CN115594701A - Preparation method of allyl-substituted aryl borate organic boron compound - Google Patents
Preparation method of allyl-substituted aryl borate organic boron compound Download PDFInfo
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- CN115594701A CN115594701A CN202211050393.8A CN202211050393A CN115594701A CN 115594701 A CN115594701 A CN 115594701A CN 202211050393 A CN202211050393 A CN 202211050393A CN 115594701 A CN115594701 A CN 115594701A
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- allyl
- substituted
- bipyridine
- nickel
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- 150000001639 boron compounds Chemical class 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 16
- -1 aryl boron Chemical compound 0.000 claims abstract description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 4
- 238000005859 coupling reaction Methods 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 31
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 15
- 239000003446 ligand Substances 0.000 claims description 9
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 6
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 4
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims description 4
- 239000002841 Lewis acid Substances 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 150000007517 lewis acids Chemical class 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 239000003638 chemical reducing agent Substances 0.000 claims description 3
- OCMNCWNTDDVHFK-UHFFFAOYSA-L dichloronickel;1,2-dimethoxyethane Chemical compound Cl[Ni]Cl.COCCOC OCMNCWNTDDVHFK-UHFFFAOYSA-L 0.000 claims description 3
- UQPSGBZICXWIAG-UHFFFAOYSA-L nickel(2+);dibromide;trihydrate Chemical compound O.O.O.Br[Ni]Br UQPSGBZICXWIAG-UHFFFAOYSA-L 0.000 claims description 3
- JRTIUDXYIUKIIE-KZUMESAESA-N (1z,5z)-cycloocta-1,5-diene;nickel Chemical compound [Ni].C\1C\C=C/CC\C=C/1.C\1C\C=C/CC\C=C/1 JRTIUDXYIUKIIE-KZUMESAESA-N 0.000 claims description 2
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 claims description 2
- JFJNVIPVOCESGZ-UHFFFAOYSA-N 2,3-dipyridin-2-ylpyridine Chemical compound N1=CC=CC=C1C1=CC=CN=C1C1=CC=CC=N1 JFJNVIPVOCESGZ-UHFFFAOYSA-N 0.000 claims description 2
- NPAXPTHCUCUHPT-UHFFFAOYSA-N 3,4,7,8-tetramethyl-1,10-phenanthroline Chemical compound CC1=CN=C2C3=NC=C(C)C(C)=C3C=CC2=C1C NPAXPTHCUCUHPT-UHFFFAOYSA-N 0.000 claims description 2
- JIVLDFFWTQYGSR-UHFFFAOYSA-N 4,7-dimethyl-[1,10]phenanthroline Chemical compound C1=CC2=C(C)C=CN=C2C2=C1C(C)=CC=N2 JIVLDFFWTQYGSR-UHFFFAOYSA-N 0.000 claims description 2
- DHDHJYNTEFLIHY-UHFFFAOYSA-N 4,7-diphenyl-1,10-phenanthroline Chemical compound C1=CC=CC=C1C1=CC=NC2=C1C=CC1=C(C=3C=CC=CC=3)C=CN=C21 DHDHJYNTEFLIHY-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910021617 Indium monochloride Inorganic materials 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 2
- CUTSCJHLMGPBEJ-UHFFFAOYSA-N [N].CN(C)C=O Chemical compound [N].CN(C)C=O CUTSCJHLMGPBEJ-UHFFFAOYSA-N 0.000 claims description 2
- ZFCODINDSKDSBA-UHFFFAOYSA-N [N].CNC(C)=O Chemical group [N].CNC(C)=O ZFCODINDSKDSBA-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- KZPXREABEBSAQM-UHFFFAOYSA-N cyclopenta-1,3-diene;nickel(2+) Chemical compound [Ni+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KZPXREABEBSAQM-UHFFFAOYSA-N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 claims description 2
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 claims description 2
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 2
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 2
- DBJLJFTWODWSOF-UHFFFAOYSA-L nickel(ii) fluoride Chemical compound F[Ni]F DBJLJFTWODWSOF-UHFFFAOYSA-L 0.000 claims description 2
- BFSQJYRFLQUZKX-UHFFFAOYSA-L nickel(ii) iodide Chemical compound I[Ni]I BFSQJYRFLQUZKX-UHFFFAOYSA-L 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims 2
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 claims 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims 2
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 claims 1
- TXNLQUKVUJITMX-UHFFFAOYSA-N 4-tert-butyl-2-(4-tert-butylpyridin-2-yl)pyridine Chemical compound CC(C)(C)C1=CC=NC(C=2N=CC=C(C=2)C(C)(C)C)=C1 TXNLQUKVUJITMX-UHFFFAOYSA-N 0.000 claims 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims 1
- 239000004411 aluminium Substances 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- 239000004327 boric acid Substances 0.000 claims 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims 1
- 239000000843 powder Substances 0.000 claims 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 claims 1
- 229910052796 boron Inorganic materials 0.000 abstract description 19
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 14
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 abstract description 10
- 239000000758 substrate Substances 0.000 abstract description 4
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 229910052759 nickel Inorganic materials 0.000 abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 24
- 239000000741 silica gel Substances 0.000 description 24
- 229910002027 silica gel Inorganic materials 0.000 description 24
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 15
- 239000011734 sodium Substances 0.000 description 15
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 239000012300 argon atmosphere Substances 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 12
- 238000001514 detection method Methods 0.000 description 12
- 239000003480 eluent Substances 0.000 description 12
- 238000001914 filtration Methods 0.000 description 12
- 238000010898 silica gel chromatography Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 11
- 238000001035 drying Methods 0.000 description 11
- 238000010791 quenching Methods 0.000 description 11
