CAJ | 학술논문

通过密度泛函理论(DFT) B3LYP, M062X 和从头算方法 MP2,给出了9-氨基奎宁作为有机催化剂和苯甲酸作为辅助催化剂催化1-溴代硝基甲烷与亚苄基丙酮的不对称共轭加成反应的详细反应机理。反应过程主要包括3个阶段：(1)亚胺离子中间体的形成；(2)亚胺离子与1-溴代硝基甲烷的亲核加成；(3)水解并伴随催化剂的还原。计算结果不仅解释了苯甲酸加合物在亚胺离子形成过程中所起的重要作用,而且提供了一般反应模型以理解这个共轭加成反应的反应机理和对映选择性。
통과밀도범함이론(DFT) B3LYP, M062X 화종두산방법 MP2,급출료9-안기규저작위유궤최화제화분갑산작위보조최화제최화1-추대초기갑완여아변기병동적불대칭공액가성반응적상세반응궤리。반응과정주요포괄3개계단：(1)아알리자중간체적형성；(2)아알리자여1-추대초기갑완적친핵가성；(3)수해병반수최화제적환원。계산결과불부해석료분갑산가합물재아알리자형성과정중소기적중요작용,이차제공료일반반응모형이리해저개공액가성반응적반응궤리화대영선택성。
Asymmetric conjugate addition of 1-bromonitromethane tobenzylidene acetone was catalyzed by 9-amino-9-deoxyepiquinine as organic catalyst and benzoic acid as co-catalyst. We had identified a detailed mechanism of the title reaction with density functional theory(B3LYP and M062X) and ab initio calculations (MP2). The reaction process includes three major stages: (1) the formation of an iminium ion intermediate;(2) the nucleophilic addition between the iminium and 1-bromonitromethane; (3) hydrolysis and recovery of catalyst. The calculated results not only explain benzoic acid as acidic additive plays an important role in the formation of the key reaction iminium intermediate, but also provide a general model to help explain the mechanism and enantioselectivity of the conjugate addition reaction.