CN115947646A - Method for photo-catalytic hydroxylation of aryl or heteroaryl halide - Google Patents
Method for photo-catalytic hydroxylation of aryl or heteroaryl halide Download PDFInfo
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- CN115947646A CN115947646A CN202211629206.1A CN202211629206A CN115947646A CN 115947646 A CN115947646 A CN 115947646A CN 202211629206 A CN202211629206 A CN 202211629206A CN 115947646 A CN115947646 A CN 115947646A
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- 238000000034 method Methods 0.000 title claims abstract description 32
- -1 heteroaryl halide Chemical class 0.000 title claims abstract description 28
- 238000005805 hydroxylation reaction Methods 0.000 title claims abstract description 18
- 230000033444 hydroxylation Effects 0.000 title claims abstract description 14
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 11
- 125000003118 aryl group Chemical group 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 145
- 150000001502 aryl halides Chemical class 0.000 claims abstract description 20
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims abstract description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011941 photocatalyst Substances 0.000 claims abstract description 13
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 12
- 150000001412 amines Chemical class 0.000 claims abstract description 10
- 229910000085 borane Inorganic materials 0.000 claims abstract description 10
- 239000007800 oxidant agent Substances 0.000 claims abstract description 10
- 150000001491 aromatic compounds Chemical class 0.000 claims abstract description 3
- 238000005286 illumination Methods 0.000 claims abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 116
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 30
- PRWATGACIORDEL-UHFFFAOYSA-N 2,4,5,6-tetra(carbazol-9-yl)benzene-1,3-dicarbonitrile Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=C(C#N)C(N2C3=CC=CC=C3C3=CC=CC=C32)=C(N2C3=CC=CC=C3C3=CC=CC=C32)C(N2C3=CC=CC=C3C3=CC=CC=C32)=C1C#N PRWATGACIORDEL-UHFFFAOYSA-N 0.000 claims description 29
- 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 description 29
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 28
- 229910052700 potassium Inorganic materials 0.000 claims description 28
- 239000011591 potassium Substances 0.000 claims description 28
- 125000005843 halogen group Chemical group 0.000 claims description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 125000001424 substituent group Chemical group 0.000 claims description 9
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 239000003446 ligand Substances 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- WVMHLYQJPRXKLC-UHFFFAOYSA-N borane;n,n-dimethylmethanamine Chemical compound B.CN(C)C WVMHLYQJPRXKLC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 229910052740 iodine Inorganic materials 0.000 claims description 6
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims description 5
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 5
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 5
- LVEYOSJUKRVCCF-UHFFFAOYSA-N 1,3-bis(diphenylphosphino)propane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCP(C=1C=CC=CC=1)C1=CC=CC=C1 LVEYOSJUKRVCCF-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 235000010290 biphenyl Nutrition 0.000 claims description 4
- 239000004305 biphenyl Substances 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 4
- 125000001072 heteroaryl group Chemical group 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000001624 naphthyl group Chemical group 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 125000004076 pyridyl group Chemical group 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- STTGYIUESPWXOW-UHFFFAOYSA-N 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline Chemical compound C=12C=CC3=C(C=4C=CC=CC=4)C=C(C)N=C3C2=NC(C)=CC=1C1=CC=CC=C1 STTGYIUESPWXOW-UHFFFAOYSA-N 0.000 claims description 2
- QHXLIQMGIGEHJP-UHFFFAOYSA-N boron;2-methylpyridine Chemical compound [B].CC1=CC=CC=N1 QHXLIQMGIGEHJP-UHFFFAOYSA-N 0.000 claims description 2
- VPEPQDBAIMZCGV-UHFFFAOYSA-N boron;5-ethyl-2-methylpyridine Chemical compound [B].CCC1=CC=C(C)N=C1 VPEPQDBAIMZCGV-UHFFFAOYSA-N 0.000 claims description 2
- VEWFZHAHZPVQES-UHFFFAOYSA-N boron;n,n-diethylethanamine Chemical compound [B].CCN(CC)CC VEWFZHAHZPVQES-UHFFFAOYSA-N 0.000 claims description 2
- NNTOJPXOCKCMKR-UHFFFAOYSA-N boron;pyridine Chemical compound [B].C1=CC=NC=C1 NNTOJPXOCKCMKR-UHFFFAOYSA-N 0.000 claims description 2
- 125000002541 furyl group Chemical group 0.000 claims description 2
- 125000002883 imidazolyl group Chemical group 0.000 claims description 2
- 125000001041 indolyl group Chemical group 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 125000005561 phenanthryl group Chemical group 0.000 claims description 2
- 125000004193 piperazinyl group Chemical group 0.000 claims description 2
- 125000000168 pyrrolyl group Chemical group 0.000 claims description 2
- 125000001544 thienyl group Chemical group 0.000 claims description 2
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 claims 2
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims 1
- IYRGXJIJGHOCFS-UHFFFAOYSA-N neocuproine Chemical compound C1=C(C)N=C2C3=NC(C)=CC=C3C=CC2=C1 IYRGXJIJGHOCFS-UHFFFAOYSA-N 0.000 claims 1
- 125000005842 heteroatom Chemical group 0.000 abstract description 12
- 239000000758 substrate Substances 0.000 abstract description 11
- 230000008901 benefit Effects 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 230000000640 hydroxylating effect Effects 0.000 abstract description 4
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000011160 research Methods 0.000 abstract description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 52
- 238000005481 NMR spectroscopy Methods 0.000 description 45
- 235000019439 ethyl acetate Nutrition 0.000 description 38
- 229910052786 argon Inorganic materials 0.000 description 26
- 239000011541 reaction mixture Substances 0.000 description 25
- 239000012300 argon atmosphere Substances 0.000 description 24
- 239000000243 solution Substances 0.000 description 24
- 238000003756 stirring Methods 0.000 description 24
- 239000000203 mixture Substances 0.000 description 21
- 239000012071 phase Substances 0.000 description 19
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 18
- 238000001035 drying Methods 0.000 description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 18
- 238000003818 flash chromatography Methods 0.000 description 18
- 239000007788 liquid Substances 0.000 description 18
- 239000012044 organic layer Substances 0.000 description 18
- 239000003208 petroleum Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 238000001816 cooling Methods 0.000 description 16
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 238000005695 dehalogenation reaction Methods 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 125000000000 cycloalkoxy group Chemical group 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 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
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 125000005493 quinolyl group Chemical group 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XSFVQEHUVOVFOW-UHFFFAOYSA-N 1,10-phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1.C1=CN=C2C3=NC=CC=C3C=CC2=C1 XSFVQEHUVOVFOW-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- OYNJAUIAADXAOW-UHFFFAOYSA-N 2,3,5,6-tetra(carbazol-9-yl)benzene-1,4-dicarbonitrile Chemical compound C1=CC=CC=2C3=CC=CC=C3N(C1=2)C1=C(C(=C(C(=C1C#N)N1C2=CC=CC=C2C=2C=CC=CC1=2)N1C2=CC=CC=C2C=2C=CC=CC1=2)C#N)N1C2=CC=CC=C2C=2C=CC=CC1=2 OYNJAUIAADXAOW-UHFFFAOYSA-N 0.000 description 1
