通过钯（0）/苯甲酸催化环状β-酮酯和1,3-二酮与炔烃的烯丙基化反应形成季碳中心。

Formation of a quaternary carbon center through the Pd(0)/PhCOOH-catalyzed allylation of cyclic beta-keto esters and 1,3-diketones with alkynes.

作者信息

Patil Nitin T, Yamamoto Yoshinori

机构信息

Department of Chemistry, Graduate School of Science, Tohoku University, Sendai 980-8578, Japan.

出版信息

J Org Chem. 2004 Sep 17;69(19):6478-81. doi: 10.1021/jo0490144.

DOI:10.1021/jo0490144

PMID:15357613

Abstract

Formation of a quaternary carbon center through the allylation of beta-keto esters and 1,3-diketones with alkynes is accomplished by the use of Pd(0)/benzoic acid catalyst. Reactions of various cyclic beta-keto esters and 1,3-diketones with alkynes in the presence of Pd(2)dba(3).CHCl(3) (5 mol %), PPh(3) (40 mol %), and PhCOOH (10 mol %) proceeded at 100 degrees C in toluene (5 M) to give the corresponding allylation products in high yields in a regio- and stereoselective manner. The possibility of asymmetric allylation is also discussed.

摘要

通过使用钯（0）/苯甲酸催化剂，可实现β-酮酯和1,3-二酮与炔烃的烯丙基化反应，从而形成季碳中心。各种环状β-酮酯和1,3-二酮在Pd₂(dba)₃·CHCl₃（5摩尔%）、三苯基膦（40摩尔%）和苯甲酸（10摩尔%）存在下，于100℃在甲苯（5M）中与炔烃反应，以区域和立体选择性的方式高产率得到相应的烯丙基化产物。同时也讨论了不对称烯丙基化的可能性。