Assembly state of catalytic modules as chiral switches in asymmetric strecker amino acid synthesis
Assembly state of catalytic modules as chiral switches in asymmetric strecker amino acid synthesis
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DOI：
10.1021/ja060841r
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发表时间：
2006-05-31
影响因子：
15
通讯作者：
Shibasaki, Masakatsu
中科院分区：
文献类型：
--
作者：
Kato, Nobuki;Mita, Tsuyoshi;Shibasaki, Masakatsu
自组装手性多金属配合物作为不对称催化剂经常表现出新颖的性质。本文报道了Strecker α，α-二取代氨基酸合成的两种不对称催化剂（晶体A和B）的三维结构。这些复合物是通过组装来自d-葡萄糖的相同手性模块构建的，但它们的组装模式不同。Strecker反应中的对映选择性急剧切换，这取决于使用哪种组装模式：原位生成的催化剂，其结构由crystalB或crystalA表示。这些发现提供了深入了解人工催化剂的高阶结构的功能重要性。
Self-assembled chiral polymetallic complexes often demonstrate novel properties as asymmetric catalysts. We report the three-dimensional structures of two such asymmetric catalysts (crystalsAandB) for Strecker α,α-disubstituted amino acid synthesis. These complexes are constructed via assembly of the same chiral modules derived fromd-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 crystalB, or by crystalA. These findings provide insight into the functional importance of higher-order structures of an artificial catalyst.