- ZOMQCVKHGOMNER-UHFFFAOYSA-N 2,4,5,6-tetrakis(N-phenylanilino)benzene-1,3-dicarbonitrile Chemical compound C(#N)C1=C(C(=C(C(=C1N(C1=CC=CC=C1)C1=CC=CC=C1)N(C1=CC=CC=C1)C1=CC=CC=C1)N(C1=CC=CC=C1)C1=CC=CC=C1)C#N)N(C1=CC=CC=C1)C1=CC=CC=C1 ZOMQCVKHGOMNER-UHFFFAOYSA-N 0.000 description 1
- MWQIRPAXTNULID-UHFFFAOYSA-N 2,9-dimethyl-1,10-phenanthroline Chemical compound C1=C(C)N=C2C3=NC(C)=CC=C3C=CC2=C1.C1=C(C)N=C2C3=NC(C)=CC=C3C=CC2=C1 MWQIRPAXTNULID-UHFFFAOYSA-N 0.000 description 1
- QMXFUIUEGUOSEV-UHFFFAOYSA-N 3,4,5,6-tetra(carbazol-9-yl)benzene-1,2-dicarbonitrile Chemical compound N#Cc1c(C#N)c(c(c(c1-n1c2ccccc2c2ccccc12)-n1c2ccccc2c2ccccc12)-n1c2ccccc2c2ccccc12)-n1c2ccccc2c2ccccc12 QMXFUIUEGUOSEV-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 125000006416 CBr Chemical group BrC* 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001499 aryl bromides Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- UORVGPXVDQYIDP-BJUDXGSMSA-N borane Chemical group [10BH3] UORVGPXVDQYIDP-BJUDXGSMSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000002390 heteroarenes Chemical class 0.000 description 1
- 238000010505 homolytic fission reaction Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 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
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of organic synthesis, and particularly relates to a method for carrying out photocatalysis on aryl or heteroaryl halide hydroxylation. The method is a double-catalytic system method for hydroxylating aryl halide or heteroaryl halide by adopting the integral action of a photocatalyst, a stable and cheap amine borane reagent and a nickel catalyst, wherein the aryl halide or the heteroaryl halide reacts under the illumination condition in the presence of the photocatalyst, the amine borane reagent and the nickel catalyst to produce an intermediate; followed by reaction in the presence of an oxidizing agent to produce the corresponding hydroxylated aromatic compound or hydroxylated heteroarene compound. The invention establishes an environment-friendly (hetero) aryl halide hydroxylation catalytic system with good substrate applicability. The method has the advantages of simple operation, mild reaction conditions, cheap and easily-obtained raw materials, good substrate applicability, good yield, wide application prospect and wide research significance.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a method for carrying out photocatalysis on aryl or heteroaryl halide hydroxylation.
Background
Phenols, hydroxylated aromatics and their derivatives are important structural components of many drugs, materials, foods and natural products. Among the various preparation schemes of phenols and hydroxylated heteroarenes, the hydroxylation of (hetero) aryl halides has been widely recognized as one of the most valuable processes in industrial technology.
In recent years, the hydroxylation reaction of the photocatalytic (hetero) aromatic hydrocarbon halide (including chloride, bromide and iodide) has attracted more and more attention in the field of cross-coupling chemistry due to the advantages of environmental protection, mild reaction conditions, good universality and the like, and a photocatalytic (hetero) aryl halide hydroxylation reaction system also attracts more and more attention. In 2018, zhang and colleagues developed a photoredox mediated hydroxylation reaction of copper-catalyzed (hetero) aryl halides at room temperature using oxygen, and this transformation has the advantage of good functional group tolerance. The Cai's group in 2019 reported a light-induced hydroxylation reaction of organic halides by which a series of functionalized phenols and fatty alcohols could be obtained simply and efficiently, with a wider substrate range and good functional group tolerance, and without the need for the addition of strong bases, consisting in the addition of sodium iodide to increase the homolytic cleavage of the C-Br (Cl) bond, thus significantly increasing the hydroxylation activity of aryl bromides and chlorides. The traditional (hetero) aryl halide hydroxylation method needs to be realized by using a high-load noble metal or transition metal catalyst and a high-quality ligand, but the method generally has the problems of difficult removal of the catalyst and the ligand during post-treatment, poor substrate usability, harsh reaction conditions and the like, and limits the large-scale synthesis application of the catalyst and the ligand, so that a hydroxylation catalytic system with mild reaction conditions, good substrate applicability and environmental friendliness is urgently needed to be developed, and meanwhile, in view of that photocatalysis is an important field of organic synthesis and is an important means for hydroxylating (hetero) aryl halide, the development of a green and economic photocatalytic dehalogenation hydroxylation strategy with mild reaction conditions, wide substrate applicability and simple post-treatment is very necessary.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a method for hydroxylating aryl halide or heteroaryl halide by photocatalysis, which is a double-catalytic-system method for hydroxylating aryl halide or heteroaryl halide by using a photocatalyst, a stable and cheap amine borane reagent and a nickel catalyst as a whole.
The invention establishes an environment-friendly (hetero) aryl halide hydroxylation catalytic system with good substrate applicability. The method has the advantages of simple operation, mild reaction conditions, cheap and easily-obtained raw materials, good substrate applicability and good yield.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a method of photocatalytic aryl or heteroaryl halide hydroxylation comprising the steps of:
(1) In a solvent, reacting aryl halide or heteroaryl halide in the presence of a photocatalyst, an amine borane reagent and a nickel catalyst under the condition of illumination to produce an intermediate;
(2) The intermediate reacts in the presence of an oxidant to generate a corresponding hydroxylated aromatic compound or a hydroxylated heteroarene compound;
the reaction formula of the method is as follows:
wherein Ar is aryl or heteroaryl; aryl is selected from phenyl, biphenyl, naphthyl, fluorenyl and phenanthryl; heteroaryl is selected from pyridyl, furyl, thienyl, pyrrolyl, imidazolyl, indolyl, quinolyl, piperazinyl;
the R group is a substituent group, and the substituent group is at least one of H, hydroxyl, C1-C6 alkyl, C1-C6 alkoxy, halogen group (including at least one of F, cl, br and I), nitro or phenyl; more preferred halogen groups are at least one of F, cl, br; more preferred C1-C6 alkyl groups are at least one of 1C to 6C containing alkyl groups including, but not limited to, methyl, ethyl, propyl, butyl, t-butyl, cycloalkyl (cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl), and the like; more preferred C1-C6 alkoxy groups are at least one of 1C to 6C alkoxy groups, including but not limited to methoxy, ethoxy, propoxy, epoxy, cycloalkoxy, and the like;
x is a halogen group (including one of Cl, br and I), and more preferably, X is at least one of Br and Cl.
More preferably, in the reaction formula, ar is selected from phenyl, biphenyl, naphthyl, fluorenyl, pyridyl, quinolyl;
the R group is a substituent, the substituent is selected from at least one of H, hydroxyl, methyl, ethyl, propyl, tert-butyl, methoxy, halogen group, nitro or phenyl, and the halogen group is selected from at least one of F, cl, br and I;
x is one of Br and Cl.
