CN115490732A - Synthesis method of chiral biphenyl diol catalyst - Google Patents
Synthesis method of chiral biphenyl diol catalyst Download PDFInfo
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- CN115490732A CN115490732A CN202211213918.5A CN202211213918A CN115490732A CN 115490732 A CN115490732 A CN 115490732A CN 202211213918 A CN202211213918 A CN 202211213918A CN 115490732 A CN115490732 A CN 115490732A
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- biphenyl
- tetramethyl
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- 239000003054 catalyst Substances 0.000 title claims abstract description 13
- 238000001308 synthesis method Methods 0.000 title abstract description 3
- 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 53
- NMVVBVMYPLMIOU-UHFFFAOYSA-N 6-tert-butyl-2-(3-tert-butyl-2-hydroxy-5,6-dimethylphenyl)-3,4-dimethylphenol Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C=2C(=C(C=C(C)C=2C)C(C)(C)C)O)=C1C NMVVBVMYPLMIOU-UHFFFAOYSA-N 0.000 claims abstract description 27
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 27
- -1 5,5',6,6' -tetramethyl-3,3 ' -di-tert-butyl-1,1 ' -biphenyl-2,2 ' -diol selenium Chemical compound 0.000 claims abstract description 21
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000003973 alkyl amines Chemical class 0.000 claims abstract description 16
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 14
- 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 33
- 238000000034 method Methods 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 8
- 229910052711 selenium Inorganic materials 0.000 claims description 7
- 239000011669 selenium Substances 0.000 claims description 7
- 125000001424 substituent group Chemical group 0.000 claims description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 4
- 239000000758 substrate Substances 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 7
- 238000010189 synthetic method Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 description 21
- 238000003756 stirring Methods 0.000 description 18
- 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
- 238000002360 preparation method Methods 0.000 description 10
- 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 8
- 239000012043 crude product Substances 0.000 description 6
- 235000019439 ethyl acetate Nutrition 0.000 description 6
- 239000000203 mixture Substances 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
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 125000006267 biphenyl group Chemical group 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- DMSZORWOGDLWGN-UHFFFAOYSA-N ctk1a3526 Chemical compound NP(N)(N)=O DMSZORWOGDLWGN-UHFFFAOYSA-N 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 239000011593 sulfur Substances 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
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 3
- 229940043279 diisopropylamine Drugs 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 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
- 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
- 235000010290 biphenyl Nutrition 0.000 description 2
- 238000006555 catalytic 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
- 238000001816 cooling Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- JXMQYKBAZRDVTC-UHFFFAOYSA-N hexa-2,4-diyne-1,6-diol Chemical compound OCC#CC#CCO JXMQYKBAZRDVTC-UHFFFAOYSA-N 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
- 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
- 150000003568 thioethers Chemical class 0.000 description 2
- XOHUEYCVLUUEJJ-UHFFFAOYSA-I 2,3-Diphosphoglycerate Chemical compound [O-]P(=O)([O-])OC(C(=O)[O-])COP([O-])([O-])=O XOHUEYCVLUUEJJ-UHFFFAOYSA-I 0.000 description 1
- PUAQLLVFLMYYJJ-UHFFFAOYSA-N 2-aminopropiophenone Chemical compound CC(N)C(=O)C1=CC=CC=C1 PUAQLLVFLMYYJJ-UHFFFAOYSA-N 0.000 description 1
- 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 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
- 150000008039 phosphoramides Chemical class 0.000 description 1
- 239000000126 substance Substances 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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—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
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0271—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds also containing elements or functional groups covered by B01J31/0201 - B01J31/0231
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- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention discloses a synthesis method of a chiral 5,5',6,6' -tetramethyl-3,3 ' -di-tert-butyl-1,1 ' -biphenyl-2,2 ' -diol catalyst, which belongs to the technical field of organic chemical synthesis, and particularly relates to a chiral 5,5',6,6' -tetramethyl-3,3 ' -di-tert-butyl-1,1 ' -biphenyl-2,2 ' -diol and phosphorus trichloride, triethylamine and an alkylamine reagent, under the combined action of selenium powder or sulfur powder and a solvent, chiral 5,5',6,6' -tetramethyl-3,3 ' -di-tert-butyl-1,1 ' -biphenyl-2,2 ' -diol compounds are generated. The invention is a synthetic method of 5,5',6,6' -tetramethyl-3,3 ' -di-tert-butyl-1,1 ' -biphenyl-2,2 ' -diol selenium/sulfide, which has the advantages of mild reaction conditions, economic and easily-obtained raw materials, good repeatability, simple reaction, wide substrate application range and good economy.
