1-炔基亚砜或砜的氢锆化反应研究及其在立体定向乙烯基亚砜或砜合成中的应用。

Studies on hydrozirconation of 1-alkynyl sulfoxides or sulfones and the application for the synthesis of stereodefined vinyl sulfoxides or sulfones.

作者信息

Huang Xian, Duan Dehui, Zheng Weixin

机构信息

Department of Chemistry, Zhejiang University (Campus Xixi), Hangzhou 310028, Zhejiang, P. R. China.

出版信息

J Org Chem. 2003 Mar 7;68(5):1958-63. doi: 10.1021/jo0111154.

DOI:10.1021/jo0111154

PMID:12608817

Abstract

The hydrozirconation reaction of 1-alkynyl sulfoxides or sulfones with Cp2Zr(H)Cl in THF at room temperature predominantly gave Z-beta-zirconated vinyl sulfoxides or sulfones with excellent regioselectivity. Compared with 1-alkynyl sulfoxides, the hydrozirconation reaction of 1-alkynyl sulfones exhibits great synthetic potential, leading to the efficient preparation of Z-beta-halovinyl sulfones, Z-beta-sulfonyl alpha,beta-unsaturated ketones, and Z-beta-alkynyl vinyl sulfones. Although the reaction mechanisms are still not clear, the neighboring group participation of the sulfinyl or sulfonyl group may be playing an important role in this unique hydrozirconation reaction.

摘要

在室温下，1-炔基亚砜或砜与Cp2Zr(H)Cl在四氢呋喃中发生氢锆化反应，主要生成具有优异区域选择性的Z-β-锆化乙烯基亚砜或砜。与1-炔基亚砜相比，1-炔基砜的氢锆化反应具有很大的合成潜力，可高效制备Z-β-卤代乙烯基砜、Z-β-磺酰基α,β-不饱和酮和Z-β-炔基乙烯基砜。尽管反应机理仍不明确，但亚磺酰基或磺酰基的邻基参与可能在这一独特的氢锆化反应中起着重要作用。