CN115490732B - Synthesis method of chiral biphenyl diol catalyst - Google Patents
Synthesis method of chiral biphenyl diol catalyst Download PDFInfo
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- CN115490732B CN115490732B CN202211213918.5A CN202211213918A CN115490732B CN 115490732 B CN115490732 B CN 115490732B CN 202211213918 A CN202211213918 A CN 202211213918A CN 115490732 B CN115490732 B CN 115490732B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 13
- 238000001308 synthesis method Methods 0.000 title abstract description 6
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 title description 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 58
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 27
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims abstract description 19
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 17
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 17
- 150000003973 alkyl amines Chemical class 0.000 claims abstract description 16
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 11
- 239000011669 selenium Substances 0.000 claims abstract description 11
- 230000009471 action Effects 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 11
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 7
- 125000001424 substituent group Chemical group 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 125000006267 biphenyl group Chemical group 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 239000000758 substrate Substances 0.000 abstract description 8
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 description 23
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 9
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 239000003446 ligand Substances 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 6
- 239000012043 crude product Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 235000019439 ethyl acetate Nutrition 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- 239000000741 silica gel Substances 0.000 description 6
- 229910002027 silica gel Inorganic materials 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- NJBCRXCAPCODGX-UHFFFAOYSA-N 2-methyl-n-(2-methylpropyl)propan-1-amine Chemical compound CC(C)CNCC(C)C NJBCRXCAPCODGX-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- DMSZORWOGDLWGN-UHFFFAOYSA-N ctk1a3526 Chemical compound NP(N)(N)=O DMSZORWOGDLWGN-UHFFFAOYSA-N 0.000 description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 3
- 229940043279 diisopropylamine Drugs 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 150000003568 thioethers Chemical class 0.000 description 3
- KKFCSVWAMOBYSW-UHFFFAOYSA-N 1,3-dimethyl-2-phenylsulfanylbenzene Chemical compound CC1=CC=CC(C)=C1SC1=CC=CC=C1 KKFCSVWAMOBYSW-UHFFFAOYSA-N 0.000 description 2
- HKTCLPBBJDIBGF-UHFFFAOYSA-N 1-phenyl-2-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC=C1C1=CC=CC=C1 HKTCLPBBJDIBGF-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- SJNALLRHIVGIBI-UHFFFAOYSA-N allyl cyanide Chemical compound C=CCC#N SJNALLRHIVGIBI-UHFFFAOYSA-N 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 238000009876 asymmetric hydrogenation reaction Methods 0.000 description 2
- JNGZXGGOCLZBFB-IVCQMTBJSA-N compound E Chemical compound N([C@@H](C)C(=O)N[C@@H]1C(N(C)C2=CC=CC=C2C(C=2C=CC=CC=2)=N1)=O)C(=O)CC1=CC(F)=CC(F)=C1 JNGZXGGOCLZBFB-IVCQMTBJSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 150000008039 phosphoramides Chemical class 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 2
- 150000003342 selenium Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 125000005000 thioaryl group Chemical group 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000007037 hydroformylation reaction Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- UPPVRFOGRCBSJP-UHFFFAOYSA-N n-dichlorophosphanyl-n-propan-2-ylpropan-2-amine Chemical compound CC(C)N(C(C)C)P(Cl)Cl UPPVRFOGRCBSJP-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65744—Esters of oxyacids of phosphorus condensed with carbocyclic or heterocyclic rings or ring systems
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0255—Phosphorus containing compounds
- B01J31/0264—Phosphorus acid amides
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
The invention discloses a synthesis method of chiral 5,5', 6' -tetramethyl-3, 3' -di-tert-butyl-1, 1' -biphenyl-2, 2' -diol catalysts, belongs to the technical field of organic chemical synthesis, and particularly relates to a chiral 5,5', 6' -tetramethyl-3, 3' -di-tert-butyl-1, 1' -biphenyl-2, 2' -diol and phosphorus trichloride, triethylamine and alkylamine reagents, wherein chiral 5,5', 6' -tetramethyl-3, 3' -di-tert-butyl-1, 1' -biphenyl-2, 2' -diol compounds are generated under the combined action of selenium powder or sulfur powder and a solvent. The invention is a synthesis method of 5,5', 6' -tetramethyl-3, 3' -di-tert-butyl-1, 1' -biphenyl-2, 2' -diol selenium/sulfide, which has the advantages of mild reaction conditions, economical and easily available raw materials, good repeatability, simple reaction, wide substrate application range and good economical efficiency.