- 230000000171 quenching effect Effects 0.000 description 11
- 239000007788 liquid Substances 0.000 description 9
- 238000001179 sorption measurement Methods 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 6
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 5
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 125000003107 substituted aryl group Chemical group 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000975 bioactive effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229930014626 natural product Natural products 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 150000001499 aryl bromides Chemical class 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- IMEVSAIFJKKDAP-UHFFFAOYSA-N 4-methoxy-2-(4-methoxypyridin-2-yl)pyridine Chemical compound COC1=CC=NC(C=2N=CC=C(OC)C=2)=C1 IMEVSAIFJKKDAP-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 101100391174 Dictyostelium discoideum forC gene Proteins 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 description 1
- DIKMWTRJIZQJMY-UHFFFAOYSA-N Racemisches Echinulin Natural products N1C(=O)C(C)NC(=O)C1CC1=C(C(C)(C)C=C)NC2=C(CC=C(C)C)C=C(CC=C(C)C)C=C12 DIKMWTRJIZQJMY-UHFFFAOYSA-N 0.000 description 1
- OXMGUTQVUIWQEK-UHFFFAOYSA-N [N].CC(=O)N(C)C Chemical group [N].CC(=O)N(C)C OXMGUTQVUIWQEK-UHFFFAOYSA-N 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 238000005937 allylation reaction Methods 0.000 description 1
- 125000000746 allylic group Chemical group 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- RRSIMIHTHWYRRA-UHFFFAOYSA-L dibromonickel;1-methoxy-2-(2-methoxyethoxy)ethane Chemical compound Br[Ni]Br.COCCOCCOC RRSIMIHTHWYRRA-UHFFFAOYSA-L 0.000 description 1
- KDJHHFWQUAOVNB-UHFFFAOYSA-L dichloronickel tricyclohexylphosphane Chemical compound Cl[Ni]Cl.C1CCC(CC1)P(C1CCCCC1)C1CCCCC1 KDJHHFWQUAOVNB-UHFFFAOYSA-L 0.000 description 1
- MJFCDPLEATUOPF-UHFFFAOYSA-L dichloronickel;triphenylphosphane Chemical compound Cl[Ni]Cl.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 MJFCDPLEATUOPF-UHFFFAOYSA-L 0.000 description 1
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- DIKMWTRJIZQJMY-NTKDMRAZSA-N echinulin Chemical compound N1C(=O)[C@@H](C)NC(=O)[C@H]1CC1=C(C(C)(C)C=C)NC2=C(CC=C(C)C)C=C(CC=C(C)C)C=C12 DIKMWTRJIZQJMY-NTKDMRAZSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000007832 transition metal-catalyzed coupling reaction Methods 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
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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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
The invention discloses a preparation method of an allyl substituted organic boron compound. The method takes trifluoromethanesulfonic acid-substituted aryl boron reagent as a raw material, and generates an organic aryl boron reagent with allyl functional groups in the structure through a coupling reaction with allyl alcohol under the catalysis of nickel. The method has the advantages of mild reaction conditions, simple and easily obtained raw materials, wide substrate applicability, good compatibility of reaction functional groups and the like.
Description
Technical Field
The invention relates to a preparation method of an organic compound, in particular to a preparation method of an organic boron compound of allyl substituted aryl borate.
Background
The functionalization reaction of natural products containing allyl has important function in organic synthesis, is an important method for constructing carbon-carbon bond and carbon heteroatom bond, and is widely applied to medicine synthesis. For example, the bioactive molecule Echinulin (org. Lett.,2017,19, 5928.) contains an important allylic fragment, and thus cannot be allylated for the synthesis of many bioactive molecules and natural products containing allylated fragments. Organoboron compounds are not only important components of polymers, materials, chemical sensors, and bioactive molecules, but are also favored synthetic building blocks. Therefore, the efficient synthesis and transformation of organoboron compounds is a direction of research that is always receiving attention in the fields of synthetic chemistry, material chemistry, and even pharmaceutical industry.
The allyl substituted aryl boron reagent has the dual characteristics of allyl and organic boron reagents, and has important application prospect in the material field and the organic synthesis field. However, allyl-substituted arylboron compounds have been reported so far. At present, the most widely used method for synthesizing allyl-substituted aryl organoboron reagents is a method of performing a formatting reaction on aryl bromide and then reacting the aryl bromide with an allyl reagent or a borate (Angew. Chem. Int. Ed.2005,44,3133, tetrahedron Lett.,2016,57,3441; etc.), and the method has the disadvantages of high reaction condition requirement, large substrate limitation and unsuitability for synthesizing functional organoboron compounds containing hydroxyl, amino, aldehyde and the like. In addition, the instability of the grignard reagent itself causes great inconvenience to the preparation and storage of the raw material. Therefore, researchers have turned their attention to transition metal catalysis, where transition metal-catalyzed coupling reactions are an important method for synthesizing allyl-substituted organosilicon reagents, and great progress has been made in recent years. (adv. Synth. 2020,362,5622.) however, such methods have relatively high reaction conditions, the required alkenyl bromide needs to be prepared by alkyne or allyl alcohol, in addition, the substrate is greatly limited, and the selectivity is difficult to control, which restricts the application of the method in the synthesis of allyl substituted aryl boron reagents.