Preferably, the molar ratio of the aryl halide or heteroaryl halide, the photocatalyst, the amine borane reagent and the nickel catalyst in the step (1) is 1: (0.01-1.0): (1.0-4.0): (0.01 to 1.0), more preferably 1:0.05:2:0.05.
preferably, the photocatalyst in the step (1) is at least one of a 4CzIPN photocatalyst and a derivative thereof, more preferably at least one of 4CzIPN, 4DPAIPN, 5CzBN, 3CzDMAPN, 4CzPN, and 4CzTPN, and the structure is as shown below, more preferably, the photocatalyst is 4CzIPN.
Preferably, the amine borane reagent in the step (1) is trimethylamine borane (CH) 3 ) 3 N-BH 3 Triethylamine borane (CH) 3 CH 2 ) 3 N-BH 3 Pyridine borane, 2-methylpyridine borane, 5-ethyl-2-methylpyridine borane, 3,5-dimethylpyridine borane, 3,5-diisopropylpyridine borane, and more preferably trimethylamine borane (CH) 3 ) 3 N-BH 3 。
Preferably, the nickel catalyst in the step (1) is NiCl 2 . 6H 2 O、NiCl 2 . DPPP、NiCl 2 . (PPh 3 ) 2 、Ni(CH 3 COO) 2 . 6H 2 O、NiCl 2 . At least one of DME, more preferably NiCl 2 . 6H 2 O。
Preferably, the N ligand of the nickel catalyst in the step (1) is at least one of 4,4 '-di-tert-butyl-2,2' -bipyridine (dtbbpy), bipyridine (bipyridine), 1,10-phenanthroline (1,10-phenanthroline), 2,9-dimethyl-1,10-phenanthroline (2,9-dimetyl-1,10-phenanthroline), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (24 zxft 3524-dimetyl-4,7-dienyl-1,10-phenanthroline), more preferably, the N ligand of the nickel catalyst is 4,4 '-di-tert-butyl-3282 zxft 3272' -bipyridine (dtbbpy), and the N ligand ratio of nickel catalyst is more preferably 5272-di-tert-butyl-7972: 2.
preferably, the solvent in the step (1) is at least one of N, N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), dimethylsulfoxide (DMSO), acetonitrile (MeCN), ethyl acetate (EtOAc), N-methylpyrrolidone (NMP), and more preferably, the solvent is N, N-dimethylacetamide (DMAc). More preferably, the solvent is used in an amount of 5 to 20mL/1mmol, more preferably 5mL/1mmol, based on the amount of (hetero) aryl halide substance.
Preferably, the light source of the lighting condition in step (1) is a CFL lamp, an LED lamp or an incandescent lamp, and more preferably, the light source is a blue LED lamp.
Preferably, the reaction temperature in the step (1) is 0 to 100 ℃, and more preferably, the temperature is 10 to 30 ℃.
Preferably, the reaction time in the step (1) is 3 to 80 hours, and more preferably, the reaction time is 18 to 36 hours.
Preferably, after the reaction in the step (1) is finished, directly adding an oxidant into a reaction system by a one-pot method, and directly converting an intermediate obtained by the reaction in the step (1) into a hydroxyl compound; alternatively, after the reaction in step (1) is completed, the reaction solution may be subjected to post-treatment purification steps such as extraction, concentration, column chromatography separation, etc., to purify the intermediate and then reacted with an oxidizing agent.
Preferably, the reaction in step (1) is carried out in an inert atmosphere, and more preferably, the addition process of the reactants, the reaction process, and the like are carried out in an inert atmosphere.
Preferably, the inert atmosphere is a gas which does not react with the reactant, the product and the reaction system, and specifically is a mixed gas of one or more of nitrogen, argon and helium.
Preferably, the oxidant in the step (2) is hydrogen peroxide (H) 2 O 2 ) At least potassium peroxymonosulfonate (Oxone)One, more preferred is potassium peroxymonosulfonate (Oxone).
Preferably, the molar ratio of (hetero) aryl halide to oxidant in step (2) is 1:5 to 10, more preferably 1:8.
preferably, a solvent is further added in the step (2), the solvent is a mixed solution of THF and a sulfuric acid solution, and THF and H are 2 SO 4 Solution volume ratio =1:3, where H 2 SO 4 The concentration of the solution is 1mol/L (providing an acidic environment) and the amount of the solvent is 20-40mL/1mmol, more preferably 35mL/1mmol, based on the amount of the (hetero) aryl halide substance.
Preferably, the reaction temperature in said step (2) is 20 to 60 ℃, more preferably 40 ℃.
Preferably, the reaction time in the step (2) is 3 to 20 hours, and more preferably, the reaction time is 10 hours.
Preferably, the reaction atmosphere in step (2) is an oxygen-containing atmosphere, including air.
Preferably, the step (2) comprises a post-treatment after the reaction is finished, and the post-treatment comprises the following operation steps: after the reaction is finished, extracting the reaction solution, concentrating an organic phase, and performing column chromatography to obtain a target product.
Preferably, the reaction formula of the method is as follows:
wherein R is a substituent group, and the substituent group is at least one of H, hydroxyl, C1-C6 alkyl, C1-C6 alkoxy, carboxyl, halogen group (F, cl, br, I), nitro or phenyl; more preferred halogen groups are at least one of F, cl, br; more preferred C1-C6 alkyl groups are at least one of 1C to 6C containing alkyl groups including, but not limited to, methyl, ethyl, propyl, butyl, t-butyl, cycloalkyl (cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl), and the like; more preferred C1-C6 alkoxy groups are at least one of alkoxy groups containing 1 to 6C atoms, including but not limited to methoxy, ethoxy, propoxy, epoxy, cycloalkoxy, and the like;
x is a halogen group (Cl, br, I), and more preferably X is at least one of Cl and Br.
Compared with the prior art, the invention has the beneficial effects that:
(1) The method has the advantages of simple, economical and easily-obtained reagent and substrate, simple reaction operation, mild condition and high reaction efficiency.
(2) The reaction system is a homogeneous phase catalytic system, and has the advantages of good substrate adaptability, wide substrate range and good selectivity on different halides.
(3) In the invention, the borane group can be converted into a hydroxyl group under the action of a double catalytic system, the selectivity is better, the amine boron group can be further functionalized after being introduced by dehalogenation, and the amine boron group is oxidized into the hydroxyl group under the action of an oxidant, so that dehalogenation hydroxylation is indirectly realized. The method disclosed by the invention has attraction to drug synthesis, realizes the acquisition of a target product by introducing boronized groups and then performing further functionalization, and has wide application prospect and research significance.
Detailed Description
The technical solutions of the present invention are further clearly and completely described below by using specific examples, and it should be understood that the described examples of the present invention are implemented on the premise of the technical solutions of the present invention, and detailed embodiments and specific operation procedures are given, but only a part of examples of the present invention is provided, and not all examples. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified, and materials, reagents and the like used in the examples are commercially available unless otherwise specified. In the following examples, e.q. represents equivalent, 1e.q. represents 1 equivalent, for example, 1 equivalent is 0.5mmol when 1e.q is 0.5mmol, and 2 equivalent is 2e.q, namely 1.0mmol, and so on, which will not be described in detail below.