Description
Technical Field
The invention belongs to the technical field of organic chemical synthesis, and particularly relates to a synthesis method of chiral 5,5', 6' -tetramethyl-3, 3' -di-tert-butyl-1, 1' -biphenyl-2, 2' -diol catalysts.
Background
For the first synthesis of this type of framework, a patent was reported in 1999. Later synthetic reports on such backbones are also focused on patents. The first chemical synthesis of this type of scaffold was reported in 2006 (Chemistry-a European journal 2006, 12, 7482-7488), siegfried r. Waldvogel reported the synthesis of this type of scaffold using electrochemical anodic oxidation. Iwao Ojima in 2003 uses phosphites of this type of backbone as ligands (org. Lett. 2003, 5, 21, 3831-3834), catalyzing asymmetric hydrogenation reactions, which are the first reported monodentate phosphite ligands from enantiomerically pure axial chiral bisphenols. Subsequently, phosphite ligands of this type of framework are also utilized to catalyze a series of chiral reactions such as asymmetric hydroformylation of allyl cyanide. By 2007, first examples of the skeleton monodentate phosphoramide ligand are reported (Angew, chem, int, ed. 2007, 46, 1497-1500) and are applied to high enantioselective asymmetric hydrogenation reaction induced under iridium catalysis. By 2008, methyl and isopropyl substituted ligands of the framework phosphoramide are synthesized by respectively utilizing hexamethylphosphoric triamide and dichloro-N, N-diisopropyl phosphoramidite. In recent years, the synthesis of phosphoramide ligands with such frameworks is mainly focused on the expansion of substituents on different nitrogen. Until 2010 Anna g.wenzel (eur.j. Org. Chem. 2010, 3027-3031) reported that-NHTf substituted sulfides of this type of backbone were used as catalysts to catalyze the reaction, which is also the only example of sulfides of this type of backbone. While alkyl substituted selenium/sulfides for phosphoramides of this backbone are not reported. Therefore, based on previous reports, the use of such backbones as ligands is relatively broad, so that the alkyl substituted selenium/sulfide of phosphoramides of such backbones we have developed is very important and necessary.
Disclosure of Invention
The invention aims to provide a synthesis method of 5,5', 6' -tetramethyl-3, 3' -di-tert-butyl-1, 1' -biphenyl-2, 2' -diol selenium/sulfide, which has the advantages of mild reaction conditions, economical and easily available raw materials, good repeatability, simple reaction, wide substrate application range and good economy.
The technical scheme adopted by the invention for achieving the purpose is as follows:
chiral 5,5', 6' -tetramethyl-3, 3' -di-tert-butyl-1, 1' -biphenyl-2, 2' -diol compounds are shown as follows:
Preferably, R 1 Is any one of ethyl, isopropyl and isobutyl, R 2 Is any one of ethyl, isopropyl and isobutyl.
Preferably, R 1 And R is R 2 Identical, R 1 Or R is 2 Is C 2-4 Any one of alkyl groups.
Preferably, the chiral 5,5', 6' -tetramethyl-3, 3' -di-tert-butyl-1, 1' -biphenyl-2, 2' -diol compound is any one of the following compounds:
the invention discloses a preparation method of chiral 5,5', 6' -tetramethyl-3, 3' -di-tert-butyl-1, 1' -biphenyl-2, 2' -diol compounds, which comprises the step of preparing chiral 5,5', 6' -tetramethyl-3, 3' -di-tert-butyl-1, 1' -biphenyl-2, 2' -diol from chiral 5,5', 6' -tetramethyl-3, 3' -di-tert-butyl-1, 1' -biphenyl-2, 2' -diol compounds under the combined action of selenium powder or sulfur powder and a solvent by using phosphorus trichloride, triethylamine and an alkylamine reagent.
