Lewis碱催化的α-胺基腈及氰醇的烯丙基官能团化反应研究及应用有机化学.pdfVIP

DOI: 10.6023/cjoc201406038 研究专题 有机化学 Chinese Journal of Organic Chemistry ACCOUNT Lewis 碱催化的α-胺基腈及氰醇的烯丙基官能团化反应研究及应用 秦天游a,b 张晓安a,b 寮渭巍*,b (a 大连理工大学精细化工国家重点实验室 大连 116024) (b 吉林大学化学学院 长春 130012) 摘要 对我们研究小组近几年在 Lewis 碱催化具有 α-位氢的 α-胺基腈类及氰醇类化合物与 Morita-Baylis-Hillman (MBH)加合物立体选择性的烯丙基化反应方面取得的初步成果进行了小结. 通过与MBH 加合物的烯丙基取代反应, 有 效地构建了具有 α-位季碳结构单元的多官能团腈类衍生物, 而且基于此发展了一类非金属催化的烯烃分子内氰官能团 化反应, 构建了 β-位有季碳结构单元的官能团化的腈类化合物. 此外对影响反应的可能因素也做了讨论, 提出了可能 的反应机理. 关键词 烯丙基化; 路易斯碱; 催化; α-胺基腈; 氰醇; 碳氰化反应 Lewis Base-Catalyzed Allylic Alkylation of α-Amino Nitriles and Cyanohydrins and Synthetic Applications Qin, Tianyoua,b Zhang, Sean Xiao-Ana,b Liao, Weiwei*,b a ( State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024) b ( Department of Organic Chemistry, College of Chemistry, Jilin University , Changchun 130012) Abstract This article summarized our recent progress in Lewis base-catalyzed the direct allylic substitutions of Mo- rita-Baylis-Hillman (MBH) adducts with α-amino nitriles and cyanohydrins bearing an α-hydrogen, which provided efficient access to functionalized α-amino nitriles and cyanohydrins incorporating quaternary carbon centers. On the basis of these, a novel metal-free carbocyanation (alkenylcyanation and acylcyanation) approach to construct functionalized nitriles incorpo- rating β-quaternary carbon center has been developed. In addition, the several factors influencing these chemical transforma- tions are discusse