原位制备联烯酯的分子间[2+2]环加成反应研究  

Intermolecular [2+2] Cycloaddition of in-situ Generated Allenylic Esters

作　　者：赵立芳[1] 同晓娟[1] 祝海涛[1] 杨得锁[1] 凡明锦[1] 

机构地区：[1]宝鸡文理学院化学化工学院,宝鸡721013

出　　处：《有机化学》2017年第3期646-651,共6页Chinese Journal of Organic Chemistry

基　　金：陕西省教育厅重点实验室(Nos.15JS006;14JS005);宝鸡文理学院博士科研启动计划(Nos.ZK15045;ZK16060)资助项目~~

摘　　要：发展便捷有效、具有高选择性的[2+2]环加成反应,对环丁烷类化合物的合成具有重要的科学意义.以一水合对甲苯磺酸(Ts OH·H_2O)作为催化剂,氯铬酸吡啶(PCC)作为氧化剂,实现了2-(3-羟基-3,3-二芳基丙炔基)苯甲醛原位制备联烯酯中间体的分子间[2+2]环加成反应,成功地构建了一系列高度取代的环丁烷类化合物.该反应具有条件温和、原子经济以及高区域选择性等优点.通过1H NMR,13C NMR,HRMS及X射线单晶衍射对产物结构进行了表征,并简要探讨了其反应机理.The development of a convenient and effective [2＋2] cycloaddition for the synthesis of highly substituted cyclo- butanes with excellent selectivity is of great scientific significance. Using p-toluenesulfonic acid monohydrate （TsOH·H2O） as catalyst and pyridinium chlorochromate （PCC） as oxidant, the intermolecular [2 ＋ 2] cycloaddition of allenylic esters generated in-situ from 2-（3-hydroxy-3,3-diphenylprop）benzaldehydes to constructure various cyclobutane compounds is reported. This protocol has some distinct advantages of mild reaction conditions, atom economy and high regioselectivity. The structures of relevant products were characterized by 1H NMR, 13C NMR, HRMS and X-ray crystal diffraction. In addition, a possible mechanism for this transformation was depicted.

关 键 词：联烯酯 炔丙醇 [2+2]环加成 环丁烷 

分 类 号：O621.25[理学—有机化学]