Preferably, phosphorus trichloride is dissolved in methylene dichloride, triethylamine is added at 0-5 ℃, then alkylamine reagent is added at room temperature, chiral 5,5', 6' -tetramethyl-3, 3 '-di-tert-butyl-1, 1' -biphenyl-2, 2 '-diol is added for reaction, selenium powder or sulfur powder is added for reaction, separation and purification are carried out, and chiral 5,5',6 '-tetramethyl-3, 3' -di-tert-butyl-1, 1 '-biphenyl-2, 2' -diol compounds are obtained.
More preferably, room temperature refers to a temperature of 20-35 ℃.
More preferably, phosphorus trichloride is added to methylene chloride so that the concentration of phosphorus trichloride is 0.05-0.4 mmol/mL.
More preferably, the triethylamine is used in a molar amount of 400 to 600% of the molar amount of phosphorus trichloride.
More preferably, the alkylamine reagent is any one of diethylamine, diisopropylamine, diisobutylamine.
More preferably, the alkylamine reagent is used in a molar amount of 80 to 120% of the molar amount of phosphorus trichloride used.
More preferably, chiral 5,5', 6' -tetramethyl-3, 3' -di-tert-butyl-1, 1' -biphenyl-2, 2' -diol is used in a molar amount of 80-120% of the molar amount of phosphorus trichloride.
More preferably, the selenium powder is used in a molar amount of 200-400% of the molar amount of chiral 5,5', 6' -tetramethyl-3, 3' -di-tert-butyl-1, 1' -biphenyl-2, 2' -diol used.
More preferably, the sulfur powder is used in a molar amount of 200 to 400% of the molar amount of chiral 5,5', 6' -tetramethyl-3, 3' -di-tert-butyl-1, 1' -biphenyl-2, 2' -diol used.
More preferably, phosphorus trichloride is dissolved in methylene dichloride, after the solution is cooled to low temperature of 0 ℃, triethylamine is dropwise added into the solution, the system is warmed to room temperature after the reaction, alkylamine reagent is dropwise added into the system, then the solution is stirred, chiral 5,5', 6' -tetramethyl-3, 3' -di-tert-butyl-1, 1' -biphenyl-2, 2' -diol is added into the system at room temperature for stirring reaction, selenium powder or sulfur powder is added into the system at room temperature for stirring reaction, and the reaction is continued, and then the compound is obtained through reduced pressure distillation and column chromatography purification.
More preferably, phosphorus trichloride is dissolved in methylene chloride, cooled to a low temperature of 0 ℃, and triethylamine is added dropwise thereto, the system is warmed to room temperature after reaction for 10 minutes, and alkylamine is added, followed by stirring for 12 h. Chiral 5,5', 6' -tetramethyl-3, 3' -di-tert-butyl-1, 1' -biphenyl-2, 2' -diol derivative is added into the system at room temperature to react with 12h under stirring, selenium is added into the system at room temperature, and the stirring reaction is continued for 12 h. Then the catalyst is obtained through reduced pressure distillation and column chromatography purification.
Preferably, the alkylamine reagent is a disubstituted amine.
More preferably, the substituents of the disubstituted amine are the same, and the substituents are any of ethyl, isopropyl, isobutyl.
Preferably, the substituent of the alkylamine reagent is C 1-5 Any one of alkyl groups。
The invention discloses application of the chiral 5,5', 6' -tetramethyl-3, 3' -di-tert-butyl-1, 1' -biphenyl-2, 2' -diol compound as a catalyst.
