCl3)δ163.2,162.5,149.3,146.5,145.1,138.0,137.3,131.8,129.2,128.3,128.4,126.51,126.47,124.2,123.0,73.7,68.5,41.6,28.9,,23.6,19.9.HRMS Calcd for[C24H31N3O2+H]+:394.2489;found:394.2487.
实施例2
吡啶-酰胺-噁唑啉配体(1b),其结构式为:
该化合物的制备方法与实施例1基本相同,区别在于:
第二步中,所用手性噁唑啉的为(S)-4-苄基-噁唑啉(D2)。
最终产物1b为棕黄色固体,产率为92%,检测结果如下:
1H NMR:(399.9MHz,CDCl3)δ9.74(s,1H),8.42(d,J=7.8Hz,1H),8.21(d,J=8.0Hz,1H),8.00(dd,J=8.0,7.8Hz,1H),7.37-7.19(m,8H),4.75-4.65(m,1H),4.49(dd,J=9.2,9.0Hz,1H),4.26(dd,J=8.2,8.0Hz,1H),3.25(dd,J=13.8,5.8Hz,1H),3.21-3.08(m,2H),2.84(dd,J=13.8,8.4Hz,1H),1.22(d,J=3.6Hz,6H),1.21(d,J=3.6Hz,6H);13CNMR:(125.8MHz,CDCl3)δ163.0,162.7,149.9,146.2,145.4,138.2,137.6,131.2,129.2,128.6,128.2,126.6,126.5,124.5,123.4,72.5,68.1,41.6,28.9,23.65,23.63.HRMSCalcd for[C28H31N3O2+H]+:442.2489;found:442.2485.
实施例3
吡啶-酰胺-噁唑啉配体(1c),其结构式为:
该化合物的制备方法与实施例1基本相同,区别在于:
第二步中,所用手性噁唑啉的为(R)-4-乙基-噁唑啉(D3)。
最终产物1c为棕黄色固体,产率为94%,检测结果如下:
1HNMR:(399.9MHz,CDCl3)δ9.74(s,1H),8.41(dd,J=7.8,0.8Hz,1H),8.22(dd,J=7.8,0.8Hz,1H),8.00(dd,J=8.0,7.8Hz,1H),7.36-7.30(m,1H),7.25-7.20(m,2H),4.60(dd,J=9.6,,8.4Hz,1H),4.40-4.30(m,1H),4.17(dd,J=8.2,8.0Hz,1H),3.20-3.09(m,2H),1.88-1.77(m,1H),1.74-1.63(m,1H),1.22(d,J=1.4Hz,6H),1.20(d,J=1.4Hz,6H),1.05(t,J=7.4Hz,3H);13C NMR:(125.8MHz,CDCl3)δ163.0,162.2,149.8,146.2,145.6,138.1,131.1,129.0,128.2,126.5,125.3,124.4,123.4,72.8,68.3,28.9,28.5,23.7,23.6,10.0.HRMS Calcd for[C23H29N3O2+H]+:380.2333;found:380.2332.
实施例4
吡啶-酰胺-噁唑啉配体(1d),其结构式为:
该化合物的制备方法与实施例1基本相同,区别在于:
第二步中,所用手性噁唑啉的为(S)-4-甲基-噁唑啉(D4)。
最终产物1d为棕黄色固体,产率为90%,检测结果如下:
1HNMR:(399.9MHz,CDCl3)δ9.68(s,1H),8.42(dd,J=7.8,0.8Hz,1H),8.22(dd,J=8.0,0.8Hz,1H),8.00(dd,J=8.0,7.8Hz,1H),7.36-7.30(m,1H),7.25-7.20(m,2H),4.64(dd,J=9.4,8.2Hz,1H),4.55-4.44(m,1H),4.08(dd,J=8.2,8.0Hz,1H),3.20-3.08(m,2H),1.43(d,J=6.6Hz,3H),1.21(d,J=6.8Hz,12H);13C NMR:(125.8MHz,CDCl3)δ163.0,162.2,149.8,146.2,145.6,138.2,131.1,128.2,126.5,124.4,123.4,74.6,62.4,28.9,23.7,23.7,21.3.HRMS Calcd for[C22H27N3O2+H]+:366.2176;found:366.2177.