Disclosure of Invention
The present invention provides a process for preparing allyl-substituted arylboron reagents that overcomes the deficiencies of the prior art.
The invention relates to an allyl-substituted aryl boron reagent, which is an allyl-substituted aryl borate organic boron compound shown as III in a formula (1), wherein the reaction formula of the method for preparing the allyl-substituted aryl boron reagent is shown in the formula (1), namely triflate-substituted aryl borate shown as I is taken as a raw material, manganese powder, zinc powder, magnesium powder or aluminum powder is taken as a reducing agent, organic bipyridine is taken as a ligand, lewis is taken as a ligand under the catalysis of nickel, and
organic boric esterification of acid as additive and II allyl alcohol in organic solvent under protection of inert gas to produce allyl substituted aryl borateCompound III, standard conditions in formula (1) mean a reaction temperature of-10 ℃ to 100 ℃, wherein: the organic solvent is any one of nitrogen methyl acetamide (DMA), nitrogen dimethyl formamide (DMF), dimethyl sulfoxide (DMSO), diethanol dimethyl ether (DME) or N-methylpyrrolidone (NMP), and the organic solvent is shown in the formula: r is 1 、R 2 、R 3 The same or different; r 1 Is any one of indole, pyridine, carbazole, methyl, phenyl, or substituted alkyl or aryl; r is 2 、R 3 Is hydrogen or methyl; bpin is a pinacol-protected boronate ester.
Preferably, the catalyst used in the reaction of the preparation method of the allyl-substituted aryl borate organic boron compound provided by the invention is any one of nickel chloride, nickel bromide, nickel iodide, nickel fluoride, nickelocene, nickel carbonate, tricyclohexylphosphine nickel chloride, triphenylphosphine nickel chloride, dimethoxyethane nickel chloride, nickel (1, 1' -bis (diphenylphosphine) ferrocene) chloride, bis- (1, 5-cyclooctadiene) nickel, diethylene glycol dimethyl ether nickel bromide or ethylene glycol dimethyl ether nickel (II) chloride.
Preferably, the first and second electrodes are formed of a metal, in the preparation method of the allyl-substituted aryl borate organic boron compound, the ligand aza ligand is 2,2 '-bipyridyl, 6' -dimethyl-2, 2 '-bipyridyl, 5' -dimethyl-2, 2-bipyridyl, 5 '-dicarboxyl-2, 2-bipyridyl, 4' -dimethyl-2, 2 '-bipyridyl, or a mixture thereof any of 4,4' -dimethoxy-2, 2 '-bipyridine, 4' -di-tert-butyl-2, 2 '-bipyridine, 4' -diphenyl-2, 2 '-bipyridine, 2' -biquinoline, 1, 10-phenanthroline, 4, 7-diphenyl-1, 10-phenanthroline, 4, 7-dimethyl-1, 10-phenanthroline, 3,4,7, 8-tetramethyl-1, 10-phenanthroline, or terpyridine.
Preferably, the Lewis acid used in the reaction in the preparation method of the allyl-substituted aryl borate organic boron compound is AlCl 3 、MgBr 2 、ZnCl 2 、BiBr 3 、InCl 3 、Mn(OTf) 3 、Cu(OTf) 2 、Ca(OTf) 2 、Sc(OTf) 3 、Ho(OTf) 3 、In(OTf) 3 Or Ha (OTf) 4 Any one of the above.
Preferably, in any one of the methods for preparing allyl-substituted arylboronic acid ester organoboron compounds described in the present invention, the compound i is a triflate-substituted arylboronic acid ester.
Preferably, in the method for preparing the allyl-substituted aryl borate organic boron compound, the triflate-substituted aryl borate is any one of 1a, 1b or 1c in formula 2
The compound II is any one of the compounds shown in the formula 3.
Preferably, in the preparation method of the allyl-substituted aryl borate organoboron compound, the catalyst used is nickel bromide.
Preferably, in the preparation method of the allyl-substituted aryl borate organoboron compound, the reducing agent is manganese powder.
Preferably, in the method for preparing the allyl substituted aryl borate organoboron compound of the present invention, the solvent is nitrogen Dimethylacetamide (DMA).
Preferably, in the preparation method of the allyl-substituted aryl borate organoboron compound, the Lewis acid is AlCl 3 。
Preferably, in the preparation method of the allyl substituted aryl borate organic boron compound, the ligand aza ligand is 2,2' -bipyridyl.
Preferably, the preparation method of the allyl-substituted aryl borate organic boron compound provided by the invention has a molar ratio of the compound of formula I to allyl alcohol electrophilic reagent of 1.5.
More preferably, the reaction temperature in the preparation method of the allyl-substituted aryl borate organic boron compound is 30 ℃.
The preparation of the allyl-substituted aryl boron compound is realized by taking allyl alcohol as an allylation reagent and taking trifluoromethanesulfonate-substituted aryl borate as a raw material through a reduction coupling method. On the other hand, allyl alcohol is used as a compound with abundant structures in natural products, the raw materials are cheap and easy to obtain, and the allyl alcohol is a relatively environment-friendly coupling reagent. However, due to the compatibility problem of the active functional group containing the triflate and the borate and the extremely high dissociation energy problem of the allyl alcohol, the substrate activity matching and selectivity are still very challenging.
Drawings
FIG. 1, FIG. 2, and FIG. 3 are nuclear magnetic H spectrum, nuclear magnetic C spectrum, and nuclear magnetic B spectrum of 2- (3-cinnamyl phenyl) -4, 5-tetramethyl-1, 3, 2-dioxaborane, respectively.