The chiral 5,5', 6' -tetramethyl-3, 3' -di-tert-butyl-1, 1' -biphenyl-2, 2' -diol compound is prepared by the following steps:
the chiral 5,5', 6' -tetramethyl-3, 3 '-di-tert-butyl-1, 1' -biphenyl-2, 2 '-diol, phosphorus trichloride, triethylamine and alkylamine reagent are adopted to generate the chiral 5,5',6 '-tetramethyl-3, 3' -di-tert-butyl-1, 1 '-biphenyl-2, 2' -diol compound under the combined action of selenium powder or sulfur powder and solvent, so that the invention has the following beneficial effects: according to the method, different chiral 5,5', 6' -tetramethyl-3, 3' -di-tert-butyl-1, 1' -biphenyl-2, 2' -diol derivative selenium/sulfide catalysts are synthesized for the first time by selecting different alkylamines; the method adopts economic and available 5,5', 6' -tetramethyl-3, 3 '-di-tert-butyl-1, 1' -biphenyl-2, 2 '-diol and cheap and easily available alkylamine as substrates, prepares chiral 5,5',6 '-tetramethyl-3, 3' -di-tert-butyl-1, 1 '-biphenyl-2, 2' -diol derivative selenium/sulfide catalyst by one-pot method, and avoids complex synthetic route in the reaction process; the substrate of the method has diversity, and can synthesize 5,5', 6' -tetramethyl-3, 3' -di-tert-butyl-1, 1' -biphenyl-2, 2' -diol derivative selenium/sulfide catalysts with various alkyl substituents.
Therefore, the method for synthesizing the 5,5', 6' -tetramethyl-3, 3' -di-tert-butyl-1, 1' -biphenyl-2, 2' -diol selenium/sulfide is mild in reaction condition, economical and easy to purchase raw materials, good in repeatability, simple in reaction, wide in substrate application range and good in economical efficiency.
Drawings
FIG. 1 is a graph showing the yields of chiral 5,5', 6' -tetramethyl-3, 3' -di-tert-butyl-1, 1' -biphenyl-2, 2' -diol compounds.
Detailed Description
The technical scheme of the invention is further described in detail below with reference to the specific embodiments and the attached drawings:
in this embodiment, the hydrogen nuclear magnetic resonance spectrum of the compound 1 H NMR、 13 C NMR) was determined from Bruker AVANCE III HD 400 with deuterated chloroform as solvent. Chemical shift (δ) is referenced in ppm with tetramethylsilane as internal standard, multiplicity as shown: s=singlet, d=doublet, t=triplet, q=quadruple, m=multiplet.
Example 1:
compounds [ (]S) -a was prepared as follows:
0.423mmol of phosphorus trichloride was dissolved in ultra-dry DCM (2 mL). The reaction was cooled to 0 ℃ and 2.12mmol Et was added dropwise thereto 3 N. After 10min, the reaction was warmed to room temperature and 0.423mmol of diisopropylamine was added, followed by stirring for 5h. After 0.423mmol of (S) - (-) -5,5', 6' -tetramethyl-3, 3' -di-tert-butyl-1, 1' -biphenyl-2, 2' -diol was added to the system at room temperature and stirred for reaction for 12 hours, 1.269mmol of selenium powder was added at room temperature and stirred for reaction for 12 hours. After completion of the reaction, it was filtered through celite, concentrated in vacuo, and dried by spin-drying. The crude product was purified on silica gel (EtOAc: petroleum ether 1:100 by volume) to give compound a as a white solid in 53% yield.