Example 1
1a (1e.q.0.5mmol), 4CzIPN (5 mol%), (CH) 3 ) 3 N-BH 3 (2e.q.)、NiCl 2 . 6H 2 O (5 mol%), dtbbpy (10 mol%), molar ratio 1:0.05:2:0.05:0.1, add to a Schlenk reaction tube with a magnetic stir bar. The reaction vessel was evacuated and backfilled with argon 3 times, then DMAc (3.5 mL) was added under argon atmosphere, after which the schlenk tube was placed 2cm from the LED (20W) lamp and the reaction was stirred for 24h. After completion of the reaction, potassium peroxymonosulfonate Oxone (8.0 e.q.) and THF H were added directly to the reaction mixture 2 SO 4 (1ml: 3ml), reacting at 40 ℃ for about 10 hours, cooling to room temperature, adding 10mL of water into the reaction solution, extracting with 3x15mL of ethyl acetate, combining organic layers, drying, desolventizing, and separating the crude mixture by flash column chromatography (the mobile phase is petroleum ether/ethyl acetate, the dosage ratio is 4:1) to obtain the target product 1b, wherein the target product is colorless liquid and the yield is 85%. The post-processing operation steps of this embodiment are applicable to other embodiments.
The product obtained is 1 H NMR data are characterized as follows: 1 H NMR(400MHz,CDCl 3 )δ7.31(t,J＝7.9Hz,2H),7.02(t,J＝7.4Hz,1H),6.93(d,J＝8.4Hz,2H),5.76(s,1H).
based on the conditions of the above examples, the molar ratios of the (hetero) aryl halide, photocatalyst, amine borane reagent, and nickel catalyst were varied as shown in the following table:
more preferably 1:0.05:2:0.05.
example 2
2a (1e.q.0.5mmol) and 4CzIPN (5 mol)％)、NiCl 2 . 6H 2 O(5mol％)、(CH 3 ) 3 N-BH 3 (2e.q.), dtbbpy (10 mol%), molar ratio 1:0.05:2:0.05:0.1, add to a Schlenk reaction tube with a magnetic stir bar. The reaction vessel was evacuated and backfilled with argon 3 times, then DMAc (3.5 mL) was added under argon atmosphere, after which the schlenk tube was placed 2cm from the LED (20W) lamp and the reaction was stirred for 24h. After completion of the reaction, potassium peroxymonosulfonate Oxone (8.0 e.q.) and THF/H were added directly to the reaction mixture 2 SO 4 (1ml: 3ml), reacting at 40 ℃ for about 10 hours, cooling to room temperature, adding 10mL of water into the reaction solution, extracting with 3x15mL of ethyl acetate, combining organic layers, drying, desolventizing, and separating the crude mixture by flash column chromatography (the mobile phase is petroleum ether/ethyl acetate, the dosage ratio is 4:1) to obtain the target product 2b, wherein the target product is colorless liquid and the yield is 70%.
The product obtained is 1 H NMR data are characterized as follows: 1 H NMR(400MHz,DMSO-d 6 )δ8.93(s,1H),6.81-6.63(m,4H),3.66(s,3H).
example 3
3a (1e.q.0.5 mmol), 4CzIPN (5 mol%), niCl 2 . 6H 2 O(5mol％)、(CH 3 ) 3 N-BH 3 (2e.q.) and dtbbpy (10 mol%) in a molar ratio of 1:0.05:2:0.05:0.1, add to a Schlenk reaction tube with a magnetic stir bar. The reaction vessel was evacuated and backfilled with argon 3 times, then DMAc (3.5 mL) was added under argon atmosphere, after which schlenk's tube was placed 2cm from the LED (20W) lamp and the reaction was stirred illuminated for 24h. After completion of the reaction, potassium peroxymonosulfonate Oxone (8.0 e.q.) and THF H were added directly to the reaction mixture 2 SO 4 (1ml: 3ml), reacting at 40 ℃ for about 10 hours, cooling to room temperature, adding 10mL of water to the reaction solution, extracting with 3 × 15mL of ethyl acetate, combining the organic layers, drying, desolventizing, and purifying the crude mixture by flash column chromatography (mobile phase is petroleum ether)Ethyl acetate, the dosage ratio is 4:1) to obtain the target product 3b, the target product is colorless liquid, and the yield is 78%.
The product obtained is 1 H NMR data are characterized as follows: 1 H NMR(400MHz,DMSO-d 6 )δ9.33(s,1H),6.95(d,J＝8.3Hz,2H),6.66(d,J＝8.4Hz,2H),2.18(s,3H).
example 4
4a (1e.q.0.5 mmol), 4CzIPN (5 mol%), niCl 2 . 6H 2 O(5mol％)、(CH 3 ) 3 N-BH 3 (2e.q.), dtbbpy (10 mol%), molar ratio 1:0.05:2:0.05:0.1, add to schleck reaction tube with magnetic stir bar. The reaction vessel was evacuated and backfilled with argon 3 times, then DMAc (3.5 mL) was added under argon atmosphere, after which schlenk's tube was placed 2cm from the LED (20W) lamp and the reaction was stirred illuminated for 24h. After completion of the reaction, potassium peroxymonosulfonate Oxone (8.0 e.q.) and THF/H were added directly to the reaction mixture 2 SO 4 (1ml: 3ml), reacting at 40 ℃ for about 10 hours, cooling to room temperature, adding 10mL of water into the reaction solution, extracting with 3x15mL of ethyl acetate, combining organic layers, drying, desolventizing, and separating the crude mixture by flash column chromatography (the mobile phase is petroleum ether/ethyl acetate, the dosage ratio is 4:1) to obtain the target product 4b, wherein the target product is colorless liquid and the yield is 74%.
The product obtained is 1 H NMR data are characterized as follows: 1 H NMR(400MHz,DMSO-d 6 )δ9.13(s,1H),7.17(d,J＝8.7Hz,2H),6.69(d,J＝8.1Hz,2H),1.23(s,9H).
example 5
A mixture of 5a (1e. Q.0.5mmol), 4CzIPN (5 mol%), niCl 2 . 6H 2 O(5mol％)、(CH 3 ) 3 N-BH 3 (2e.q.)、dtbbpy (10 mol%), molar ratio 1:0.05:2:0.05:0.1, add to a Schlenk reaction tube with a magnetic stir bar. The reaction vessel was evacuated and backfilled with argon 3 times, then DMAc (3.5 mL) was added under argon atmosphere, after which the schlenk tube was placed 2cm from the LED (20W) lamp and the reaction was stirred for 24h. After completion of the reaction, potassium peroxymonosulfonate Oxone (8.0 e.q.) and THF/H were added directly to the reaction mixture 2 SO 4 (1ml: 3ml), reacting at 40 ℃ for about 10 hours, cooling to room temperature, adding 10mL of water into the reaction solution, extracting with 3x15mL of ethyl acetate, combining organic layers, drying, desolventizing, and separating the crude mixture by flash column chromatography (the mobile phase is petroleum ether/ethyl acetate, the dosage ratio is 4:1) to obtain the target product 5b, wherein the target product is colorless liquid and the yield is 73%.
