Impact of Host Flexibility on Selectivity in a Supramolecular Host-Catalyzed Enantioselective aza-Darzens Reaction,Journal of the American Chemical Society

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Impact of Host Flexibility on Selectivity in a Supramolecular Host-Catalyzed Enantioselective aza-Darzens Reaction
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2022-06-14 , DOI: 10.1021/jacs.2c04182
Stephen M Bierschenk _{1,

2} , Judy Y Pan _{1,

2} , Nicholas S Settineri ₂ , Ulrike Warzok ₂ , Robert G Bergman _{1,

2} , Kenneth N Raymond _{1,

2} , F Dean Toste _{1,

2}

Affiliation

A highly enantioselective aza-Darzens reaction (up to 99% ee) catalyzed by an enantiopure supramolecular host has been discovered. To understand the role of host structure on reaction outcome, nine new gallium(III)-based enantiopure supramolecular assemblies were prepared via substitution of the external chiral amide. Despite the distal nature of the substitution in these catalysts, changes in enantioselectivity (61 to 90% ee) in the aziridine product were observed. The enantioselectivities were correlated to the flexibility of the supramolecular host scaffold as measured by the kinetics of exchange of a model cationic guest. This correlation led to the development of a best-in-class catalyst by substituting the gallium(III)-based host with one based on indium(III), which generated the most flexible and selective catalyst.

中文翻译：

主体灵活性对超分子主体催化的对映选择性氮杂-Darzens 反应选择性的影响

已发现由对映纯超分子主体催化的高度对映选择性 aza-Darzens 反应（高达 99% ee）。为了了解主体结构对反应结果的作用，通过取代外部手性酰胺制备了九种新的基于镓 (III) 的对映体纯超分子组装体。尽管这些催化剂中的取代具有远端性质，但观察到氮丙啶产物的对映选择性（61% 至 90% ee）发生了变化。如通过模型阳离子客体的交换动力学所测量的，对映选择性与超分子宿主支架的灵活性相关。这种相关性导致通过用基于铟（III）的主体替代基于镓（III）的主体来开发同类最佳的催化剂，从而产生最灵活和选择性的催化剂。

更新日期：2022-06-14

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