Description
Technical Field
The invention belongs to the technical field of organic chemical synthesis, and particularly relates to a synthetic method of a chiral 5,5',6,6' -tetramethyl-3,3 ' -di-tert-butyl-1,1 ' -biphenyl-2,2 ' -diol catalyst.
Background
For the first synthesis of such a backbone, a patent was reported in 1999. Later reports on the synthesis of the skeletons are also concentrated in patents. The literature on the first chemical synthesis of this type of scaffold is reported in 2006 (Chemistry-A European journal. 2006, 12, 7482-7488), siegfried R. Waldvogel, which reports the synthesis of this type of scaffold using electrochemical anodic oxidation. Iwao Ojima in 2003 catalyzed asymmetric hydrogenation using phosphites of this type of backbone as ligands (org. Lett. 2003, 5, 21, 3831-3834), which was the first reported monodentate phosphite ligand from enantiomerically pure axially chiral bisphenols. Subsequently, a series of chiral reactions such as asymmetric hydroformylation of allyl cyanide are catalyzed by phosphite ligands with the skeleton. In 2007, the first example of the ligand of the monodentate phosphoramide with the framework is reported (Angew. Chem. Int. Ed. 2007, 46, 1497-1500), and the ligand is applied to the high enantioselective asymmetric hydrogenation reaction induced under the catalysis of iridium. In 2008, hexamethylphosphoric triamide and dichloro-N, N-diisopropyl phosphoramidite are respectively utilized to synthesize methyl and isopropyl substituted ligands of the skeleton phosphoramide. In recent years, the synthesis of the phosphoramide ligand of the skeleton is mainly focused on the development of substituents on different nitrogen. Until 2010 Anna g. Wenzel (eur. J. Org. Chem. 2010, 3027-3031) reported that-NHTf substituted sulphides of this type of framework catalyzed reactions as catalysts, which was also the only example reported for sulphides of this type of framework. No alkyl substituted selenium/sulfide compounds have been reported for phosphoramides of this backbone. Therefore, based on previous reports, the application of this skeleton as ligand is relatively wide, so we have developed the alkyl substituted selenium/sulfide of phosphoramide of this skeleton is very important and necessary.
Disclosure of Invention
The invention aims to provide a synthetic method of 5,5',6,6' -tetramethyl-3,3 ' -di-tert-butyl-1,1 ' -biphenyl-2,2 ' -diol selenium/sulfide, which has the advantages of mild reaction conditions, economic and easily-available raw materials, good repeatability, simple reaction, wide substrate application range and good economy.
The technical scheme adopted by the invention for realizing the purpose is as follows:
a chiral 5,5',6,6' -tetramethyl-3,3 ' -di-tert-butyl-1,1 ' -biphenyl-2,2 ' -diol compound, as shown below:
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 2 Same, R 1 Or R 2 Is C 2-4 Any of alkyl groups.
Preferably, the chiral 5,5',6,6' -tetramethyl-3,3 ' -di-tert-butyl-1,1 ' -biphenyl-2,2 ' -diol compound is any one of the following:
the invention discloses a preparation method of a chiral 5,5',6,6' -tetramethyl-3,3 ' -di-tert-butyl-1,1 ' -biphenyl-2,2 ' -diol compound, which is characterized in that a chiral 5,5',6,6' -tetramethyl-3,3 ' -di-tert-butyl-1,1 ' -biphenyl-2,2 ' -diol, phosphorus trichloride, triethylamine and an alkylamine reagent are reacted under the combined action of selenium powder or sulfur powder and a solvent to generate the chiral 5,5',6,6' -tetramethyl-3,3 ' -di-tert-butyl-1,1 ' -biphenyl-2,2 ' -diol compound.
