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Method for catalyzing asymmetrically synthesized axially chiral biaryl diphenol

A synthetic method and asymmetric technology, applied in the field of catalytic asymmetric synthesis of axial chiral biaryl diphenols, can solve the problems of low yield, less research and reports, etc., and achieve the advantages of convenient source, easy preparation, and no heavy metal pollution Effect

Active Publication Date: 2015-12-16
SOUTH UNIVERSITY OF SCIENCE AND TECHNOLOGY OF CHINA
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Problems solved by technology

[0004] Among the currently known methods for synthesizing axially chiral biaryl diphenols with enantioselectivity, metal-catalyzed asymmetric oxidative cross-coupling reactions are used, although oxidative cross-coupling reactions can directly obtain asymmetric biaryl diphenols. phenol, but this method is only applicable to some compounds with specific substituents; another method is kinetic resolution, the defect of this method is that the yield is lower than 50%, and there are few related studies and reports

Method used

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  • Method for catalyzing asymmetrically synthesized axially chiral biaryl diphenol
  • Method for catalyzing asymmetrically synthesized axially chiral biaryl diphenol
  • Method for catalyzing asymmetrically synthesized axially chiral biaryl diphenol

Examples

Experimental program
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Effect test

Embodiment 1

[0034] General synthetic method of 1,4-dihydroxybenzene-2-carboxylate

[0035]

[0036] Dissolve 2,5-dihydroxybenzoic acid (6.3 g, 40 mmol) and substituted benzyl bromide (174 mmol) in DMF (N, N-dimethylformamide, 100 mL), and add KHCO under stirring 3 (10.7g, 107mmol) solid, the resulting mixture was heated to 70°C and stirred for 24h, then the reaction solution was cooled to room temperature, diluted with 1M dilute hydrochloric acid (200mL), extracted with DCM (100mLx2), and the obtained organic phase was washed with water (100mLx2), MgSO4 was dried, the solvent was concentrated, and DCM / PE (petroleum ether) = 2 / 1 was used as the eluting solvent, and the obtained residue was purified by silica gel column chromatography to obtain the product.

[0037]

[0038] Yield 74%; 1 HNMR (400MHz, CDCl 3 )δ10.32(s,1H),7.44-7.30(m,6H),7.02-6.99(m,1H),6.88(d,J=8.8Hz,1H),5.36(s,2H),4.70(s ,1H); 13 CNMR (100Hz, CDCl 3 ) δ 169.43, 155.86, 148.14, 135.21, 128.85, 128.72, 128.42, 12...

Embodiment 2

[0047] General Synthesis of 2-Alkoxycarbonyl-1,4-Benzoquinones

[0048]

[0049] Silver oxide (3.0mmol) and MgSO 4 (3.0mmol) was added to a solution of 1,4-dihydroxybenzene-2-carboxylate (1.0mmol) in ether (20mL), the resulting reaction solution was stirred at 25°C for 1.5h, filtered, and the filtrate was concentrated to obtain the product.

[0050]

[0051] Yield 95%; 1 HNMR (400MHz, CDCl 3 )δ=7.14(d, J=1.6Hz, 1H), 6.88-6.83(m, 2H), 3.93(s, 3H); 13 CNMR (100Hz, CDCl 3 ) δ 186.86, 182.86, 163.21, 137.07, 137.02, 136.63, 136.23, 53.02.

[0052]

[0053] Yield 96%; 1 HNMR (400MHz, CDCl 3 )δ=7.09(d, J=1.6Hz, 1H), 6.85-6.80(m, 2H), 4.37(q, J=7.1Hz, 2H), 1.36(t, J=7.1Hz, 6H); 13 CNMR (100Hz, CDCl 3 ) δ 187.11, 183.19, 162.24, 137.03, 136.67, 135.91, 135.79, 61.98, 13.99.

