γ-羟基-顺式烯烃的对映选择性汞环化反应

Enantioselective mercuriocyclization of gamma-hydroxy-cis-alkenes.

作者信息

Kang Sung Ho, Kim Mihyong

机构信息

Center for Molecular Design and Synthesis, Department of Chemistry, School of Molecular Science, Korea.

出版信息

J Am Chem Soc. 2003 Apr 23;125(16):4684-5. doi: 10.1021/ja029777d.

DOI:10.1021/ja029777d

PMID:12696867

Abstract

Asymmetric mercuriocyclization of gamma-hydroxy-(Z)-alkenes has been achieved using Hg(II) complexed with tartrate-derived 4-(2-naphthyl)bisoxazoline as chiral ligand to give rise to 2-monosubstituted tetrahydrofurans in 86-95% ee. Not only the linker connecting two oxazolines but also their 4-substituents were found crucial for high enantioselectivity. In addition, tuning the ketal protecting group of tartrate as well as adding MeOH and K(2)CO(3) worked beneficially.

摘要

使用与酒石酸衍生的4-(2-萘基)双恶唑啉络合的Hg(II)作为手性配体，实现了γ-羟基-(Z)-烯烃的不对称汞环化反应，得到对映体过量率为86-95%的2-单取代四氢呋喃。发现连接两个恶唑啉的连接基及其4-取代基对高对映选择性至关重要。此外，调节酒石酸的缩酮保护基以及加入甲醇和碳酸钾有有益效果。