实施例5
吡啶-酰胺-噁唑啉配体(1e),其结构式为:
该化合物的制备方法与实施例1基本相同,区别在于:
第二步中,所用手性噁唑啉的为(S)-4-叔丁基-噁唑啉(D5)。
最终产物1e为棕黄色固体,产率为93%,检测结果如下:
白色固体,产率为90%。1H NMR:(399.9MHz,CDCl3)δ9.80(br,1H),8.40(dd,J=7.8,1.0Hz,1H),8.23(dd,J=8.0,1.0Hz,1H),8.00(dd,J=8.0,7.8Hz,1H),7.36-7.29(m,1H),7.25-7.19(m,2H),4.48(dd,J=10.2,8.8Hz,1H),4.34(dd,J=8.8,8.4Hz,1H),4.16(dd,J=10.2,8.4Hz,1H),3.21-3.09(m,2H),1.22(dd,J=6.7,5.6Hz,2H),0.99(s,9H);13CNMR:(125.8MHz,CDCl3)δ162.9,162.0,149.8,146.1,145.6,138.1,131.2,128.1,126.5,124.2,123.4,76.4,69.4,34.0,28.9,25.9,23.6.HRMS Calcd for[C25H33N3O2+Na]+:430.2465;found:430.2472.
实施例6
吡啶-酰胺-噁唑啉配体(1f),其结构式为:
该化合物的制备方法与实施例1基本相同,区别在于:
第二步中,所用手性噁唑啉的为4,4-二甲基-噁唑啉(D6)。
最终产物1f为棕黄色固体,产率为93%,检测结果如下:
1H NMR:(399.9MHz,CDCl3)δ9.64(br,1H),8.40(dd,J=7.8,1.0Hz,1H),8.23(dd,J=8.0,1.0Hz,1H),7.99(dd,J=8.0,7.8Hz,1H),7.33(dd,J=7.8,7.6Hz,1H),7.25-7.19(m,2H),4.22(s,2H),3.20-3.09(m,2H),1.44(s,6H),1.21(d,J=7.0Hz,12H);13C NMR:(125.8MHz,CDCl3)δ163.0,160.8,149.8,146.3,145.8,138.1,131.2,128.2,126.6,124.4,123.4,79.7,68.1,28.9,28.3,23.7;HRMS Calcd for[C23H29N3O2+H]+:380.2333;found:380.2331.
实施例7
吡啶-酰胺-噁唑啉-铁配合物的合成
室温,氮气氛下,反应瓶内依次加入1a(1mmol),干燥四氢呋喃(THF)(5mL)和氯化亚铁(FeCl2)(0.95mmol),反应液逐渐变紫色悬浊液,搅拌反应5小时后抽滤,滤饼用乙醚洗涤三次(每次5mL),收集滤饼,油泵抽干得到紫色粉末状固体(2a),产率为88%。
Anal.Calcd for C24H31Cl2FeN3O2:C,55.41;H,6.01;N,8.08;Found C,55.32;H,6.11;N,8.00.
实施例8
吡啶-酰胺-噁唑啉-钴配合物的合成
室温,氮气氛下,反应瓶内依次加入1a(1mmol),干燥四氢呋喃(THF)(5mL)和氯化钴(CoCl2)(0.95mmol),反应液逐渐变蓝绿色悬浊液,搅拌反应5小时后抽滤,滤饼用乙醚洗涤三次(每次5mL),收集滤饼,油泵抽干得到浅蓝色粉末状固体(2b),产率为96%。
Anal.Calcd for C24H31Cl2CoN3O2:C,55.08;H,5.97;N,8.03;Found C,54.88;H,6.11;N,7.72.
实施例9
吡啶-酰胺-噁唑啉-铜配合物的合成
室温,氮气氛下,反应瓶内依次加入1a(1mmol),干燥四氢呋喃(THF)(5mL)和氯化铜(CuCl2)(0.95mmol),反应液逐渐变黄绿色悬浊液,搅拌反应5小时后抽滤,滤饼用乙醚洗涤三次(每次5mL),收集滤饼,油泵抽干得到黄色粉末状固体(2c),产率为98%。
Anal.Calcd for C24H31Cl2CuN3O2:C,54.60;H,5.92;N,7.96;Found C,54.22;H,6.01;N,7.55.
实施例10
吡啶-酰胺-噁唑啉-锰配合物的合成
室温,氮气氛下,反应瓶内依次加入1a(1mmol),干燥四氢呋喃(THF)(5mL)和氯化锰(MnCl2)(0.95mmol),反应液逐渐变浅黄色悬浊液,搅拌反应5小时后抽滤,滤饼用乙醚洗涤三次(每次5mL),收集滤饼,油泵抽干得到黄白色粉末状固体(2d),产率为94%。
Anal.Calcd for C24H31Cl2CuN3O2:C,55.50;H,6.02;N,8.09;Found C,54.18;H,6.21;N,7.87.
