催化模块作为不对称斯特雷克氨基酸合成中的手性开关的组装状态。

Assembly state of catalytic modules as chiral switches in asymmetric Strecker amino acid synthesis.

作者信息

Kato Nobuki, Mita Tsuyoshi, Kanai Motomu, Therrien Bruno, Kawano Masaki, Yamaguchi Kentaro, Danjo Hiroshi, Sei Yoshihisa, Sato Akihiro, Furusho Sanae, Shibasaki Masakatsu

机构信息

Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo Bunkyo-ku, Tokyo 113-0033, Japan.

出版信息

J Am Chem Soc. 2006 May 31;128(21):6768-9. doi: 10.1021/ja060841r.

DOI:10.1021/ja060841r

PMID:16719439

Abstract

Self-assembled chiral polymetallic complexes often demonstrate novel properties as asymmetric catalysts. We report the three-dimensional structures of two such asymmetric catalysts (crystals A and B) for Strecker alpha,alpha-disubstituted amino acid synthesis. These complexes are constructed via assembly of the same chiral modules derived from d-glucose, but their assembly modes differ. The enantioselectivity in the Strecker reaction was dramatically switched, depending on which assembly mode was used: the catalyst generated in situ whose structure is represented by crystal B, or by crystal A. These findings provide insight into the functional importance of higher-order structures of an artificial catalyst.

摘要

自组装手性多金属配合物通常作为不对称催化剂表现出新颖的性质。我们报道了两种用于Streckerα,α-二取代氨基酸合成的此类不对称催化剂（晶体A和晶体B）的三维结构。这些配合物是通过组装源自d-葡萄糖的相同手性模块构建而成的，但它们的组装模式不同。取决于使用哪种组装模式，Strecker反应中的对映选择性会发生显著变化：由晶体B或晶体A代表其结构的原位生成的催化剂。这些发现为人工催化剂高阶结构的功能重要性提供了深入见解。