通过铑（I）-（R，S）-联萘膦催化的不对称氢甲酰化反应及随后的氧化反应合成α-杂芳基丙酸

Synthesis of alpha-heteroarylpropanoic acid via asymmetric hydroformylation catalyzed by Rh(I)-(R,S)-BINAPHOS and the subsequent oxidation.

作者信息

Tanaka Ryo, Nakano Koji, Nozaki Kyoko

机构信息

Department of Chemistry and Biotechnology, Graduate School of Engineering, The University of Tokyo, 7-3-1 Hongo, Tokyo, Japan.

出版信息

J Org Chem. 2007 Nov 9;72(23):8671-6. doi: 10.1021/jo0712190. Epub 2007 Oct 10.

DOI:10.1021/jo0712190

PMID:17927247

Abstract

The asymmetric hydroformylation of vinyl heteroarenes (vinylfurans and vinylthiophenes) was investigated by using Rh(I)-BINAPHOS derivatives as a catalyst. The hydroformylation of vinylthiophenes 1 gave the corresponding branched aldehydes 2 with high enantiopurities as major products. Oxidation of the aldehydes 2 successfully afforded alpha-heteroarylpropanoic acids 4 in good yields. In addition, the aldehydes 2 were reduced to alcohols 5 without loss of enantiomeric excess.

摘要

使用铑（I）-联萘磷衍生物作为催化剂，研究了乙烯基杂芳烃（乙烯基呋喃和乙烯基噻吩）的不对称氢甲酰化反应。乙烯基噻吩1的氢甲酰化反应以高对映体纯度的相应支链醛2作为主要产物。醛2的氧化反应成功地以良好的产率得到了α-杂芳基丙酸4。此外，醛2被还原为醇5，且对映体过量没有损失。