实施例11
吡啶-酰胺-噁唑啉-锌配合物的合成
室温,氮气氛下,反应瓶内依次加入1a(1mmol),干燥四氢呋喃(THF)(5mL)和氯化锰(MnCl2)(0.95mmol),反应液逐渐变白色悬浊液,搅拌反应5小时后抽滤,滤饼用乙醚洗涤三次(每次5mL),收集滤饼,油泵抽干得到白色粉末状固体(2e),产率为85%。
Anal.Calcd for C24H31Cl2CuN3O2:C,54.41;H,5.90;N,7.93;Found C,54.12;H,6.00;N,5.82.
实施例12
(手性)吡啶-酰胺-噁唑啉-FeCl2配合物催化1,2-二取代烯烃的不对称硼氢化反应
室温,氮气氛下,在一干燥的反应试管中加入(手性)吡啶-酰胺-噁唑啉-FeCl2配合物(2a)(0.005mmol),烯烃(0.5mmol),频那醇硼烷(HBpin)(0.5mmol),干燥四氢呋喃(1mL),注射入三乙基硼氢化钠溶液(0.010mmol),然后在室温下搅拌1小时后柱层析分离得到硼氢化产物,产率为97%。
无色油状液体,98%ee,[α]20 D=-25.3。1H NMR(400MHz,CDCl3)δ7.15(d,J=8.8Hz,2H),6.80(d,J=8.8Hz,2H,),3.81(s,3H),2.17(t,J=7.8Hz,1H),1.90-1.78(m,1H),1.69-1.57(m,1H),1.22(s,6H),1.20(s,6H),0.90(t,J=7.3Hz,3H);13C NMR(126MHz,CDCl3)δ157.2,135.3,129.2,113.6,83.1,55.2,33.1,26.0,24.7,24.6,13.9;11B NMR(96MHz,CDCl3)δ32.3.
实施例13
氯化亚铁催化1,2-二取代烯烃的不对称硼氢化反应(对比实施例)
室温,氮气氛下,在一干燥的反应试管中氯化亚铁(FeCl2)(0.005mmol),烯烃(0.5mmol),频那醇硼烷(HBpin)(0.5mmol),干燥四氢呋喃(1mL),注射入三乙基硼氢化钠溶液(0.010mmol),然后在室温下搅拌1小时。反应结束后经气相-质谱监测未发现产物。
实施例14
(手性)吡啶-酰胺-噁唑啉-CoCl2配合物催化单取代烯烃的马氏不对称硼氢化反应
室温,氮气氛下,在一干燥的反应试管中加入(手性)吡啶-酰胺-噁唑啉-CoCl2配合物(2b)(0.005mmol),烯烃(0.5mmol),频那醇硼烷(HBpin)(0.5mmol),干燥甲苯(1mL),注射入三乙基硼氢化钠溶液(0.010mmol),然后在室温下搅拌10分钟后柱层析分离得到硼氢化产物,产率为99%。
无色油状液体,97%ee,[α]20 D=+16.7。1H NMR(400MHz,CDCl3)δ7.15(d,J=8.5Hz,2H),6.83(d,J=8.5Hz,2H),3.79(s,3H),2.38(q,J=7.5Hz,1H),1.31(d,J=7.5Hz,3H),1.22(s,6H),1.21(s,6H);13C NMR(126MHz,CDCl3)δ157.2,137.0,128.6,113.7,83.2,55.2,24.62,24.59,17.4;11B NMR(96MHz,CDCl3)δ32.8.
实施例15
氯化钴催化单取代烯烃的马氏不对称硼氢化反应(对比实施例)
室温,氮气氛下,在一干燥的反应试管中加入氯化钴(CoCl2)(0.005mmol),烯烃(0.5mmol),频那醇硼烷(HBpin)(0.5mmol),干燥甲苯(1mL),注射入三乙基硼氢化钠溶液(0.010mmol),然后在室温下搅拌1小时。反应结束后经气相-质谱监测未发现产物。
实施例16
(手性)吡啶-酰胺-噁唑啉-CuCl2配合物催化炔烃的立体选择性硼氢化反应
室温,氮气氛下,在一干燥的反应试管中加入(手性)吡啶-酰胺-噁唑啉-CuCl2配合物(2c)(0.005mmol),炔烃(0.5mmol),联硼酸频那醇酯(B2pin2)(0.75mmol),甲醇(MeOH)(10equiv.),四氢呋喃(1mL)和叔丁醇钠(0.025mmol),然后在室温下搅拌反应2小时后柱层析分离得到立体选择性硼氢化产物(E式),产率为92%。
无色油状液体。1HNMR(400MHz,CDCl3)δ7.76(d,J=18.0Hz,1H),7.28(d,J=8.0Hz,2H),6.62(d,J=8.0Hz,2H),6.34(d,J=18.0Hz,1H),3.23(s,3H),1.14(s,12H);13C NMR(126MHz,CDCl3)δ160.7,145.1,130.8,128.7,116.0,114.2,83.0,54.6,24.8;11B NMR(96MHz,CDCl3)δ30.9.
