吡啶丙氨酸（pal）-肽催化对映选择性的丙二烯酸酯加成到N-酰基亚胺上。

Pyridylalanine (pal)-peptide catalyzed enantioselective allenoate additions to N-acyl imines.

作者信息

Cowen Bryan J, Saunders Lindsey B, Miller Scott J

机构信息

Department of Chemistry, Yale University, P.O. Box 208107, New Haven, Connecticut 06520-8107, USA.

出版信息

J Am Chem Soc. 2009 May 6;131(17):6105-7. doi: 10.1021/ja901279m.

DOI:10.1021/ja901279m

PMID:19354290

Abstract

An amine-catalyzed reaction has been discovered that couples alpha-allenic esters with N-acyl imines in good to excellent yields (up to 88%). Extension of this methodology from the study of achiral pyridine-based catalysis to chiral peptide-based scaffolds is presented. The approach culminated in the identification of a tetrameric peptide sequence containing an embedded pyridylalanine (Pal) residue as an efficient asymmetric catalyst for enantioselective coupling reactions. The unique allenic products are obtained with enantiomer ratios of up to approximately 95:5 (up to >98:2 following recrystallization).

摘要

人们发现了一种胺催化反应，该反应能使α-联烯酸酯与N-酰基亚胺以良好至优异的产率（高达88%）发生偶联。本文介绍了这种方法从基于非手性吡啶的催化研究扩展到基于手性肽的支架的过程。该方法最终确定了一种含有嵌入吡啶基丙氨酸（Pal）残基的四聚体肽序列，作为对映选择性偶联反应的有效不对称催化剂。所得到的独特联烯产物的对映体比例高达约95:5（重结晶后高达>98:2）。