Koide Hiroshige, Hata Takeshi, Uemura Motokazu
Department of Chemistry, Faculty of Integrated Arts and Sciences, Osaka Prefecture University, Sakai, Osaka 599-8531 Japan.
J Org Chem. 2002 Mar 22;67(6):1929-35. doi: 10.1021/jo011052p.
Axially chiral benzamides and anilides were prepared by enantiotopic lithiation at the distinguished benzylic methyl of prochiral tricarbonylchromium complexes of N,N-diethyl 2,6-dimethylbenzamide (1) and N-methyl-N-acyl 2,6-dimethylaniline (14 and 21) with a chiral lithium amide base followed by electrophilic substitution in good yields with high optical purity. The resulting axially chiral chromium-complexed benzamides and anilides were oxidized under air to give chromium-free axially chiral benzamides and anilides in an enantiomerically active form without axial bond rotation at room temperature.
通过使用手性酰胺锂碱，对N,N - 二乙基2,6 - 二甲基苯甲酰胺（1）和N - 甲基 - N - 酰基2,6 - 二甲基苯胺（14和21）的前手性三羰基铬配合物中独特的苄基甲基进行对映异位锂化反应，随后进行亲电取代反应，以高光学纯度和良好产率制备了轴手性苯甲酰胺和苯胺。所得的轴手性铬配合的苯甲酰胺和苯胺在空气中被氧化，在室温下以对映体活性形式得到无铬的轴手性苯甲酰胺和苯胺，且不存在轴向键旋转。
