二甲基锌介导的烯基锆茂向α-酮酯和α-亚胺酯的加成反应。

Dimethylzinc-mediated addition of alkenylzirconocenes to alpha-keto and alpha-imino esters.

作者信息

Wipf Peter, Stephenson Corey R J

机构信息

Department of Chemistry, University of Pittsburgh, Pittsburgh, Pennsylvania 15260, USA. wipf+@pitt.edu

出版信息

Org Lett. 2003 Jul 10;5(14):2449-52. doi: 10.1021/ol0347141.

DOI:10.1021/ol0347141

PMID:12841752

Abstract

[reaction: see text] Hydrozirconation of alkynes followed by in situ transmetalation to dimethylzinc and 1,2-addition to activated ketones and N-diphenylphosphinoylimines leads to tertiary allylic alcohols and amines in high overall yield. With 8-phenylmenthol as the chiral auxiliary, si-face attack proceeds in good to excellent diastereoselectivities.

摘要

[反应：见正文] 炔烃经锆氢化反应，然后原位转金属化为二甲基锌，并对活化酮和N-二苯基膦酰亚胺进行1,2-加成，可高收率地得到叔烯丙醇和叔烯丙胺。以8-苯基薄荷醇作为手性助剂时，硅面进攻具有良好至优异的非对映选择性。