实施例17
氯化铜催化炔烃的立体选择性硼氢化反应(对比实施例)
室温,氮气氛下,在一干燥的反应试管中加入氯化铜(CuCl2)(0.005mmol),炔烃(0.5mmol),联硼酸频那醇酯(B2pin2)(0.75mmol),甲醇(MeOH)(10equiv.),四氢呋喃(1mL)和叔丁醇钠(0.025mmol),然后在室温下搅拌反应2小时。反应结束后经气相-质谱监测产物小于10%。
应当理解,这些实施例的用途仅用于说明本发明而非意欲限制本发明的保护范围。此外,也应理解,在阅读了本发明的技术内容之后,本领域技术人员可以对本发明作各种改动、修改和/或变型,所有的这些等价形式同样落于本申请所附权利要求书所限定的保护范围之内。
Claims (10)
1.吡啶-酰胺-噁唑啉配体,其特征在于:其为式(1)所述的化合物
或者为式(1)所述化合物的对映体或消旋体,其中,
R1和R2分别独立为C1~C10的烃基、苄基、苯基或取代的苯基、杂芳基中的一种。
2.如权利要求1所述的吡啶-酰胺-噁唑啉配体,其特征在于:R1为甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、苯基或苄基中的一种。
3.如权利要求2所述的吡啶-酰胺-噁唑啉配体,其特征在于:R2为取代的苯基,取代的苯基中的取代基为C1~C6的烃基、烃氧基以及卤素,取代基数量为1-5。
4.吡啶-酰胺-噁唑啉配体的合成方法,其特征在于:包括如下步骤:
第一步:惰性气氛下,6-溴-2-吡啶甲酸和草酰氯在催化量的N,N-二甲基甲酰胺作用下在溶剂中反应一段时间后生成相应的6-溴-2-吡啶甲酰氯;随后,6-溴-2-吡啶甲酰氯和胺在四氢呋喃溶剂中回流反应一段时间后得到中间体6-溴-2-吡啶酰胺;
第二步:惰性气氛下,在溶剂中,中间体6-溴-2-吡啶酰胺和手性噁唑啉在叔丁醇锂、催化量的醋酸钯和1,2-双(二苯膦)乙烷的作用下,经过偶联反应一定时间得到吡啶-酰胺-噁唑啉配体。
5.如权利要求4所述的吡啶-酰胺-噁唑啉配体的合成方法,其特征在于:第一步中的溶剂为二氯甲烷。
6.如权利要求4所述的吡啶-酰胺-噁唑啉配体的合成方法,其特征在于:第二步中的溶剂为二氧六环。
7.二苯胺-膦-噁唑啉金属配合物,其特征在于:该配合物是由权利要求1-3任一项所述的二苯胺-膦-噁唑啉配体与元素周期表的过渡族的过渡金属形成,且具有如式(2)所述的通式
其中,M为过渡金属Fe、Co、Ni、Cu、Ag、Au、Ru、Rh、Pd、Os、Ir中的一种;
X选自卤化物、拟卤化物、羧酸、磺酸、膦酸的阴离子中的任意一种;
E为H或烃基;
n1为X的个数,为0、1、2、3;
n2为E的个数,为0或1。
8.如权利要求7所述的二苯胺-膦-噁唑啉金属配合物,其特征在于:R1为甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、苯基或芳基中的一种。
9.如权利要求7所述的二苯胺-膦-噁唑啉金属配合物,其特征在于:R2优选为取代的苯基,取代的苯基中取代基为C1~C6的烃基、烃氧基以及卤代烃基,取代基数量为1-5。
10.二苯胺-膦-噁唑啉配体以及二苯胺-膦-噁唑啉金属配合物的用途,其特征在于:利用催化量的至少一种二苯胺-膦-噁唑啉配体或二苯胺-膦-噁唑啉金属配合物作为催化剂通过催化反应制备光学选择性有机化合物。
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