1 （400MHz，Chloroform-d）δ7.22（s，1H），7.11（s，1H），3.69（dp，J=20.4，6.8Hz，2H），2.29–2.15（m，6H），1.86（s，3H），1.66（s，3H），1.56（s，9H），1.44（s，9H），1.22（dd，J=19.7，6.8Hz，12H）； 13 CNMR（101MHz，CDCl 3 ）δ147.16，146.99，144.04，143.95，138.34，138.30，136.63，136.59，135.04，135.01，134.99，133.27，133.25，132.14，132.12，130.29，130.27，129.74，129.71，129.24，129.21，128.29，128.27，50.02，35.49，35.14，33.31，32.08，23.48，23.02，23.00，20.59，20.33，16.69，16.52。
Example 2:
compounds [ (]S) -B, the synthetic route is as follows:
0.423mmol of phosphorus trichloride was dissolved in ultra-dry DCM (2 mL). The reaction was cooled to 0 ℃ and 2.12mmol Et was added dropwise thereto 3 N. After 10min, the reaction was warmed to room temperature and 0.423mmol of diisopropylamine was added, followed by stirring for 5h. After 0.423mmol of (S) - (-) -5,5', 6' -tetramethyl-3, 3' -di-tert-butyl-1, 1' -biphenyl-2, 2' -diol was added to the system at room temperature and stirred for reaction for 12 hours, 1.269mmol of sulfur powder was added at room temperature and stirred for reaction for 12 hours. After completion of the reaction, it was filtered through celite, concentrated in vacuo, and dried by spin-drying. The crude product was purified on silica gel (EtOAc: petroleum ether 1:100 by volume) to give compound B as a white solid in 44% yield.
1 （400MHz，Chloroform-d）δ7.21（s，1H），7.11（s，1H），3.45（dp，J=20.5，6.8Hz，2H），2.25（d，J=1.4Hz，3H），2.22（d，J=1.5Hz，3H），1.86（s，3H），1.66（s，3H），1.54（s，9H），1.44（s，9H），1.22（t，J=7.3Hz，12H）； 13 CNMR（101MHz，CDCl 3 ）δ147.18，147.04，144.18，144.08，138.38，138.34，136.72，136.68，134.98，134.96，134.93，133.11，133.09，132.02，132.00，130.01，129.99，129.64，129.62，129.08，129.05，128.18，128.16，49.34，35.37，35.20，33.03，32.10，23.07，20.57，20.34，16.70，16.49。
Example 3:
compounds [ (]S) -C was prepared as follows:
0.141mmol of phosphorus trichloride was dissolved in ultra-dry DCM (2 mL). The reaction was cooled to 0 ℃ and 0.705mmol Et was added dropwise thereto 3 N. After 10min, the reaction was warmed to room temperature and 0.141mmol of diisobutylamine was added, followed by stirring for 5h. After 0.141mmol of (S) - (-) -5,5', 6' -tetramethyl-3, 3' -di-tert-butyl-1, 1' -biphenyl-2, 2' -diol was added to the system at room temperature and stirred for reaction for 12 hours, 0.423mmol of selenium powder was added at room temperature and stirred for reaction for 12 hours. After completion of the reaction, it was filtered through celite, concentrated in vacuo, and dried by spin-drying. The crude product was purified on silica gel (EtOAc: petroleum ether 1:120 by volume) to give compound C as a white solid in 79% yield.
1 （400MHz，Chloroform-d）δ7.15（s，1H），7.03（s，1H），2.98（s，2H），2.49（ddd，J=13.9，11.3，6.2Hz，2H），2.18（s，3H），2.14（d，J=1.6Hz，3H），1.77（s，3H），1.70（td，J=13.6，12.4，5.6Hz，2H），1.61（s，3H），1.47（d，J=1.3Hz，9H），1.35（d，J=1.2Hz，9H），0.73（d，J=6.7Hz，6H），0.68（d，J=6.6Hz，6H）； 13 CNMR（101MHz，CDCl 3 ）δ146.92，146.77，142.95，142.86，137.21，137.17，135.69，135.65，134.09，134.08，133.77，133.75，132.22，132.20，131.43，131.40，129.22，129.21，128.52，128.50，128.02，128.00，127.20，127.18，58.08，58.06，34.48，33.83，32.18，30.09，27.30，27.27，19.94，19.92，19.45，19.19，15.41，15.39。
Example 4:
compounds [ (]S) -D was prepared as follows:
dissolving 0.141mmol of phosphorus trichloride in ultra-dryIn DCM (2 mL). The reaction was cooled to 0 ℃ and 0.705mmol Et was added dropwise thereto 3 N. After 10min, the reaction was warmed to room temperature and 0.141mmol of diisobutylamine was added, followed by stirring for 5h. After 0.141mmol of (S) - (-) -5,5', 6' -tetramethyl-3, 3' -di-tert-butyl-1, 1' -biphenyl-2, 2' -diol was added to the system at room temperature and stirred for reaction for 12 hours, 0.423mmol of sulfur powder was added at room temperature and stirred for reaction for 12 hours. After completion of the reaction, it was filtered through celite, concentrated in vacuo, and dried by spin-drying. The crude product was purified on silica gel (EtOAc: petroleum ether 1:120 by volume) to give compound D as a white solid in 81% yield.