The product obtained is 1 H NMR data are characterized as follows: 1 H NMR(500MHz,DMSO-d 6 )δ9.08(s,1H),6.40(d,J＝0.6Hz,1H),6.37(d,J＝0.5Hz,2H),2.17–2.15(m,6H).
example 6
Mixing 6a (1e.q.0.5mmol), 4CzIPN (5 mol%), niCl 2 . 6H 2 O(5mol％)、(CH 3 ) 3 N-BH 3 (2e.q.), dtbbpy (10 mol%), molar ratio 1:0.05:2:0.05:0.1, add to a Schlenk reaction tube with a magnetic stir bar. The reaction vessel was evacuated and backfilled with argon 3 times, then DMAc (3.5 mL) was added under argon atmosphere, after which schlenk's tube was placed 2cm from the LED (20W) lamp and the reaction was stirred illuminated for 24h. After completion of the reaction, potassium peroxymonosulfonate Oxone (8.0 e.q.) and THF H were added directly to the reaction mixture 2 SO 4 (1mlLiquid, yield 68%.
The product obtained is 1 H NMR data are characterized as follows: 1 H NMR(500MHz,CDCl 3 )δ6.97-6.89(m,2H),6.84–6.76(m,2H),6.38(s,1H).
example 7
7a (1e.q.0.5 mmol), 4CzIPN (5 mol%), niCl 2 . 6H 2 O(5mol％)、(CH 3 ) 3 N-BH 3 (2e.q.) and dtbbpy (10 mol%) in a molar ratio of 1:0.05:2:0.05:0.1, add to a Schlenk reaction tube with a magnetic stir bar. The reaction vessel was evacuated and backfilled with argon 3 times, then DMAc (3.5 mL) was added under argon atmosphere, after which the schlenk tube was placed 2cm from the LED (20W) lamp and the reaction was stirred for 24h. After completion of the reaction, potassium peroxymonosulfonate Oxone (8.0 e.q.) and THF H were added directly to the reaction mixture 2 SO 4 (1ml: 3ml), reacting at 40 ℃ for about 10 hours, cooling to room temperature, adding 10mL of water into the reaction solution, extracting with 3x15mL of ethyl acetate, combining organic layers, drying, desolventizing, and separating the crude mixture by flash column chromatography (the mobile phase is petroleum ether/ethyl acetate, the dosage ratio is 4:1) to obtain the target product 7b, wherein the target product is colorless liquid and the yield is 69%.
The 1H NMR data of the product obtained are characterized as follows: 1H NMR (400MHz, CDCl) 3 )δ7.13–6.95(m,1H),6.81–6.60(m,2H),5.40(d,J＝4.6Hz,1H),2.25(dd,J＝7.1,2.4Hz,6H).
Example 8
A mixture of 8a (1e. Q.0.5mmol), 4CzIPN (5 mol%), niCl 2 . 6H 2 O(5mol％)、(CH 3 ) 3 N-BH 3 (2e.q.) and dtbbpy (10 mol%) in a molar ratio of 1:0.05:2:0.05:0.1, adding into a Schlenk reaction tube with a magnetic stirring rodIn (1). The reaction vessel was evacuated and backfilled with argon 3 times, then DMAc (3.5 mL) was added under argon atmosphere, after which the schlenk tube was placed 2cm from the LED (20W) lamp and the reaction was stirred for 24h. After completion of the reaction, potassium peroxymonosulfonate Oxone (8.0 e.q.) and THF H were added directly to the reaction mixture 2 SO 4 (1ml.
The 1H NMR data of the product obtained are characterized as follows: 1H NMR (400MHz, CDCl3) delta 7.77 (s, 1H), 7.21-7.07 (m, 2H), 6.95-6.74 (m, 2H), 2.89 (ddd, J =11.3,8.0,5.6Hz, 1H), 1.47-1.11 (m, 6H).
Example 9
9a (1e.q.0.5mmol), 4CzIPN (5 mol%), niCl 2 . 6H 2 O(5mol％)、(CH 3 ) 3 N-BH 3 (2e.q.) and dtbbpy (10 mol%) in a molar ratio of 1:0.05:2:0.05:0.1, add to a Schlenk reaction tube with a magnetic stir bar. The reaction vessel was evacuated and backfilled with argon 3 times, then DMAc (3.5 mL) was added under argon atmosphere, after which the schlenk tube was placed 2cm from the LED (20W) lamp and the reaction was stirred for 24h. After completion of the reaction, potassium peroxymonosulfonate Oxone (8.0 e.q.) and THF H were added directly to the reaction mixture 2 SO 4 (1ml.
The product obtained is 1 H NMR data are characterized as follows: 1 H NMR(400MHz,CDCl 3 )δ9.47(s,1H),8.04(dd,J＝8.5,2.0Hz,1H),7.40(td,J＝7.9,2.0Hz,1H),7.30(dd,J＝6.3,3.7Hz,2H),7.18(d,J＝7.6Hz,1H),2.74(d,J＝2.1Hz,3H).
example 10
10a (1e.q.0.5 mmol), 4CzIPN (5 mol%), niCl 2 . 6H 2 O(5mol％)、(CH 3 ) 3 N-BH 3 (2e.q.) and dtbbpy (10 mol%) in a molar ratio of 1:0.05:2:0.05:0.1, add to a Schlenk reaction tube with a magnetic stir bar. The reaction vessel was evacuated and backfilled with argon 3 times, then DMAc (3.5 mL) was added under argon atmosphere, after which the schlenk tube was placed 2cm from the LED (20W) lamp and the reaction was stirred for 24h. After completion of the reaction, potassium peroxymonosulfonate Oxone (8.0 e.q.) and THF H were added directly to the reaction mixture 2 SO 4 (1ml: 3ml), reacting at 40 ℃ for about 10 hours, cooling to room temperature, adding 10mL of water into the reaction solution, extracting with 3x15mL of ethyl acetate, combining organic layers, drying, desolventizing, and separating the crude mixture by flash column chromatography (the mobile phase is petroleum ether/ethyl acetate, the dosage ratio is 4:1) to obtain the target product 10b, wherein the target product is colorless liquid and the yield is 66%.
The 1H NMR data of the product obtained are characterized as follows: 1 H NMR(400MHz,DMSO-d 6 )δ9.33(s,1H),6.95(d,J＝8.3Hz,2H),6.66(d,J＝8.4Hz,2H),2.18(s,3H).
example 11
11a (1e.q.0.5 mmol), 4CzIPN (5 mol%), niCl 2 . 6H 2 O(5mol％)、(CH 3 ) 3 N-BH 3 (2e.q.) and dtbbpy (10 mol%) in a molar ratio of 1:0.05:2:0.05:0.1, add to a Schlenk reaction tube with a magnetic stir bar. Evacuating the reaction vesselArgon was backfilled for 3 times, DMAc (3.5 mL) was added under argon, the Schlenk tube was placed 2cm from the LED (20W) lamp, and the reaction was stirred and illuminated for 24h. After completion of the reaction, potassium peroxymonosulfonate Oxone (8.0 e.q.) and THF H were added directly to the reaction mixture 2 SO 4 (1ml.