Detailed Description
Example 1
standard conditions: the reaction was carried out in a glove box under argon atmosphere. Sequentially adding NiBr into the reaction tube 2 (4.4mg, 0.02mmol), manganese powder (33.4mg, 0.6mmol), 2-bipyridine (3.1mg, 0.02mmol), alCl 3 (2.7mg, 0.02mmol), then 1a (105.6mg, 0.3mmol) and 2a (26.8mg, 0.2mmol) were added and 1mL of DMA solution was added to the reaction tube by syringe. After stirring for 24h at room temperature, quenching with water, extracting with ethyl acetate, drying with anhydrous sodium sulfate, filtering, concentrating, and performing silica gel column chromatography (200-300 mesh silica gel) to obtain the target product 3a. (Note: the alkenylboron compound was readily decomposed by adsorption on a silica gel column, loss was large, and separation was carried out rapidly with an appropriate eluent.) (pale yellow oily liquid, 52.5mg, yield 82%).
The product detection data were as follows:
1 H NMR(400MHz,CDCl 3 ):δ7.69-7.67(m,2H),7.36-7.32(m,4H),7.30-7.26(m,2H),7.21-7.17(m,1H),6.45(d,J＝16.0Hz,1H),6.39-6.31(m,1H),3.55(d,J＝6.4Hz,2H),1.34(s,12H)。 13 C NMR(100MHz,CDCl 3 ):δ139.6,137.7,135.1,132.8,131.8,131.0,129.5,128.6,128.1,127.2,126.3,83.9,39.5,25.0.[not:the carbon attached to boron was not observed because ofquadrupole broadening caused by the 11B nucleus]。 11 B NMR(128MHz,CDCl 3 ):δ30.03。IR(neat,cm -1 ):3417,2954,1599,1470,1415,1247,1107,839,759,723。GC-MS(EI)calcd for C 21 H 25 BO 2 320.19,found:320.20.
example 2
standard conditions: the reaction was carried out in a glove box under argon atmosphere. Sequentially adding NiBr into the reaction tube 2 (4.4mg, 0.02mmol), manganese powder (33.4mg, 0.6mmol), 2-bipyridine (3.1mg, 0.02mmol), alCl 3 (2.7mg, 0.02mmol) followed by 1a (105.6mg, 0.3mmol) and 2b (29.6mg, 0.2mmol) was added and 1mL of DMA solution was added to the reaction tube using a syringe. After stirring for 24h at room temperature, quenching with water, extracting with ethyl acetate, drying with anhydrous sodium sulfate, filtering, concentrating, and performing silica gel column chromatography (200-300 mesh silica gel) to obtain the target product 3b. (Note: organoboron compound was easily adsorbed and decomposed in silica gel column, loss was large, and separation was carried out rapidly with an appropriate eluent.) (pale yellow oily liquid, 56.1mg, yield 84%).
The product detection data were as follows:
1 H NMR(400MHz,CDCl 3 ):δ7.68-7.66(m,2H),7.35-7.31(m,2H),7.24(d,J＝8.4Hz,2H),7.09(d,J＝8.0Hz,2H),6.41(d,J＝15.6Hz,1H),6.33-6.25(m,1H),3.54(d,J＝6.8Hz,2H),2.31(s,3H),1.34(s,12H)。 13 C NMR(100MHz,CDCl 3 ):δ139.7,136.9,135.1,134.9,132.8,131.8,130.9,129.3,128.5,128.1,126.2,83.9,39.5,25.0.21.3.[not:the carbon attached to boron was not observed because of quadrupole broadening caused by the 11 B nucleus]。 11 B NMR(128MHz,CDCl 3 ):δ30.03。IR(neat,cm -1 ):2977,1610,1514,1398,1361,1272,1143,1089,964,860,659。GC-MS(EI)calcd for C 22 H 27 BO 2 334.21,found:334.20.
example 3
standard conditions: the reaction was carried out in a glove box under argon atmosphere. Sequentially adding NiBr into the reaction tube 2 (4.4mg, 0.02mmol), manganese powder (33.4mg, 0.6mmol), 2-bipyridine (3.1mg, 0.02mmol), alCl 3 (2.7mg, 0.02mmol), then 1a (105.6mg, 0.3mmol) and 2c (32.8mg, 0.2mmol) were added and 1mL of DMA solution was added to the reaction tube using a syringe. After stirring for 24h at room temperature, quenching with water, extracting with ethyl acetate, drying with anhydrous sodium sulfate, filtering, concentrating, and performing silica gel column chromatography (200-300 mesh silica gel) to obtain the target product 3c. (Note: organoboron Compound is easily decomposed by adsorption on a silica gel column with a large loss, and is rapidly separated with an appropriate eluent.) (pale yellow oily liquid, 61.6mg, yield 88%).