Preferably, phosphorus trichloride is dissolved in dichloromethane, triethylamine is added at 0-5 ℃, then alkylamine reagent is added at room temperature, chiral 5,5',6,6' -tetramethyl-3,3 '-di-tert-butyl-1,1' -biphenyl-2,2 '-diol is added for reaction, then selenium powder or sulfur powder is added for reaction, and separation and purification are carried out to obtain chiral 5,5',6,6 '-tetramethyl-3,3' -di-tert-butyl-1,1 '-biphenyl-2,2' -diol compound.
More preferably, room temperature means a temperature of 20-35 ℃.
More preferably, phosphorus trichloride is added to methylene chloride so that the concentration of phosphorus trichloride is 0.05 to 0.4 mmol/mL.
More preferably, 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, and 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',6,6' -tetramethyl-3,3 ' -di-tert-butyl-1,1 ' -biphenyl-2,2 ' -diol is used in a molar amount of 80 to 120% of the molar amount of phosphorus trichloride used.
More preferably, the selenium powder is used in a molar amount of 200-400% of the chiral 5,5',6,6' -tetramethyl-3,3 ' -di-tert-butyl-1,1 ' -biphenyl-2,2 ' -diol.
More preferably, the sulfur powder is used in a molar amount of 200-400% of the chiral 5,5',6,6' -tetramethyl-3,3 ' -di-tert-butyl-1,1 ' -biphenyl-2,2 ' -diol.
More preferably, phosphorus trichloride is dissolved in dichloromethane, after cooling to 0 ℃ at low temperature, triethylamine is dropwise added into the solution, the system is heated to room temperature after reaction, alkylamine reagent is dropwise added, then stirring is carried out, chiral 5,5',6,6' -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 continuous stirring reaction, and then the compound is obtained after reduced pressure distillation and column chromatography purification.
More preferably, phosphorus trichloride is dissolved in dichloromethane, after cooling to a low temperature of 0 ℃, triethylamine is added dropwise thereto, after reacting for 10min, the system is raised to room temperature, alkylamine is added, and then 12h is stirred. Chiral 5,5',6,6' -tetramethyl-3,3 ' -di-tert-butyl-1,1 ' -biphenyl-2,2 ' -diol derivatives were added to the system at room temperature to stir 12h, selenium was added at room temperature, and the reaction was continued to stir 12 h. Then the catalyst is obtained by reduced pressure distillation and column chromatography purification.
Preferably, the alkylamine reagent is a disubstituted amine.
More preferably, the disubstituted amines have the same substituent, and the substituent is any of ethyl, isopropyl and isobutyl.
Preferably, the substituent of the alkylamine reagent is C 1-5 Any of alkyl groups.
The invention discloses application of the chiral 5,5',6,6' -tetramethyl-3,3 ' -di-tert-butyl-1,1 ' -biphenyl-2,2 ' -diol compound as a catalyst.
The preparation route of the chiral 5,5',6,6' -tetramethyl-3,3 ' -di-tert-butyl-1,1 ' -biphenyl-2,2 ' -diol compound is as follows:
the invention adopts chiral 5,5',6,6' -tetramethyl-3,3 '-di-tert-butyl-1,1' -biphenyl-2,2 '-diol and phosphorus trichloride, triethylamine and alkylamine reagent to generate chiral 5,5',6,6 '-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, thereby having the following advantages: the method realizes the synthesis of different chiral 5,5',6,6' -tetramethyl-3,3 ' -di-tert-butyl-1,1 ' -biphenyl-2,2 ' -diol derivative selenium/sulfide catalysts for the first time by selecting different alkylamines; the method adopts the economically available 5,5',6,6' -tetramethyl-3,3 '-di-tert-butyl-1,1' -biphenyl-2,2 '-diol and cheap and easily available alkylamine as substrates, and prepares the chiral 5,5',6,6 '-tetramethyl-3,3' -di-tert-butyl-1,1 '-biphenyl-2,2' -diol derivative selenium/sulfide catalyst by a one-pot method, and the reaction process avoids a complex synthetic route; the method has diversified substrates, and can synthesize 5,5',6,6' -tetramethyl-3,3 ' -di-tert-butyl-1,1 ' -biphenyl-2,2 ' -diol derivative selenium/sulfide catalysts with various alkyl substituents.
