Syntheses and Crystal Structures of Chiral BINOL Derivatives and Their Applications in Enantioselective Lewis Acid Catalyzed Addition of Diethylzinc to Aldehydes  

作　　者：刘国华 余焓 姚美 方海斌 薛允宁 

机构地区：[1]Department of Chemistry, College of Life and Environmental Science, Shanghai Normal University

出　　处：《Chinese Journal of Structural Chemistry》2007年第4期477-483,共7页结构化学（英文）

基　　金：Supported by Shanghai Municipal Education Commission (No. 05D215);Shanghai Sciences and Technologies Development Fund (No. 05JC14074); National Natural Science Foundation of China (No. 20673072) ;Shanghai Leading Academic Discipline Project (No. T0402)

摘　　要：Two novel chiral BINOL derivatives with bis（benzylamine） groups at the 3,3- positions have been synthesized through the condensation reaction between 2,2＇-bis（methoxymethyleneoxy）-1,1＇-binaphthyl-3,3＇-dicarboxylic acid and benzylamine or N-phenyl benzylamine in the presence of triethylamine. Suitable single crystal of （R）-N,N＇-dibenzyl-2,2＇-dihydroxy-1, 1＇-binaphthly-3,3＇-diformamide （R）-3 for X-ray diffraction was obtained by recrystallization at room temperature from the mixture solvents. Crystallographic data of （R）-3： C40H36N2O6, Mr = 640.71, monoclinic, space group P21, a = 6.746（3）, b = 21.883（9）, c = 11.723（5）A,β = 104.605（7）°, Z= 2, V= 1674.7（12）A^3, Dc = 1.271 g/cm^3, F（000） = 676, R = 0.0729, wR = 0.1687 andμ（MoKa） = 0.086 mm^-1. Two chiral BINOL ligands were found to be effective in the enantioselective addition of diethylzinc to aldehydes and much different enantioselectivity was observed both in the presence and absence of Ti（Oipr）4. in the former case, （R）-3 showed moderate enantioselectivity, which was lower than that of （R）-BINOL＇s; and in the latter case, （R）-4 gave the highest enantioselectivity up to 93.3% ee.Two novel chiral BINOL derivatives with bis（benzylamine） groups at the 3,3- positions have been synthesized through the condensation reaction between 2,2＇-bis（methoxymethyleneoxy）-1,1＇-binaphthyl-3,3＇-dicarboxylic acid and benzylamine or N-phenyl benzylamine in the presence of triethylamine. Suitable single crystal of （R）-N,N＇-dibenzyl-2,2＇-dihydroxy-1, 1＇-binaphthly-3,3＇-diformamide （R）-3 for X-ray diffraction was obtained by recrystallization at room temperature from the mixture solvents. Crystallographic data of （R）-3： C40H36N2O6, Mr = 640.71, monoclinic, space group P21, a = 6.746（3）, b = 21.883（9）, c = 11.723（5）A,β = 104.605（7）°, Z= 2, V= 1674.7（12）A^3, Dc = 1.271 g/cm^3, F（000） = 676, R = 0.0729, wR = 0.1687 andμ（MoKa） = 0.086 mm^-1. Two chiral BINOL ligands were found to be effective in the enantioselective addition of diethylzinc to aldehydes and much different enantioselectivity was observed both in the presence and absence of Ti（Oipr）4. in the former case, （R）-3 showed moderate enantioselectivity, which was lower than that of （R）-BINOL＇s; and in the latter case, （R）-4 gave the highest enantioselectivity up to 93.3% ee.

关 键 词：crystal structure BINOL derivative asymmetric addition 

分 类 号：O643.32[理学—物理化学]