The product detection data were as follows:
1 H NMR(400MHz,CDCl 3 ):δ7.68-7.66(m,2H),7.34-7.24(m,4H),6.83-6.81(m,2H),6.36(d,J＝16.0Hz,1H),6.24-6.17(m,1H),3.78(s,3H),3.53(d,J＝6.8Hz,2H),1.34(s,12H)。 13 C NMR(100MHz,CDCl 3 ):δ159.0,139.9,135.1,132.8,131.8,130.5,130.4,128.1,127.4,114.0,83.9,55.4,39.5,25.0.[not:the carbon attached to boron was not observedbecause ofquadrupole broadening caused by the 11 B nucleus]。 11 B NMR(128MHz,CDCl 3 ):δ29.80。IR(neat,cm -1 ):3415,2954,1600,1488,1445,1249,1107,1039,839,752。HRMS(ESI):[M+Na] + calcd for C 22 H 27 BO 3 Na 373.1945,found:373.1949.
example 4
standard conditions: the reaction was carried out in a glove box under argon atmosphere. Sequentially adding NiBr into the reaction tube 2 (4.4mg, 0.02mmol), manganese powder (33.4mg, 0.6mmol), 2-bipyridine (3.1mg, 0.02mmol), alCl 3 (2.7mg, 0.02mmol), then 1a (105.6mg, 0.3mmol) and 2d (26.8mg, 0.2mmol) were added and 1mL of DMA solution was added to the reaction tube using a syringe. After stirring for 24h at room temperature, quenching with water, extracting with ethyl acetate, drying with anhydrous sodium sulfate, filtering, concentrating, and performing silica gel column chromatography (200-300 mesh silica gel) to obtain the target product 3d. (Note: organoboron Compound is easily decomposed by adsorption on silica gel column with a large loss, and is rapidly separated with an appropriate eluent.) (pale yellow oily liquid, 49.9mg, yield 78%).
The product detection data were as follows:
1 H NMR(400MHz,CDCl 3 ):δ7.70(s,1H),7.64(d,J＝6.8Hz 1H),7.43(d,J＝8.0Hz,2H),7.32-7.22(m,5H),5.48(s,1H),4.97(s,1H),3.83(s,2H),1.34(d,J＝0.8Hz,12H)。 13 C NMR(100MHz,CDCl 3 ):δ147.1,141.1,138.7,135.6,132.8,132.0,128.4,127.9,127.5,126.3,114.8,83.9,41.6,25.0.[not:the carbon attached to boron was not observed because of quadrupole broadening caused by the 11 B nucleus]。 11 B NMR(128MHz,CDCl 3 ):δ30.04。IR(neat,cm -1 ):2976,1610,1398,1361,1274,1145,1089,962,860,750。GC-MS(EI)calcd for C 21 H 25 BO 2 320.19,found:320.20.
example 5
standard conditions: the reaction was carried out in a glove box under argon atmosphere. Sequentially adding NiBr into the reaction tube 2 (4.4mg, 0.02mmol), manganese powder (33.4mg, 0.6mmol), 2-bipyridine (3.1mg, 0.02mmol), alCl 3 (2.7mg, 0.02mmol) and then 1a (105.6mg, 0.3mmol) and 2e (38.8mg, 0.2m)mol), 1mL of DMA solution was added to the reaction tube with a syringe. After stirring for 24h at room temperature, quenching with water, extracting with ethyl acetate, drying with anhydrous sodium sulfate, filtering, concentrating, and performing silica gel column chromatography (200-300 mesh silica gel) to obtain the target product 3e. (Note: organoboron compound was easily adsorbed and decomposed in silica gel column, loss was large, and separation was carried out rapidly with an appropriate eluent.) (pale yellow oily liquid, 60.0mg, yield 79%).
The product detection data were as follows:
1 H NMR(400MHz,CDCl 3 ):δ7.69-7.67(m,2H),7.36-7.25(m,2H),6.91-6.87(m,2H),6.79(d,J＝8.4Hz,1H),6.38(d,J＝15.6Hz,1H),6.25-6.18(m,1H),3.87(4.0Hz,6H),3.54(d,J＝6.8Hz,2H),1.34(s,12H)。 13 C NMR(100MHz,CDCl 3 ):δ149.1,148.5,139.8,135.1,132.8,131.8,130.8,130.6,128.1,127.7,119.3,111.3,108.8,83.9,56.1,55.9,39.5,25.0.[not:the carbon attached to boron was not observed because of quadrupole broadening caused by the 11 B nucleus]。 11 B NMR(128MHz,CDCl 3 ):δ29.99。IR(neat,cm -1 ):3523,3442,2954,1601,1512,1247,1172,1109,966,837。HRMS(ESI):[M+Na] + calcd for C 23 H 29 BO 4 Na 403.2051,found:403.2055
example 6
standard conditions: the reaction was carried out in a glove box under argon atmosphere. Sequentially adding NiBr into the reaction tube 2 4.4mg,0.02mmol, manganese powder (33.4 mg,0.6 mmol), 2-bipyridine (3.1mg, 0.02mmol), alCl 3 (2.7mg, 0.02mmol) followed by 1a (105.6mg, 0.3mmol) and 2f (30.4mg, 0.2mmol) was added and 1mL of DMA solution was added to the reaction tube using a syringe. After stirring for 24h at room temperature, quenching with water, extracting with ethyl acetate, drying with anhydrous sodium sulfate, filtering, concentrating, and performing silica gel column chromatography (200-300 mesh silica gel) to obtain the target product 3f. (Note: organoboron Compound is easily decomposed by adsorption in silica gel columnThe losses are large and the separation is rapid with a suitable eluent. ) (pale yellow oily liquid, 44.0mg, yield 65%).