Therefore, the invention is a synthetic method of 5,5',6,6' -tetramethyl-3,3 ' -di-tert-butyl-1,1 ' -biphenyl-2,2 ' -diol selenium/sulfide, which has the advantages of mild reaction conditions, economic and easily-obtained raw materials, good repeatability, simple reaction, wide substrate application range and good economy.
Drawings
FIG. 1 is a graph of the yields of chiral 5,5',6,6' -tetramethyl-3,3 ' -di-tert-butyl-1,1 ' -biphenyl-2,2 ' -diol compounds.
Detailed Description
The technical solution of the present invention is further described in detail below with reference to the following detailed description and the accompanying drawings:
in the present embodiment, the hydrogen nuclear magnetic resonance spectrum of the compound (b) ((b)) 1 H NMR、 13 C NMR) was determined from Bruker AVANCE III HD 400 and the solvent was deuterated chloroform. Chemical shifts (δ) are quoted in ppm, with tetramethylsilane as an internal standard, and the multiplicities are shown: s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet.
Example 1:
compound (A) to (B)S) The preparation of A, the synthetic route is shown below:
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 And N is added. After 10min, the reaction was warmed to room temperature and 0.423mmol diisopropylamine was added, followed by stirring for 5h. 0.423mmol (S) - (-) - -5,5',6,6' -tetramethyl-3,3 ' -di-tert-butyl-1,1 ' -biphenyl-2,2 ' -diol is stirred and reacted for 12 hours, then 1.269mmol selenium powder is added under the condition of room temperature, and stirred and reacted for 12 hours. After completion of the reaction, it was filtered through celite, concentrated in vacuo and spin-dried. The crude product was purified by silica gel (EtOAc: petroleum ether volume ratio 1: 100) 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:
compound (A) to (B)S) The preparation of-B, the synthetic route is shown below:
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 And N is added. After 10min, the reaction was allowed to warm to room temperature and 0.423mmol diisopropylamine was added, followed by stirring for 5h. 0.423mmol (S) - (-) -5,5',6,6' -tetramethyl-3,3 ' -di-tert-butyl-1,1 ' -biphenyl-2,2 ' -diol was added to the system at room temperature, and after 12 hours of stirring reaction, 1.269mmol of sulfur powder was added at room temperature, and the mixture was stirred for 12 hours. After completion of the reaction, the mixture was filtered through celite, concentrated in vacuo and spin-dried. The crude product was purified by silica gel (EtOAc: petroleum ether in volume ratio 1.
