季铵盐中N-手性在不对称烷基化反应中的作用研究SignificanceofN.PDF

2011 年第 31 卷 有 机 化 学 Vol. 31, 2011 第 3 期, 341～345 Chinese Journal of Organic Chemistry No. 3, 341～345 ·研究论文· 季铵盐中 N-手性在不对称烷基化反应中的作用研究 a,b a,b a *,a 鲁 军 廖霞俐 陈晓珍 王 淳 (a 中国科学院成都生物研究所天然产物中心 成都 610041) (b 中国科学院研究生院 北京 100049) 摘要 为了探明手性季铵盐中N-手性在不对称烷基化反应中的作用, 从天然氨基酸出发合成了4 个仅含C-手性的季铵 盐, 将它们与 4 个同时含有 C-和 N-手性的季铵盐用于催化二苯亚胺甘氨酸叔丁酯的不对称烷基化反应, 通过对烷基化 产物的 ee 值进行比较, 结果表明简单的链状季铵盐中的N-手性不能对烷基化产物的 ee 值产生明显影响. 关键词 N-手性季铵盐; 不对称催化; 氨基酸; 烷基化 Significance of N-Stereogenic Centre in Quaternary Ammonium Salts in Asymmetric Alkylation Lu, Juna,b Liao, Xialia,b Chen, Xiaozhena Wang, Chun*,a a ( Chengdu Institute of Biology, Chinese Academy of Sciences, Chengdu 610041) (b Graduate School of Chinese Academy of Sciences, Beijing 100049) Abstract To elucidate the asymmetric inductive effect of the N-stereogenic centre in quaternary ammo- nium salts, four quaternary ammonium salts with C-chiral centre were synthesized from amino acids. These salts together with four previously synthesized salts containing both N- and C-chiral centres, were applied as asymmetric phase-transfer catalysts in the enantioselective alkylation of N-(diphenylmethylene)-glycine tert-butyl ester with benzyl bromide. The relationship between the ee values of products and the structures of catalysts indicated that the N-stereogenic centre alone showed no significant effect on the enantioselectivity of a