不对称合成 ⅩⅥ.(十)-樟脑亚胺的立体控制反应和樟脑结构的研究——(十)-樟脑缩苄胺转动势能计算和构象分析

Asymmetric SynthesisⅩ Ⅵ. Study on the Relationship Between the Stereocontrolled Reaction and Structure of (+)-Camphor Imine——The Calculation on Rotational Energy and the Configuration Analysis of (+)—Camphor Benzylimine

本文对N-(对-硝基)苄基-1,7,7-三甲基-双环[2.2.1]庚烷-2-亚胺(3)和N-[11—[12-羟基-12-二苯基]甲基]苄基-1,7,7-三甲基-双环[2.2.1]庚烷-2-亚胺(4)进行了X-射线晶体结构分析。采用MOPAC程序的MNDO方法对(+)-樟脑缩苄胺即N-苄基-1,7,7-三甲基-双环[2.2.1]庚烷-2-亚胺(2a)的内部转动势能进行了理论计算。结果表明,(+)-樟脑缩苄胺(2a)以反式(trans)构象形式存在,它在不对称反应中的立体选择性主要受樟脑环上方C10甲基的控制。

X-ray crystal structure analysis of N-(p-nitro) benzyl-1, 7, 7-trimethyl-bicyclo[2. 2. 1] heptan-2-imine(3) and N-[11-(12-hydroxy-12-diphenyl)-methy1] benzyl-1, 7, 7-trimethyl-bicyclo[2. 2. 1] heptan-2-imine(4) has been achieved. The rotational energy of N-benzyl-1, 7, 7-trimethyl-bicyclo[2. 2. 1] heptan-2-imine(2a) is calculated by MNDO method of MOPAC program. The result is shown that (+)-camphor imine(2a) is kept up a trans configuration and the stereoselectivity of(2a) in asymmetric reaction has been controlled mainly by C10-methyl of(+)-camphor.