一种温和且高效的立体选择性形成C-O键的方法：使用锌（II）醇盐的钯催化烯丙基醚化反应。

A mild and efficient method for the stereoselective formation of C-O bonds: palladium-catalyzed allylic etherification using zinc(II) alkoxides.

作者信息

Kim Hahn, Lee Chulbom

机构信息

Department of Chemistry, Princeton University, Princeton, New Jersey 08544, USA.

出版信息

Org Lett. 2002 Nov 28;4(24):4369-71. doi: 10.1021/ol027104u.

DOI:10.1021/ol027104u

PMID:12443100

Abstract

[reaction: see text] A highly chemo- and stereoselective palladium-catalyzed allylic etherification reaction is described. The use of zinc(II) alkoxides proved effective in promoting the addition of the oxygen nucleophile derived from aliphatic alcohols to eta(3)-allylpalladium complexes. Using diethylzinc (0.5 equiv), 5 mol % of Pd(OAc)(2), and 7.5 mol % of 2-di(tert-butyl)phosphinobiphenyl in THF, the cross-coupling reaction between various aliphatic alcohols and allylic acetates proceeded at ambient temperature to furnish allylic ethers with high stereoselectivity.

摘要

[反应：见正文] 描述了一种高度化学选择性和立体选择性的钯催化烯丙基醚化反应。事实证明，使用锌（II）醇盐可有效促进脂肪醇衍生的氧亲核试剂加成到η(3)-烯丙基钯配合物上。在四氢呋喃中使用二乙基锌（0.5当量）、5摩尔%的醋酸钯（Pd(OAc)₂）和7.5摩尔%的2-二（叔丁基）膦基联苯，各种脂肪醇与烯丙基醋酸酯之间的交叉偶联反应在室温下进行，以高立体选择性提供烯丙基醚。