1 （400MHz，Chloroform-d）δ7.14（s，1H），7.03（s，1H），2.89（s，2H），2.43（ddd，J=14.0，11.1，6.3Hz，2H），2.16（dd，J=15.7，1.4Hz，6H），1.77（s，3H），1.68（dt，J=13.5，6.8Hz，2H），1.61（s，3H），1.45（s，9H），1.35（s，9H），0.70（dd，J=22.6，6.7Hz，12H）； 13 CNMR（101MHz，CDCl 3 ）δ146.93，146.79，143.13，143.04，137.36，137.31，135.86，135.82，134.08，134.06，133.82，133.80，132.21，132.19，131.37，131.35，129.06，129.04，128.51，128.49，128.03，128.01，127.17，127.16，58.10，58.07，34.45，33.96，31.95，30.15，27.43，27.39，20.01，19.93，19.50，19.24，15.48，15.46。
Example 5:
compounds [ (]S) -E, the synthetic route is as follows:
0.141mmol of phosphorus trichloride was dissolved in ultra-dry DCM (2 mL). The reaction was cooled to 0 ℃ and 0.705mmol Et was added dropwise thereto 3 N. After 10min, the reaction was warmed to room temperature, and 0.141mmol of diethylamine was added, followed by stirring for 5h. To the system was added 0.141mmol of (S) - (-) -5,5', 6' -tetramethyl-3, 3' -di-tert-butyl-1 at room temperatureAfter the reaction of 1 '-biphenyl-2, 2' -diol with stirring for 12 hours, 0.423mmol of sulfur powder was added at room temperature and the reaction was stirred for 12 hours. After completion of the reaction, it was filtered through celite, concentrated in vacuo, and dried by spin-drying. The crude product was purified on silica gel (EtOAc: petroleum ether 1:120 by volume) to give compound E as a white solid in 82% yield.
1 （400MHz，Chloroform-d）δ7.22（s，1H），7.13（s，1H），3.24（tt，J=14.0，7.0Hz，2H），3.03–2.76（m，2H），2.24（dd，J=13.1，1.5Hz，6H），1.85（s，3H），1.74（s，3H），1.53（s，9H），1.41（s，9H），1.05（t，J=7.0Hz，6H）； 13 CNMR（101MHz，CDCl 3 ）δ147.28，147.12，144.11，144.02，138.30，138.26，137.08，137.04，135.21，135.19，134.97，134.95，133.34，133.32，132.61，132.59，130.14，130.13，129.43，129.41，129.30，129.28，128.37，128.35，44.23，44.19，35.49，34.90，33.14，31.62，31.32，31.25，20.54，20.51，16.78，16.72，15.03，15.00。
Example 6:
compounds [ (]S) -F, the synthetic route is as follows:
0.141mmol of phosphorus trichloride was dissolved in ultra-dry DCM (2 mL). The reaction was cooled to 0 ℃ and 0.705mmol Et was added dropwise thereto 3 N. After 10min, the reaction was warmed to room temperature, and 0.141mmol of diethylamine was added, followed by stirring for 5h. After 0.141mmol of (S) - (-) -5,5', 6' -tetramethyl-3, 3' -di-tert-butyl-1, 1' -biphenyl-2, 2' -diol was added to the system at room temperature and stirred for reaction for 12 hours, 0.423mmol of sulfur powder was added at room temperature and stirred for reaction for 12 hours. After completion of the reaction, it was filtered through celite, concentrated in vacuo, and dried by spin-drying. The crude product was purified on silica gel (EtOAc: petroleum ether 1:120 by volume) to give compound F as a white solid in 89% yield.
