使用锌、异丙基碘、H8BINOL和四异丙氧基钛对脂肪族、芳香族和乙烯基醛进行对映选择性炔烃加成反应

Enantioselective Alkyne Addition to Aliphatic, Aromatic, and Vinyl Aldehydes Using Zn, (i)PrI, H8BINOL, and Ti(O(i)Pr)4.

作者信息

Huang Wen-Cai, Liu Winnie, Wu Xue-Dan, Ying Jun, Pu Lin

机构信息

Department of Pharmaceutical and Bioengineering, School of Chemical Engineering, Sichuan University , Chengdu, China 610065.

Department of Chemistry, University of Virginia , Charlottesville, Virginia 22904-4319, United States.

出版信息

J Org Chem. 2015 Nov 20;80(22):11480-4. doi: 10.1021/acs.joc.5b02185. Epub 2015 Nov 12.

DOI:10.1021/acs.joc.5b02185

PMID:26545154

Abstract

A new catalytic system based on the readily available Zn, (i)PrI, H8BINOL, and Ti(O(i)Pr)4 has been developed which avoids the use of pyrophoric ZnEt2. It can effectively catalyze the reaction of various terminal alkynes with aromatic, aliphatic, and vinyl aldehydes to generate chiral propargylic alcohols at room temperature with up to 98% yield and 98% enantiomeric excess. This new system signifciantly expands the substrate scope of the previously reported system using Zn, EtI, BINOL, and Ti(O(i)Pr)4.

摘要

一种基于易于获得的锌、异丙基碘、H8BINOL和四异丙氧基钛开发的新型催化体系已被研制出来，该体系避免了使用自燃性的二乙基锌。它能够在室温下有效地催化各种末端炔烃与芳香醛、脂肪醛和乙烯基醛的反应，生成手性炔丙醇，产率高达98%，对映体过量值高达98%。这种新体系显著扩大了先前报道的使用锌、碘乙烷、联萘酚和四异丙氧基钛的体系的底物范围。