The product detection data were as follows:
1 H NMR(400MHz,CDCl 3 ):δ7.68-7.67(m,2H),7.33-7.28(m,4H),6.99-6.95(m,2H),6.40(d,J＝16.0Hz,1H),6.30-6.22(m,1H),3.54(d,J＝6.8Hz,2H),1.35(s,12H)。 13 C NMR(100MHz,CDCl 3 ):δ139.5,135.1,133.8(d,J C-F ＝12Hz),132.9,131.8,129.9,129.3(d,J C-F ＝8Hz),128.1,127.7(d,J C-F ＝8Hz),115.6115.4,84.0,39.5,25.0[not:the carbon attached to boron was not observed because ofquadrupole broadening caused by the 11 B nucleus]。 11 B NMR(128MHz,CDCl 3 ):δ29.82。IR(neat,cm -1 ):3527,2954,1687,1600,1512,1247,1106,1037,835,748。GC-MS(EI)calcd for C 21 H 24 BFO 2 338.18,found:338.19.
example 7
standard conditions: the reaction was carried out in a glove box under argon atmosphere. Sequentially adding NiBr into the reaction tube 2 (4.4mg, 0.02mmol), manganese powder (33.4mg, 0.6mmol), 2-bipyridine (3.1mg, 0.02mmol), alCl 3 (2.7mg, 0.02mmol) followed by 1a (105.6mg, 0.3mmol) and 2g (33.4mg, 0.2mmol) were added and 1mL of DMA solution was added to the reaction tube using a syringe. After stirring for 24h at room temperature, quenching with water, extracting with ethyl acetate, drying with anhydrous sodium sulfate, filtering, concentrating, and performing silica gel column chromatography (200-300 mesh silica gel) to obtain 3g of the target product. (Note: organoboron Compound is easily decomposed by adsorption on a silica gel column with a large loss, and is rapidly separated with an appropriate eluent.) (pale yellow oily liquid, 50.3mg, yield 71%).
The product detection data were as follows:
1 H NMR(400MHz,CDCl 3 ):δ7.69-7.68(m,2H),7.33-7.31(m,2H),7.27-7.22(m,4H),6.38(d,J＝15.6Hz,1H),6.35-6.28(m,1H),3.53(d,J＝5.6Hz,2H),1.34(s,12H)。 13 C NMR(100MHz,CDCl 3 ):δ139.3,136.2,135.1,132.9,132.7,131.8,130.3,129.8,128.7,128.1,127.5,83.9,39.5,25.0.[not:the carbon attached to boron was not observed because ofquadrupole broadening caused by the 11 B nucleus]。 11 B NMR(128MHz,CDCl 3 ):δ29.86。IR(neat,cm -1 ):3556,3415,2858,1620,1425,1276,1107,968,846,750。GC-MS(EI)calcd for C 21 H 24 BClO 2 354.15,found:354.16.
example 8
standard conditions: the reaction was carried out in a glove box under argon atmosphere. Sequentially adding NiBr into the reaction tube 2 (4.4mg, 0.02mmol), manganese powder (33.4mg, 0.6mmol), 2-bipyridine (3.1mg, 0.02mmol), alCl 3 (2.7mg, 0.02mmol) followed by 1a (105.6mg, 0.3mmol) and 2h (35.4mg, 0.2mmol) were added and 1mL of DMA solution was added to the reaction tube using a syringe. After stirring for 24h at room temperature, quenching with water, extracting with ethyl acetate, drying with anhydrous sodium sulfate, filtering, concentrating, and performing silica gel column chromatography (200-300 mesh silica gel) to obtain the target product for 3h. (Note: organoboron Compound is easily decomposed by adsorption on silica gel column with a large loss, and is rapidly separated with an appropriate eluent.) (pale yellow solid 46-48 ℃ C., 50.9mg, yield 76%).
The product detection data were as follows:
1 H NMR(600MHz,CDCl 3 ):δ7.68-7.65(m,2H),7.35-7.34(m,1H),7.32-7.29(m,1H),7.25-7.24(m,2H),6.67-6.66(m,2H),6.37(d,J＝15.6Hz,1H),6.16-6.12(m,1H),3.52(d,J＝7.2Hz,2H),2.93(s,6H),1.34(s,12H)。 13 C NMR(150MHz,CDCl 3 ):δ149.9,140.3,135.1,132.7,131.8,130.9,128.0,127.2,126.4,125.3,112.7,83.9,40.8,39.6,25.0.[not:the carbon attached to boron was not observed because of quadrupole broadening causedby the 11 B nucleus]。 11 B NMR(128MHz,CDCl 3 ):δ30.25。IR(neat,cm -1 ):3631,3529,3445,2954.1687,1600,1512,1247,837,750。HRMS(ESI):[M+Na] + calcd forC 23 H 30 BNO 2 Na 386.2262,found:386.2266
example 9
standard conditions: the reaction was carried out in a glove box under argon atmosphere. Sequentially adding NiBr into the reaction tube 2 4.4mg,0.02mmol, manganese powder (33.4 mg,0.6 mmol), 2-bipyridine (3.1mg, 0.02mmol), alCl 3 (2.7mg, 0.02mmol), then 1a (105.6mg, 0.3mmol) and 2i (24.8mg, 0.2mmol) were added, and 1mL of DMA solution was added to the reaction tube by syringe. After stirring for 24h at room temperature, quenching with water, extracting with ethyl acetate, drying with anhydrous sodium sulfate, filtering, concentrating, and performing silica gel column chromatography (200-300 mesh silica gel) to obtain the target product 3i. (Note: organoboron Compound is easily decomposed by adsorption on silica gel column with a large loss, and is rapidly separated with an appropriate eluent.) (pale yellow oily liquid, 48.4mg, yield 78%).