1 （400MHz，Chloroform-d）δ7.21（s，1H），7.12（s，1H），3.29–3.07（m，2H），2.88（tq，J=14.2，7.0Hz，2H），2.26（s，3H），2.23（s，3H），1.85（s，3H），1.74（s，3H），1.51（s，6H），1.41（s，6H），1.05（t，J=7.1Hz，9H）； 13 CNMR（101MHz，CDCl 3 ）δ147.30，147.16，144.17，138.36，138.31，137.11，137.07，135.14，135.12，134.93，133.23，132.47，129.93，129.91，129.35，129.18，128.30，128.28，43.91，43.87，35.40，34.95，32.87，31.30，20.53，20.51，16.80，16.71，15.07，15.05。
The results of the yields of compounds A-F obtained by the methods of examples 1-6 are shown in FIG. 1, wherein S1 is compound A, S2 is compound B, S3 is compound C, S4 is compound D, S5 is compound E, and S6 is compound F.
Example 7:
the preparation of the axial chiral sulfur-containing diphenyl derivative G is shown in the following synthetic route:
2'-isopropyl- [1,1' -biphenyl ] under anhydrous and anaerobic conditions]-2,6-diol (G-0, cas No. 2414175-61-2) and thioaryl reagent 2- ((2, 6-dimethylphenyl) thio) benzol [ d]Isothiazol-3 (2H) -one1,1-dioxide (G-1, cas No. 2376073-20-8), catalyst (C) and [. Sup.R) Adding chiral phosphoric acid into the dried reaction tube, and reacting at-50 ℃ at low temperatureAfter 0.5mL of ultra-dry dichloromethane is added into a tube and reacted for 24 hours in an argon atmosphere, the system is heated to-30 ℃ for continuous reaction for 4 hours, the reaction is heated to-20 ℃ again and reacted for 10 hours, and the reaction system is subjected to column chromatography purification to prepare the axial chiral sulfur-containing diphenyl derivative G (product conformation reference document:JACS.2022，144，2943-2952.）。 1 HNMR（400MHz，Chloroform-d）δ7.48（m，2H），7.34（m，1H），7.22–7.07（m，4H），6.91（dd，J=8.6，1.9Hz，1H），6.49（dd，J=8.6，1.9Hz，1H），6.04–5.85（m，1H），4.70（s，1H），2.73（tt，J=6.9，3.5Hz，1H），2.47（d，J=2.2Hz，6H），1.13（dd，J=6.6，2.1Hz，6H）； 13 CNMR（101MHz，CDCl 3 ) Delta 153.52, 152.62, 149.80, 142.50, 132.73, 131.65, 131.25, 129.94, 129.15, 128.80, 128.72, 127.03, 126.72, 114.73, 112.08, 108.54, 30.51, 24.12, 23.94, 22.13.HPLC separation of isomers at 30 ℃, n-hexane:iPrOH=85:15 (volume ratio), flow rate 1mL/min, smaller retention time: 6.84min, main retention time: 8.00min, er=52:48.
Example 8:
the preparation of the axial chiral sulfur-containing diphenyl derivative G is shown in the following synthetic route:
2'-isopropyl- [1,1' -biphenyl ] under anhydrous and anaerobic conditions]-2,6-diol (G-0, cas No. 2414175-61-2) and thioaryl groupsReagent 2- ((2, 6-dimethylphenyl) thio) benzol [ d]Isothiazol-3 (2H) -one1,1-dioxide (G-1, cas No. 2376073-20-8), catalyst (C), compound (H) and [. Sup.R) Adding chiral phosphoric acid into a dried reaction tube, adding 0.5mL of ultra-dry dichloromethane into the reaction tube at the low temperature of minus 50 ℃, reacting for 24 hours in an argon atmosphere, heating the system to minus 30 ℃, continuously reacting for 4 hours, heating the reaction to minus 20 ℃ again, reacting for 10 hours, and purifying the reaction system by column chromatography to obtain the axial chiral sulfur-containing diphenyl derivative G. The yield was 90%. The ee value was 18%.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
The above embodiments are merely for illustrating the present invention and not for limiting the same, and various changes and modifications may be made by one of ordinary skill in the art without departing from the spirit and scope of the invention. Therefore, all equivalent technical solutions are also within the scope of the present invention, which is defined by the claims.