The product obtained is 1 H NMR data are characterized as follows: 1 H NMR(400MHz,CDCl 3 )δ7.31(t,J＝7.9Hz,2H),7.02(t,J＝7.4Hz,1H),6.93(d,J＝8.4Hz,2H),5.76(s,1H).
example 12
12a (1e.q.0.5 mmol), 4CzIPN (5 mol%), niCl 2 . 6H 2 O(5mol％)、(CH 3 ) 3 N-BH 3 (2e.q.) and dtbbpy (10 mol%) in a molar ratio of 1:0.05:2:0.05:0.1, add to a Schlenk reaction tube with a magnetic stir bar. The reaction vessel was evacuated and backfilled with argon 3 times, then DMAc (3.5 mL) was added under argon atmosphere, after which the schlenk tube was placed 2cm from the LED (20W) lamp and the reaction was stirred for 24h. After completion of the reaction, potassium peroxymonosulfonate Oxone (8.0 e.q.) and THF H were added directly to the reaction mixture 2 SO 4 (1ml: 3ml), reacting at 40 ℃ for about 10 hours, cooling to room temperature, adding 10mL of water into the reaction solution, extracting with 3x15mL of ethyl acetate, combining organic layers, drying, desolventizing, and separating the crude mixture by flash column chromatography (the mobile phase is petroleum ether/ethyl acetate, the dosage ratio is 4:1) to obtain the target product 12b, wherein the target product is colorless liquid and the yield is 70%.
The product obtained is 1 H NMR data are characterized as follows: 1 H NMR(400MHz,DMSO-d 6 )δ9.13(s,1H),7.17(d,J＝8.7Hz,2H),6.69(d,J＝8.1Hz,2H),1.23(s,9H).
example 13
13a (1e.q.0.5 mmol), 4CzIPN (5 mol%), niCl 2 . 6H 2 O(5mol％)、(CH 3 ) 3 N-BH 3 (2e.q.), dtbbpy (10 mol%), molar ratio 1:0.05:2:0.05:0.1, add to a Schlenk reaction tube with a magnetic stir bar. The reaction vessel was evacuated and backfilled with argon 3 times, then DMAc (3.5 mL) was added under argon atmosphere, after which the schlenk tube was placed 2cm from the LED (20W) lamp and the reaction was stirred for 24h. After completion of the reaction, potassium peroxymonosulfonate Oxone (8.0 e.q.) and THF/H were added directly to the reaction mixture 2 SO 4 (1ml: 3ml), reacting at 40 ℃ for about 10 hours, cooling to room temperature, adding 10mL of water into the reaction solution, extracting with 3x15mL of ethyl acetate, combining organic layers, drying, desolventizing, and separating the crude mixture by flash column chromatography (the mobile phase is petroleum ether/ethyl acetate, the dosage ratio is 4:1) to obtain the target product 13b, wherein the target product is colorless liquid and the yield is 72%.
The product obtained is 1 H NMR data are characterized as follows: 1 H NMR(500MHz,DMSO-d 6 )δ9.08(s,1H),6.40(d,J＝0.6Hz,1H),6.37(d,J＝0.5Hz,2H),2.17–2.15(m,6H).
example 14
14a (1e.q.0.5mmol), 4CzIPN (5 mol%), niCl 2 . 6H 2 O(5mol％)、(CH 3 ) 3 N-BH 3 (2e.q.) and dtbbpy (10 mol%) in a molar ratio of 1:0.05:2:0.05:0.1, add to a Schlenk reaction tube with a magnetic stir bar. The reaction vessel was evacuated and backfilled with argon 3 times, then DMAc (3.5 mL) was added under an argon atmosphere,the Schlenk tube was then placed 2cm from the LED (20W) lamp and the reaction stirred for 24h. After completion of the reaction, potassium peroxymonosulfonate Oxone (8.0 e.q.) and THF H were added directly to the reaction mixture 2 SO 4 (1ml: 3ml), reacting at 40 ℃ for about 10h, cooling to room temperature, adding 10mL of water into the reaction solution, extracting with 3x15mL of ethyl acetate, combining the organic layers, drying, desolventizing, and purifying the crude mixture by flash column chromatography (the mobile phase is petroleum ether/ethyl acetate, the dosage ratio is 4:1) to obtain the target product 14b, wherein the target product is colorless liquid and the yield is 72%.
The product obtained is 1 H NMR data are characterized as follows: 1 H NMR(400MHz,DMSO-d 6 )δ9.92(s,1H),8.15(d,J＝2.6Hz,1H),8.03(dd,J＝4.4,1.4Hz,1H),7.23-7.12(m,2H).
example 15
15a (1e.q.0.5 mmol), 4CzIPN (5 mol%), niCl 2 . 6H 2 O(5mol％)、(CH 3 ) 3 N-BH 3 (2e.q.) and dtbbpy (10 mol%) in a molar ratio of 1:0.05:2:0.05:0.1, add to a Schlenk reaction tube with a magnetic stir bar. The reaction vessel was evacuated and backfilled with argon 3 times, then DMAc (3.5 mL) was added under argon atmosphere, after which the schlenk tube was placed 2cm from the LED (20W) lamp and the reaction was stirred for 24h. After completion of the reaction, potassium peroxymonosulfonate Oxone (8.0 e.q.) and THF H were added directly to the reaction mixture 2 SO 4 (1ml: 3ml), reacting at 40 ℃ for about 10 hours, cooling to room temperature, adding 10mL of water into the reaction solution, extracting with 3x15mL of ethyl acetate, combining organic layers, drying, desolventizing, and separating the crude mixture by flash column chromatography (the mobile phase is petroleum ether/ethyl acetate, the dosage ratio is 4:1) to obtain the target product 15b, wherein the target product is colorless liquid and the yield is 72%.
The product obtained is 1 H NMR data are characterized as follows: 1 H NMR(400MHz,DMSO-d 6 )δ9.92(s,1H),8.15(d,J＝2.6Hz,1H),8.03(dd,J＝4.4,1.4Hz,1H),7.23-7.12(m,2H).
example 16
16a (1e.q.0.5 mmol), 4CzIPN (5 mol%), niCl 2 . 6H 2 O(5mol％)、(CH 3 ) 3 N-BH 3 (2e.q.) and dtbbpy (10 mol%) in a molar ratio of 1:0.05:2:0.05:0.1, add to a Schlenk reaction tube with a magnetic stir bar. The reaction vessel was evacuated and backfilled with argon 3 times, then DMAc (3.5 mL) was added under argon atmosphere, after which schlenk's tube was placed 2cm from the LED (20W) lamp and the reaction was stirred illuminated for 24h. After completion of the reaction, potassium peroxymonosulfonate Oxone (8.0 e.q.) and THF/H were added directly to the reaction mixture 2 SO 4 (1ml.
The product obtained is 1 H NMR data are characterized as follows: 1 H NMR(500MHz,DMSO-d 6 )δ9.15(s,2H),6.93(t,J＝8.0Hz,1H),6.26–6.18(m,3H).
example 17
17a (1e.q.0.5 mmol), 4CzIPN (5 mol%), niCl 2 . 6H 2 O(5mol％)、(CH 3 ) 3 N-BH 3 (2e.q.), dtbbpy (10 mol%), molar ratio 1:0.05:2:0.05:0.1, add to a Schlenk reaction tube with a magnetic stir bar. The reaction vessel was evacuated and backfilled with argon 3 times, then DMAc (3.5 mL) was added under argon atmosphere, then Schlenk's tube was placed 2cm from the LED (20W) lamp, the reaction was stirred and illuminatedAnd (5) 24h. After completion of the reaction, potassium peroxymonosulfonate Oxone (8.0 e.q.) and THF H were added directly to the reaction mixture 2 SO 4 (1ml: 3ml), reacting at 40 ℃ for about 10 hours, cooling to room temperature, adding 10mL of water into the reaction solution, extracting with 3x15mL of ethyl acetate, combining organic layers, drying, desolventizing, and separating the crude mixture by flash column chromatography (the mobile phase is petroleum ether/ethyl acetate, the dosage ratio is 4:1) to obtain the target product 17b, wherein the target product is colorless liquid and the yield is 70%.