The product detection data were as follows:
1 H NMR(400MHz,CDCl 3 ):δ7.68-7.67(m,2H),7.35-7.29(m,3H),6.35-6.28(m,2H),6.21(d,J＝15.6Hz,1H),6.15-6.14(m,1H),3.52(d,J＝6.8Hz,2H),1.34(s,12H)。 13 C NMR(100MHz,CDCl 3 ):δ153.2,141.5,139.3,135.2,132.9,131.8,128.6,128.1,119.7,111.2,106.7,83.9,39.2,25.0.[not:the carbon attached to boron was not observed because ofquadrupole broadening caused by the 11 B nucleus]。 11 B NMR(128MHz,CDCl 3 ):δ29.98。IR(neat,cm -1 ):3556,3411,1618,1359,1276,1145,968,865,750。HRMS(ESI):[M+Na] + calcd for C 19 H 23 BO 3 Na 333.1632,found:333.1635.
example 10
standard conditions: the reaction was carried out in a glove box under argon atmosphere. Sequentially adding NiBr into the reaction tube 2 4.4mg,0.02mmol, manganese powder (33.4 mg,0.6 mmol), 2-bipyridine (3.1mg, 0.02mmol), alCl 3 (2.7mg, 0.02mmol), then 1a (105.6mg, 0.3mmol) and 2j (27.1mg, 0.2mmol) were added and 1mL of DMA solution was added to the reaction tube using a syringe. After stirring for 24h at room temperature, quenching with water, extracting with ethyl acetate, drying with anhydrous sodium sulfate, filtering, concentrating, and performing silica gel column chromatography (200-300 mesh silica gel) to obtain the target product 3j. (Note: organoboron compound was easily adsorbed and decomposed in silica gel column, loss was large, and separation was carried out rapidly with an appropriate eluent.) (pale yellow oily liquid, 39.8mg, yield 62%).
The product detection data were as follows:
1 H NMR(600MHz,CDCl 3 ):δ8.56(d,J＝2.4Hz,1H),8.42(d,J＝5.4Hz 1H),7.69-7.63(m,3H),7.34-7.33(m,2H),7.21-7.18(m,1H),6.43-6.41(m,2H),3.57(d,J＝6.2Hz,2H),1.35(s,12H)。 13 C NMR(150MHz,CDCl 3 ):δ148.2,138.9,135.1,133.2,133.0,132.7,132.0,131.8,128.2,127.5,123.5,83.9,39.5,25.0.[not:the carbon attached to boron was not observed because of quadrupole broadening caused by the 11 B nucleus]。 11 B NMR(128MHz,CDCl 3 ):δ30.09。IR(neat,cm -1 ):3529,3442,3346,2954,1678,1600,1359,1247,839,754。HRMS(ESI):[M+Na] + calcd for C 20 H 24 BNO 2 Na 344.1792,found:344.1796.
example 11
standard conditions: the reaction was carried out in a glove box under argon atmosphere. Sequentially adding NiBr into the reaction tube 2 (4.4mg, 0.02mmol), manganese powder (33.4mg, 0.6mmol), 2-bipyridine (3.1mg, 0.02mmol), alCl 3 (2.7mg, 0.02mmol) followed by 1a (105.6mg, 0.3mmol) and 2k (34.6mg, 0.2mmol) was added and 1mL of DMA solution was added to the reaction tube using a syringe. After stirring for 24h at room temperature, quenching with water, extracting with ethyl acetate, drying with anhydrous sodium sulfate, filtering, concentrating, and performing silica gel column chromatography (200-300 mesh silica gel) to obtain the target product 3k. (Note: organoboron Compound is easily decomposed by adsorption on a silica gel column with a large loss and is rapidly separated with an appropriate eluent.) (pale yellow solid mp:101-103 ℃,43.8mg, yield 61%).
The product detection data were as follows:
1 H NMR(600MHz,CDCl 3 ):δ8.07(s,1H),7.72(s,1H),7.67(d,J＝7.2Hz,1H),7.57(s,1H),7.37(d,J＝7.2Hz,1H),7.33-7.30(m,1H),7.24(s,2H),7.10(t,J＝2.4Hz,1H),6.55(d,J＝15.6Hz,1H),6.48(t,J＝2.4Hz,1H),6.30-6.25(m,1H),3.56(d,J＝7.2Hz,2H),1.33(s,12H)。 13 C NMR(150MHz,CDCl 3 ):δ140.2,135.3,135.1,132.6,132.0,131.8,129.7,128.1,128.0,126.5,124.6,120.5,118.8,111.1,102.8,83.9,39.5,24.9.[not:the carbon attached to boron was not observed because ofquadrupole broadening caused by the 11 B nucleus]。 11 B NMR(128MHz,CDCl 3 ):δ30.29。IR(neat,cm -1 ):3552,3415,2981,1608,1512,1359,1276,1143,964,750。HRMS(ESI):[M+Na] + calcd for C 23 H 26 BNO 2 Na 382.1949,found:382.1951。
example 12
standard conditions: the reaction was carried out in a glove box under argon atmosphere. Sequentially adding NiBr into the reaction tube 2 (4.4mg, 0.02mmol), manganese powder (33.4mg, 0.6mmol), 2-bipyridine (3.1mg, 0.02mmol), alCl 3 (2.7 mg, 0.02mmol), 1a (105.6 mg,0.3 mmol) and 2l (50.2mg, 0.2mmol) were then added, and 1mL of DMA solution was added to the reaction tube by syringe. After stirring the reaction at room temperature for 24h, quenched with water, extracted with ethyl acetate, anhydrous sulfurDrying sodium, filtering, concentrating, and performing silica gel column chromatography (200-300 mesh silica gel) to obtain 3l of a target product. (Note: organoboron compound is easily decomposed by adsorption on silica gel column with a large loss, and is rapidly separated by using an appropriate eluent.) (yellow solid, mp: 62.9mg at 135-137 ℃ C., yield 72%).