[0054]

[0055] Yield 94%; 1 HNMR (400MHz, CDCl 3 )δ=7.09(d,J=1.6Hz,1H),6.83-6.82(m,2H),4.26(t,J=6.4Hz,2H),1.91-1.74(m,2H),1.01(t,J =7.2Hz,3H); 13 CNMR (100Hz, CDCl 3 ) δ 186.88, 182.87,...

Embodiment 3

[0069] Synthesis of 7-phenyl-2-naphthol

[0070]

[0071] Phenylboronic acid (0.24g, 2.0mmol), Ba(OH) 2 ·8H 2 O (0.9g, 2.8mmol), Pd (PPh 3 ) 4 (0.06g, 0.05mmol), 1,4-dioxane (10mL), H 2 O (3mL) and 7-bromo-2-naphthol (1.5mmol) were refluxed under nitrogen for 24h, cooled to room temperature, 1,4-dioxane was removed, and the resulting phase was dissolved in DCM (30mL), 1M hydrochloric acid Wash (20mL×3), wash with saturated brine (20mL×2), Na 2 SO 4 After drying, the solvent was removed, and the residue was purified by silica gel column chromatography (PE / DCM=2 / 1) to obtain the product.

[0072] Yield 72%; 1 HNMR (400MHz, CDCl 3 )δ=7.88-7.83(m, 2H), 7.79(d, J=8.8Hz, 1H), 7.72(d, J=8.2Hz, 2H), 7.61(d, J=8.5Hz, 1H), 7.48( t, J=7.6Hz, 2H), 7.38(t, J=7.2Hz, 1H), 7.21-7.20(m, 1H), 7.12-7.10(m, 1H), 5.06(s, 1H); 13 CNMR (100Hz, CDCl 3 )δ 153.84, 141.30, 139.41, 134.99, 129.76, 128.96, 128.42, 128.25, 127.56, 124.46, 123.61, 117.93, 109.91.

[0073] Synthesis of 6-pheny...

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Abstract

The invention discloses a method for catalyzing asymmetrically synthesized axially chiral biaryl diphenol. In an organic solvent, chiral phosphoric acid is taken as a catalyst, a compound shown in a formula III is obtained by reaction on a compound shown in a formula I and a compound shown in a formula II, wherein R1 is alkoxyl, an ester group, halogen, alkyl, hydroxyl, aryl, a formyl group or amide; R2 is alkoxyl, cyano, an ester group, alkyl, aryl, halogen or H. According to the method disclosed by the invention, in a mild reaction condition, simple and easily prepared raw materials are used to synthesize the axially chiral biaryl diphenol with a high yield. The synthetic method disclosed by the invention has good enantioselectivity and the ee value of the obtained product is very high; the synthetic method disclosed by the invention can endure various functional groups and a substituent of 2-naphthol can be an electron-withdrawing substituent or an electron donating substituent. The catalyst used in the method is convenient in source and free of heavy metal pollution, and has an industrialized prospect. The formulae are shown in the description.

Description

technical field [0001] The invention relates to a method for catalytically asymmetrically synthesizing axial chiral biaryl diphenols, in particular to asymmetrically synthesizing axial chiral biaryl diphenols through organocatalytic arylation of 2-naphthol. Background technique [0002] Axichiral BINOL and its derivatives have been widely used in asymmetric reactions, and they can also be transformed into corresponding BINAP and phosphoric acid, which can be used as ligands or catalysts in various asymmetric reactions. Therefore, how to construct their skeletons has attracted the attention of organic chemists. Recent studies have shown that asymmetric BINOL derivatives biaryl diphenols can also be used as effective chiral ligands or catalysts. In biologically active natural product molecules, the biaryl diphenol backbone also widely exists, such as Vancomycin (Vancomycin), Gossypol (Gossypol) and Knipholone. [0003] [0004] Among the currently known methods for synthe...

Claims

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Application Information

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IPC IPC(8): C07C69/94C07C67/343C07B53/00
CPCC07B2200/07C07C67/343C07C69/94
Inventor 谭斌刘心元陈叶辉程道娟张健
Owner SOUTH UNIVERSITY OF SCIENCE AND TECHNOLOGY OF CHINA
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