The product obtained is 1 H NMR data are characterized as follows: 1 H NMR(400MHz,DMSO-d 6 )δ8.66(s,2H),6.59(s,4H).
example 18
18a (1e.q.0.5 mmol), 4CzIPN (5 mol%), niCl 2 . 6H 2 O(5mol％)、(CH 3 ) 3 N-BH 3 (2e.q.) and dtbbpy (10 mol%) in a molar ratio of 1:0.05:2:0.05:0.1, add to a Schlenk reaction tube with a magnetic stir bar. The reaction vessel was evacuated and backfilled with argon 3 times, then DMAc (3.5 mL) was added under argon atmosphere, after which the schlenk tube was placed 2cm from the LED (20W) lamp and the reaction was stirred for 24h. After completion of the reaction, potassium peroxymonosulfonate Oxone (8.0 e.q.) and THF H were added directly to the reaction mixture 2 SO 4 (1ml.
The product obtained is 1 H NMR data are characterized as follows: 1 H NMR(400MHz,DMSO-d 6 )δ8.66(s,2H),6.59(s,4H).
example 19
19a (1e.q.0.5 mmol), 4CzIPN (5 mol%) and NiCl 2 . 6H 2 O(5mol％)、(CH 3 ) 3 N-BH 3 (2e.q.) and dtbbpy (10 mol%) in a molar ratio of 1:0.05:2:0.05:0.1, add to a Schlenk reaction tube with a magnetic stir bar. The reaction vessel was evacuated and backfilled with argon 3 times, then DMAc (3.5 mL) was added under argon atmosphere, after which the schlenk tube was placed 2cm from the LED (20W) lamp and the reaction was stirred for 24h. After completion of the reaction, potassium peroxymonosulfonate Oxone (8.0 e.q.) and THF H were added directly to the reaction mixture 2 SO 4 (1ml: 3ml), reacting at 40 ℃ for about 10 hours, cooling to room temperature, adding 10mL of water into the reaction solution, extracting with 3x15mL of ethyl acetate, combining organic layers, drying, desolventizing, and separating the crude mixture by flash column chromatography (the mobile phase is petroleum ether/ethyl acetate, the dosage ratio is 4:1) to obtain the target product 19b, wherein the target product is colorless liquid and the yield is 69%.
The product obtained is 1 H NMR data are characterized as follows: 1 H NMR(500MHz,CDCl 3 )δ6.97-6.89(m,2H),6.84–6.76(m,2H),6.38(s,1H).
example 20
20a (1e.q.0.5 mmol), 4CzIPN (5 mol%), niCl 2 . 6H 2 O(5mol％)、(CH 3 ) 3 N-BH 3 (2e.q.) and dtbbpy (10 mol%) in a molar ratio of 1:0.05:2:0.05:0.1, add to a Schlenk reaction tube with a magnetic stir bar. The reaction vessel was evacuated and backfilled with argon 3 times, then DMAc (3.5 mL) was added under argon atmosphere, after which the schlenk tube was placed 2cm from the LED (20W) lamp and the reaction was stirred for 24h. After completion of the reaction, potassium peroxymonosulfonate Oxone (8.0 e.q.) and THF H were added directly to the reaction mixture 2 SO 4 (1mlAdding 10mL of water into the reaction solution, extracting with 3x15mL of ethyl acetate, combining organic layers, drying, desolventizing, and separating the crude mixture by flash column chromatography (the mobile phase is petroleum ether/ethyl acetate, the dosage ratio is 4:1) to obtain the target product 20b, wherein the target product is colorless liquid, and the yield is 75%.
The product obtained is 1 H NMR data are characterized as follows: 1 H NMR(400MHz,DMSO-d 6 )δ11.66(s,1H),7.48-7.28(m,2H),6.32(d,J＝9.2Hz,1H),6.15(td,J＝6.5,0.8Hz,1H).
example 21
A mixture of 21a (1e. Q.0.5 mmol), 4CzIPN (5 mol%), niCl 2 . 6H 2 O(5mol％)、(CH 3 ) 3 N-BH 3 (2e.q.), dtbbpy (10 mol%), molar ratio 1:0.05:2:0.05:0.1, add to schleck reaction tube with magnetic stir bar. The reaction vessel was evacuated and backfilled with argon 3 times, then DMAc (3.5 mL) was added under argon atmosphere, after which the schlenk tube was placed 2cm from the LED (20W) lamp and the reaction was stirred for 24h. After completion of the reaction, potassium peroxymonosulfonate Oxone (8.0 e.q.) and THF/H were added directly to the reaction mixture 2 SO 4 (1ml: 3ml), reacting at 40 ℃ for about 10 hours, cooling to room temperature, adding 10mL of water into the reaction solution, extracting with 3x15mL of ethyl acetate, combining organic layers, drying, desolventizing, and separating the crude mixture by flash column chromatography (the mobile phase is petroleum ether/ethyl acetate, the dosage ratio is 4:1) to obtain the target product 21b, wherein the target product is colorless liquid and the yield is 69%.
The product obtained is 1 H NMR data are characterized as follows: 1 H NMR(400MHz,DMSO-d 6 )δ9.92(s,1H),8.15(d,J＝2.6Hz,1H),8.03(dd,J＝4.4,1.4Hz,1H),7.23-7.12(m,2H).
example 22
22a (1e.q.0.5 mmol), 4CzIPN (5 mol%), niCl 2 . 6H 2 O(5mol％)、(CH 3 ) 3 N-BH 3 (2e.q.) and dtbbpy (10 mol%) in a molar ratio of 1:0.05:2:0.05:0.1, add to a Schlenk reaction tube with a magnetic stir bar. The reaction vessel was evacuated and backfilled with argon 3 times, then DMAc (3.5 mL) was added under argon atmosphere, after which the schlenk tube was placed 2cm from the LED (20W) lamp and the reaction was stirred for 24h. After completion of the reaction, potassium peroxymonosulfonate Oxone (8.0 e.q.) and THF H were added directly to the reaction mixture 2 SO 4 (1ml.
The product obtained is 1 H NMR data are characterized as follows: 1 H NMR(400MHz,DMSO-d 6 )δ10.17(s,1H),8.23-8.11(m,1H),7.86-7.77(m,1H),7.50-7.41(m,2H),7.37-7.28(m,2H),6.91(dd,J＝6.8,1.4Hz,1H).
example 23
23a (1e.q.0.5 mmol), 4CzIPN (5 mol%), niCl 2 . 6H 2 O(5mol％)、(CH 3 ) 3 N-BH 3 (2e.q.), dtbbpy (10 mol%), molar ratio 1:0.05:2:0.05:0.1, add to schleck reaction tube with magnetic stir bar. The reaction vessel was evacuated and backfilled with argon 3 times, then DMAc (3.5 mL) was added under argon atmosphere, after which schlenk's tube was placed 2cm from the LED (20W) lamp and the reaction was stirred illuminated for 24h. After completion of the reaction, potassium peroxymonosulfonate Oxone (8.0 e.q.) and THF/H were added directly to the reaction mixture 2 SO 4 (1mlAdding 10mL of water, extracting with 3x15mL of ethyl acetate, combining organic layers, drying, desolventizing, and separating the crude mixture by flash column chromatography (the mobile phase is petroleum ether/ethyl acetate, the dosage ratio is 4:1) to obtain the target product 23b which is colorless liquid, and the yield is 73%.
