Highly Selective Nucleophilic 4-Aryl-2,3-allenylation of Malonates  

作　　者：Shihua Song Shengming Ma 

机构地区：[1]Laborotory of Molecular Recognition and Synthesis,Department of Chemistry,Zhejiang University,Hangzhou,Zhejiang 310027,China

出　　处：《Chinese Journal of Chemistry》2020年第11期1233-1238,共6页中国化学（英文版）

基　　金：Financial support from the National Natural Science Foundation of China(Nos.21690063 and 21572202)is greatly appreciated.We thank Mr.Jie Lin in this group for reproducing the preparation of(Ra)-3cb and(Ra,Ra)-4ea.Shengming Ma is a Qiu ShiAdjunct Professor at Zhejiang University.

摘　　要：of main observation and conclusion Allenes are a class of very important compounds and the development of straightforward,efficient,and highly enantioselective synthetic strategies for allenes have attracted extensive interests.Along this line,it is well known that aryl-substituted allenes may be readily racemized,thus,difficult to prepare in high ee.Herein,an efficient palladium-catalyzed nucleophilic allenylation of malonates w ith racemic 4-aryl-2,3-butadienyl carbonates has been developed.The selectivity issue of mono-vs.bis-allenylation with 2-non-substituted malonates has been addressed.By utilizing(R)-(-)-DTBM-SEGPHOS(5,5'-bisldi(3,5,-di-t-butyl-A-methoxyphenyOphosphino)-4,4'-bi-l,3-benzodioxole)as a chiral ligand,various aryl-substituted allenes and bisallenes have been prepared with good to excellent yields with high chemoselectivity and enantioselectivity under mild reaction conditions.Au-catalyzed cycloisomerization and APK(allenic Pauson-Khand)reactions affording optically active mono-and bicyclic products have been demonstrated.

关 键 词：SUBSTITUTED catalyzed PALLADIUM 

分 类 号：O62[理学—有机化学]