Claims (7)
1. Chiral 5,5', 6' -tetramethyl-3, 3' -di-tert-butyl-1, 1' -biphenyl-2, 2' -diol compounds are shown as follows:
2. A chiral 5,5', 6' -tetramethyl-3, 3' -di-tert-butyl-1, 1' -biphenyl-2, 2' -diol compound according to claim 1, which is any one of the following:
3. the method for preparing chiral 5,5', 6' -tetramethyl-3, 3' -di-tert-butyl-1, 1' -biphenyl-2, 2' -diol compound according to claim 1, wherein the method comprises the following steps: chiral 5,5', 6' -tetramethyl-3, 3 '-di-tert-butyl-1, 1' -biphenyl-2, 2 '-diol, phosphorus trichloride, triethylamine and alkylamine reagent are reacted under the combined action of selenium powder or sulfur powder and solvent to generate chiral 5,5',6 '-tetramethyl-3, 3' -di-tert-butyl-1, 1 '-biphenyl-2, 2' -diol compounds.
4. The process for preparing chiral 5,5', 6' -tetramethyl-3, 3' -di-tert-butyl-1, 1' -biphenyl-2, 2' -diol according to claim 3, wherein the process comprises the steps of: dissolving phosphorus trichloride in dichloromethane, adding triethylamine at 0-5 ℃, then adding alkylamine reagent at room temperature, then adding chiral 5,5', 6' -tetramethyl-3, 3 '-di-tert-butyl-1, 1' -biphenyl-2, 2 '-diol for reaction, then adding selenium powder or sulfur powder for reaction, separating and purifying to obtain chiral 5,5',6 '-tetramethyl-3, 3' -di-tert-butyl-1, 1 '-biphenyl-2, 2' -diol compounds.
5. The process for preparing chiral 5,5', 6' -tetramethyl-3, 3' -di-tert-butyl-1, 1' -biphenyl-2, 2' -diol according to claim 3, wherein the process comprises the steps of: the substituent of the alkylamine reagent is any one of ethyl, isopropyl and isobutyl.
6. The process for preparing chiral 5,5', 6' -tetramethyl-3, 3' -di-tert-butyl-1, 1' -biphenyl-2, 2' -diol according to claim 3, wherein the process comprises the steps of: the alkylamine reagent is a disubstituted amine; the substituents of the disubstituted amine are the same, and the substituents are any one of ethyl, isopropyl and isobutyl.
7. Use of chiral 5,5', 6' -tetramethyl-3, 3' -di-tert-butyl-1, 1' -biphenyl-2, 2' -diol compounds according to any one of claims 1-2 as catalysts for the catalytic preparation of chiral sulfur-containing diphenyl derivatives of the formula
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| CN111205328A (en) * | 2020-02-27 | 2020-05-29 | 上海交通大学 | Chiral sulfur/selenium compound and preparation method and application thereof |
| CN111285901A (en) * | 2020-02-27 | 2020-06-16 | 上海交通大学 | Chiral sulfur/selenium compound based on 1,1' -bi-2-naphthol framework and preparation method and application thereof |
| CN114733566A (en) * | 2022-01-30 | 2022-07-12 | 上海师范大学 | Chiral super-strong carbonic acid catalyst based on BINOL skeleton and preparation method and application thereof |
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| CN111205328A (en) * | 2020-02-27 | 2020-05-29 | 上海交通大学 | Chiral sulfur/selenium compound and preparation method and application thereof |
| CN111285901A (en) * | 2020-02-27 | 2020-06-16 | 上海交通大学 | Chiral sulfur/selenium compound based on 1,1' -bi-2-naphthol framework and preparation method and application thereof |
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