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:
compound (A) to (B)S) The preparation of-C, the synthetic route is shown below:
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 And N is added. After 10min, the reaction was warmed to room temperature and 0.141mmol of diisobutylamine was added, followed by stirring for 5h. 0.141mmol (S) - (-) -5,5',6,6' -tetramethyl-3,3 ' -di-tert-butyl-1,1 ' -biphenyl-2,2 ' -diol is added to the system at room temperature, and after 12 hours of stirring reaction, 0.423mmol selenium powder is added at room temperature, and the stirring reaction is carried out for 12 hours. After completion of the reaction, the mixture was filtered through celite, concentrated in vacuo and spin-dried. The crude product was purified by silica gel (EtOAc: petroleum ether volume ratio 1: 120) 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:
compound (A) to (B)S) Preparation of-D, the synthetic route is shown below:
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 And N is added. After 10min, the reaction was warmed to room temperature and 0.141mmol of diisobutylamine was added, followed by stirring for 5h. 0.141mmol (S) - (-) -5,5',6,6' -tetramethyl-3,3 ' -di-tert-butyl-1,1 ' -biphenyl-2,2 ' -diol was added to the system at room temperature, and after 12 hours of stirring reaction, 0.423mmol of sulfur powder was added at room temperature, and the reaction was stirred for 12 hours. After completion of the reaction, the mixture was filtered through celite, concentrated in vacuo and spin-dried. The crude product was purified by silica gel (EtOAc: petroleum ether volume ratio 1: 120) 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:
compound (A) to (B)S) Preparation of-E, the synthetic route is shown below:
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 And N is added. After 10min, the reaction was warmed to room temperature and 0.141mmol diethylamine was added, followed by stirring for 5h. 0.141mmol (S) - (-) -5,5',6,6' -tetramethyl-3,3 ' -di-tert-butyl-1,1 ' -biphenyl-2,2 ' -diol was added to the system at room temperature, and after 12 hours of stirring reaction, 0.423mmol of sulfur powder was added at room temperature, and the reaction was carried out for 12 hours of stirring reaction. After completion of the reaction, the mixture was filtered through celite, concentrated in vacuo and spin-dried. The crude product was purified by silica gel (EtOAc: petroleum ether volume ratio 1: 120) 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:
compound (A) to (B)S) The preparation of F, the synthetic route is shown below:
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 And N is added. After 10min, the reaction was warmed to room temperature and 0.141mmol diethylamine was added, followed by stirring for 5h. 0.141mmol (S) - (-) -5,5',6,6' -tetramethyl-3,3 ' -di-tert-butyl-1,1 ' -biphenyl-2,2 ' -diol was added to the system at room temperature, and after 12 hours of stirring reaction, 0.423mmol of sulfur powder was added at room temperature, and the reaction was stirred for 12 hours. After completion of the reaction, the mixture was filtered through celite, concentrated in vacuo and spin-dried. The crude product was purified by silica gel (EtOAc: petroleum ether volume ratio 1: 120) 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 the compounds A to F obtained by the respective methods in examples 1 to 6 are shown in FIG. 1, wherein S1 is the compound A, S2 is the compound B, S3 is the compound C, S4 is the compound D, S5 is the compound E, and S6 is the compound F.
Example 7:
the preparation of the axial chiral sulfur-containing diphenyl derivative G has the following synthetic route:
2 '-isoproyl- [1,1' -biphenyl under anhydrous and anaerobic conditions]2,6-diol (G-0, cas number: 2414175-61-2) and the thioaryl reagent 2- ((2,6-dimethylphenyl) thio) benzol [ d]isothiazol-3 (2H) -one1,1-dioxide (G-1, cas number: 2376073-20-8), catalyst (C) and (C)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-50 ℃, reacting for 24 hours in an argon atmosphere, raising the temperature of the system to-30 ℃, continuing to react for 4 hours, raising the temperature of the reaction system to-20 ℃, reacting for 10 hours, and purifying the reaction system by column chromatography to obtain the axial chiral sulfur-containing diphenyl derivative G (product conformation reference: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 ) δ 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, temperature 30 ℃, n-hexane:i-PrOH =85 (volume ratio), flow rate 1mL/min, smaller retention time: 6.84min, main retention time: 8.00min, er = 52.
Example 8:
the preparation of the axial chiral sulfur-containing diphenyl derivative G has the following synthetic route:
2 '-isoproyl- [1,1' -biphenyl under anhydrous and anaerobic conditions]2,6-diol (G-0, cas number: 2414175-61-2) and the thioaryl reagent 2- ((2,6-dimethylphenyl) thio) benzol [ d]isothiazol-3 (2H) -one1,1-dioxide (G-1, cas number: 2376073-20-8), catalyst (C), compound (H) and (C)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-50 ℃, reacting for 24 hours in an argon atmosphere, raising the temperature of the system to-30 ℃, continuing to react for 4 hours, raising the temperature of the reaction system to-20 ℃, reacting for 10 hours, and carrying out column chromatography purification on the reaction system to obtain the axial chiral sulfur-containing diphenyl derivative G. The yield was 90%. The ee value was 18%.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, 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 embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
The above embodiments are merely illustrative, and not restrictive, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention. Therefore, all equivalent technical solutions also belong to the scope of the present invention, and the protection scope of the present invention should be defined by the claims.
