高对映选择性有机催化的七元环状亚胺二苯并1,4-氧氮杂卓和丙酮的直接Mannich反应(英文)  

Highly enantioselective direct Mannich reaction of seven-membered cyclic imines dibenzo[b,f][1,4]oxazepines with acetone via organocatalysis

作　　者：汪游清[1] 任圆圆[1] 

机构地区：[1]河南大学天然药物与免疫工程重点实验室,河南开封475004

出　　处：《催化学报》2015年第1期93-99,共7页

基　　金：supported by the National Natural Science Foundation of China (21002022);the Chinese Ministry of Education (the Scientific Research Foundation for the Returned Overseas Chinese Scholars)~~

摘　　要：用脯氨酸作为催化剂,研究了各种取代的二苯并1,4-氧氮杂卓衍生物类七元环状亚胺和丙酮的直接Mannich反应,该反应能高对映选择得到一系列旋光活性的含有β羰基的七元环状氮杂环化合物(93%–98%ee).用丁酮作为Mannich给体时,能得到专一的区域选择性和96%–97%ee的产物.进一步通过X射线单晶衍射分析其中一个产物的衍生物,确定了产物手性中心绝对构型为R,其它同类型产物绝对构型随后通过化学类比方法推断确认.Various substituted dibenzo[b,f][1,4]oxazepines as seven-membered cyclic imines underwent a highly enantioselective direct Mannich reaction with acetone when catalyzed by proline. These reactions gave a range of optically active β-carbonyl seven-membered N-heterocycles with excellent enantioselectivity（93%–98% ee）. With 2-butanone as a Mannich donor, the single regioselective product was obtained with 96%–97% ee. The absolute configuration of the product was assigned to be R by X-ray single crystal analysis of its derivative.

关 键 词：丙酮 不对称催化 七元环状亚胺 MANNICH反应 有机催化 

分 类 号：O643.32[理学—物理化学]