The product obtained is 1 H NMR data are characterized as follows: 1 H NMR(400MHz,DMSO-d 6 )δ9.59(s,1H),7.57(d,J＝7.4Hz,2H),7.49(d,J＝8.6Hz,2H),7.41(t,J＝7.7Hz,2H),7.27(t,J＝7.3Hz,1H),6.87(d,J＝8.6Hz,2H).
example 24
24a (1e.q.0.5 mmol), 4CzIPN (5 mol%), niCl 2 . 6H 2 O(5mol％)、(CH 3 ) 3 N-BH 3 (2e.q.), dtbbpy (10 mol%), molar ratio 1:0.05:2:0.05:0.1, add to schleck reaction tube with magnetic stir bar. The reaction vessel was evacuated and backfilled with argon 3 times, then DMAc (3.5 mL) was added under argon atmosphere, after which schlenk's tube was placed 2cm from the LED (20W) lamp and the reaction was stirred illuminated for 24h. After completion of the reaction, potassium peroxymonosulfonate Oxone (8.0 e.q.) and THF/H were added directly to the reaction mixture 2 SO 4 (1ml: 3ml), reacting at 40 ℃ for about 10 hours, cooling to room temperature, adding 10mL of water into the reaction solution, extracting with 3x15mL of ethyl acetate, combining organic layers, drying, desolventizing, and separating the crude mixture by flash column chromatography (the mobile phase is petroleum ether/ethyl acetate, the dosage ratio is 4:1) to obtain the target product 24b, wherein the target product is colorless liquid and the yield is 74%.
The product obtained is 1 H NMR data are characterized as follows: 1 H NMR(500MHz,DMSO-d6)δ9.48(s,1H),7.71(d,J＝7.5Hz,1H),7.66(d,J＝8.2Hz,1H),7.49(d,J＝7.4Hz,1H),7.31(t,J＝7.4Hz,1H),7.19(td,J＝7.4,1.0Hz,1H),6.98(d,J＝1.8Hz,1H),6.79(dd,J＝8.2,2.2Hz,1H),3.82(s,2H).
example 25
25a (1e.q.0.5 mmol), 4CzIPN (5 mol%), niCl 2 . 6H 2 O(5mol％)、(CH 3 ) 3 N-BH 3 (2e.q.) and dtbbpy (10 mol%) in a molar ratio of 1:0.05:2:0.05:0.1, add to schleck reaction tube with magnetic stir bar. The reaction vessel was evacuated and backfilled with argon 3 times, then DMAc (3.5 mL) was added under argon atmosphere, after which the schlenk tube was placed 2cm from the LED (20W) lamp and the reaction was stirred for 24h. After completion of the reaction, potassium peroxymonosulfonate Oxone (8.0 e.q.) and THF/H were added directly to the reaction mixture 2 SO 4 (1ml: 3ml), reacting at 40 ℃ for about 10 hours, cooling to room temperature, adding 10mL of water into the reaction solution, extracting with 3x15mL of ethyl acetate, combining organic layers, drying, desolventizing, and separating the crude mixture by flash column chromatography (the mobile phase is petroleum ether/ethyl acetate, the dosage ratio is 4:1) to obtain the target product 25b, wherein the target product is colorless liquid and the yield is 71%.
The product obtained is 1 H NMR data are characterized as follows: 1 H NMR(500MHz,DMSO-d 6 )δ13.00(s,1H)；13C NMR(100MHz,DMSO-d6)δ139.5,139.4,138.7,136.7,134.5,132.9.
the above-described embodiments are merely preferred embodiments of the present invention, which is not intended to be limiting in any way, and other variations and modifications are possible without departing from the scope of the invention as set forth in the appended claims.
Claims (10)
1. A method of photocatalytic aryl or heteroaryl halide hydroxylation comprising the steps of:
(1) In a solvent, reacting aryl halide or heteroaryl halide in the presence of a photocatalyst, an amine borane reagent and a nickel catalyst under the condition of illumination to produce an intermediate;
(2) The intermediate reacts in the presence of an oxidant to generate a corresponding hydroxylated aromatic compound or a hydroxylated heteroarene compound;
the reaction formula of the method is as follows:
wherein Ar is aryl or heteroaryl; aryl is selected from phenyl, biphenyl, naphthyl, fluorenyl and phenanthryl; heteroaryl is selected from pyridyl, furyl, thienyl, pyrrolyl, imidazolyl, indolyl, quinolinyl, piperazinyl;
the R group is a substituent group, and the substituent group is at least one of H, hydroxyl, C1-C6 alkyl, C1-C6 alkoxy, a halogen group, nitro or phenyl;
x is a halogen group.
2. The method of claim 1, wherein Ar is selected from the group consisting of phenyl, biphenyl, naphthyl, fluorenyl, pyridyl, quinolinyl;
the R group is a substituent selected from at least one of H, hydroxyl, methyl, ethyl, propyl, tert-butyl, methoxy, halogen group, nitro or phenyl, and the halogen group is selected from at least one of F, cl, br and I;
x is one of Br and Cl.
3. The method of any one of claims 1 or 2, wherein the molar ratio of aryl halide or heteroaryl halide, photocatalyst, amine borane reagent, and nickel catalyst in step (1) is 1: (0.01-1.0): (1.0-4.0): (0.01-1.0).
4. The method of any one of claims 1 or 2, wherein the photocatalyst in step (1) is at least one of a 4CzIPN photocatalyst and derivatives thereof.
5. The method of any one of claims 1 or 2, wherein the amine borane reagent in step (1) is at least one of trimethylamine borane, triethylamine borane, pyridine borane, 2-methylpyridine borane, 5-ethyl-2-methylpyridine borane, 3,5-dimethylpyridine borane and 3,5-diisopropylpyridine borane.
6. The method of claim 1 or 2, wherein the nickel catalyst in step (1) is NiCl 2. 6H 2 O、NiCl 2 . DPPP、NiCl 2 . (PPh 3 ) 2 、Ni(CH 3 COO) 2 . 6H 2 O、NiCl 2 . At least one of DMEs.
7. The method of any one of claims 1 or 2, wherein the N ligand of the nickel catalyst in step (1) is at least one of 4,4 '-di-tert-butyl-2,2' -bipyridine, 1,10-phenanthroline, 2,9-dimethyl-1,10-phenanthroline, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline.
8. The method of any one of claims 1 or 2, wherein the solvent in step (1) is at least one of N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, acetonitrile, ethyl acetate, and N-methylpyrrolidone.
9. The method of any one of claims 1 or 2, wherein the oxidant in step (2) is at least one of hydrogen peroxide and potassium peroxymonosulfonate.
10. The method of any one of claims 1 or 2, wherein the molar ratio of aryl halide or heteroaryl halide to oxidant in step (2) is 1:5 to 10.
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