Claims (10)
1. A chiral 5,5',6,6' -tetramethyl-3,3 ' -di-tert-butyl-1,1 ' -biphenyl-2,2 ' -diol compound is shown below:
2. The chiral 5,5',6,6' -tetramethyl-3,3 ' -di-tert-butyl-1,1 ' -biphenyl-2,2 ' -diol compound of claim 1, wherein: r is 1 Is any one of ethyl, isopropyl and isobutyl, R 2 Is any one of ethyl, isopropyl and isobutyl.
3. The chiral 5,5',6,6' -tetramethyl-3,3 ' -di-tert-butyl-1,1 ' -biphenyl-2,2 ' -diol compound of claim 1, wherein: r 1 And R 2 Same as R 1 Or R 2 Is C 2-4 Any of alkyl groups.
4. The chiral 5,5',6,6' -tetramethyl-3,3 ' -di-tert-butyl-1,1 ' -biphenyl-2,2 ' -diol compound of claim 1, which is any one of:
5. the method for preparing the chiral 5,5',6,6' -tetramethyl-3,3 ' -di-tert-butyl-1,1 ' -biphenyl-2,2 ' -diol compound as claimed in claim 1, wherein: chiral 5,5',6,6' -tetramethyl-3,3 '-di-tert-butyl-1,1' -biphenyl-2,2 '-diol and phosphorus trichloride, triethylamine and alkylamine reagents are reacted under the combined action of selenium powder or sulfur powder and solvent to produce chiral 5,5',6,6 '-tetramethyl-3,3' -di-tert-butyl-1,1 '-biphenyl-2,2' -diol compounds.
6. The method for preparing the chiral 5,5',6,6' -tetramethyl-3,3 ' -di-tert-butyl-1,1 ' -biphenyl-2,2 ' -diol compound according to claim 5, wherein the method comprises the following steps: dissolving phosphorus trichloride in dichloromethane, adding triethylamine at 0-5 ℃, then adding alkylamine reagent at room temperature, then adding chiral 5,5',6,6' -tetramethyl-3,3 '-ditert-butyl-1,1' -biphenyl-2,2 '-diol for reaction, then adding selenium powder or sulfur powder for reaction, and separating and purifying to obtain chiral 5,5',6,6 '-tetramethyl-3,3' -ditert-butyl-1,1 '-biphenyl-2,2' -diol compounds.
7. The method for preparing the chiral 5,5',6,6' -tetramethyl-3,3 ' -di-tert-butyl-1,1 ' -biphenyl-2,2 ' -diol compound according to claim 5, wherein the method comprises the following steps: the substituent of the alkylamine reagent is C 1-5 Any of alkyl groups.
8. The method for preparing the chiral 5,5',6,6' -tetramethyl-3,3 ' -di-tert-butyl-1,1 ' -biphenyl-2,2 ' -diol compound according to claim 5, wherein the method comprises the following steps: the alkylamine reagent is a disubstituted amine.
9. The method for preparing the chiral 5,5',6,6' -tetramethyl-3,3 ' -di-tert-butyl-1,1 ' -biphenyl-2,2 ' -diol compound according to claim 8, wherein the method comprises the following steps: the substituent of the disubstituted amine is the same, and the substituent is any one of ethyl, isopropyl and isobutyl.
10. Use of the chiral 5,5',6,6' -tetramethyl-3,3 ' -di-tert-butyl-1,1 ' -biphenyl-2,2 ' -diol compound of any of claims 1-4 as a catalyst.
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