The product detection data were as follows:
1 H NMR(600MHz,CDCl 3 ):δ8.07-8.05(s,2H),7.75(s,1H),7.70-7.69(m,1H),7.48(d,J＝9.0Hz,1H),7.43-7.39(m,2H),7.35-7.32(m,2H),7.26(d,J＝9.0Hz,1H),7.20-7.18(m,1H),6.62(d,J＝15.6Hz,1H),6.39-6.34(m,1H),4.27(dd,J＝7.2Hz,14.4Hz,2H),3.60(d,J＝6.6Hz,2H),1.37-1.35(m,3H),1.33(s,12H)。 13 C NMR(150MHz,CDCl 3 ):δ140.4,140.1,139.4,135.2,132.7,131.9,131.7,128.9,128.1,126.7,125.7,124.2,123.2,123.1,120.5,118.9,118.3,108.6,108.5,83.9,39.7,37.6,25.0,13.9.[not:the carbon attached to boron was not observed because ofquadrupole broadening caused by the 11 B nucleus]。 11 B NMR(128MHz,CDCl 3 ):δ29.98。IR(neat,cm -1 ):3529,3442,2981,1658,1602,1425,1358,1247,1143,914,748。HRMS(ESI):[M+Na] + calcd for C 29 H 32 BNO 2 Na 460.2418,found:460.2421。
although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments described above, or equivalents may be substituted for elements thereof. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A process for preparing allyl-substituted arylboronic acid esters as shown in III features that the aryl boronic acid ester as shown in I is used as raw material, the manganese powder, zinc powder, magnesium powder or aluminium powder as reducer and the organic bipyridine as ligand under the catalysis of Ni
In the method, lewis acid is used as an additive, and the additive and II-shown allyl alcohol are subjected to coupling reaction in an organic solvent under the protection of inert gas to generate an allyl-substituted aryl borate organic boron compound III, wherein the reaction temperature is-10-100 ℃, and the reaction temperature is as follows: the organic solvent is nitrogen methyl acetamide (DMA), the solvent is any one of nitrogen dimethyl formamide (DMF), dimethyl sulfoxide (DMSO), diethanol dimethyl ether (DME) or N-methyl pyrrolidone (NMP), and the formula is as follows: r 1 、R 2 、R 3 The same or different; r is 1 Is any one of indole, pyridine, carbazole, methyl, phenyl, or substituted alkyl or aryl; r is 2 、R 3 Is hydrogen or methyl; bpin is boric acid ester protected by pinacol.
2. The method for preparing an allyl-substituted organoborate compound of the aryl group or the aryl boronic acid ester of the allyl-substituted aryl boronic acid ester according to claim 1, wherein the catalyst used in the reaction is any one of nickel chloride, nickel bromide, nickel iodide, nickel fluoride, nickelocene, nickel carbonate, tricyclohexylphosphine, nickel chloride, triphenylphosphine, nickel chloride, dimethoxyethane, nickel chloride, (1, 1' -bis (diphenylphosphino) ferrocene) nickel chloride, bis- (1, 5-cyclooctadiene) nickel, diethylene glycol dimethyl ether, nickel bromide, or nickel (II) ethylene glycol dimethyl ether chloride.
3. The process for preparing an allyl-substituted organoborate compound of the aryl boronic ester type according to claim 2, wherein: the ligand aza ligand is 2,2 '-bipyridine, 6' -dimethyl-2, 2 '-bipyridine, 5' -dimethyl-2, 2-bipyridine, 5 '-dicarboxy-2, 2-bipyridine, 4' -dimethyl-2, 2 '-bipyridine, 4' -dimethoxy-2, 2 '-bipyridine any of 4,4' -di-t-butyl-2, 2 '-bipyridine, 4' -diphenyl-2, 2 '-bipyridine, 2' -biquinoline, 1, 10-phenanthroline, 4, 7-diphenyl-1, 10-phenanthroline, 4, 7-dimethyl-1, 10-phenanthroline, 3,4,7, 8-tetramethyl-1, 10-phenanthroline, or terpyridine.
4. The process for producing an allyl-substituted arylboronic acid ester organoboron compound according to claim 3, wherein: the Lewis acid used in the reaction is AlCl 3 、MgBr 2 、ZnCl 2 、BiBr 3 、InCl 3 、Mn(OTf) 3 、Cu(OTf) 2 、Ca(OTf) 2 、Sc(OTf) 3 、Ho(OTf) 3 、In(OTf) 3 Or Ha (OTf) 4 Any one of the above.
5. The process for preparing an organoboron compound of the allyl-substituted arylboronic acid ester type according to any one of claims 1 to 4, wherein the compound I is a trifluoromethanesulfonate-substituted arylboronic acid ester.
6. The process for preparing an organoboron allyl-substituted arylborate according to claim 5, wherein the trifluoromethanesulfonate-substituted arylborate is any one of 1a, 1b and 1c in formula 2
The compound II is any one of the formula 3.
7. The process for preparing an allyl-substituted organoboronate compound of claim 6.
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