探究产物加速脯氨酸介导反应中的活性催化剂。

Probing the active catalyst in product-accelerated proline-mediated reactions.

作者信息

Iwamura Hiroshi, Wells David H, Mathew Suju P, Klussmann Martin, Armstrong Alan, Blackmond Donna G

机构信息

Department of Chemistry, Imperial College, London SW7 2AZ, United Kingdom.

出版信息

J Am Chem Soc. 2004 Dec 22;126(50):16312-3. doi: 10.1021/ja0444177.

DOI:10.1021/ja0444177

PMID:15600319

Abstract

A new catalytic cycle involving only soluble proline complexes or adducts is proposed for the reactions in eq 1 based on kinetic observations and molecular modeling studies. This reaction pathway circumventing free proline and incorporating hydrogen-bonded reaction product helps to rationalize the observations of accelerating reaction rate in both the alpha-aminooxylation and alpha-amination reactions.

摘要

基于动力学观察和分子模拟研究，针对式（1）中的反应提出了一种仅涉及可溶性脯氨酸络合物或加合物的新催化循环。这种避开游离脯氨酸并包含氢键合反应产物的反应途径，有助于解释在α-氨基氧基化和α-胺化反应中反应速率加快的现象。