Understanding Rate Acceleration and Stereoinduction of an Asymmetric Giese Reaction Mediated by a Chiral Rhodium Catalyst,Journal of the American Chemical Society

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Understanding Rate Acceleration and Stereoinduction of an Asymmetric Giese Reaction Mediated by a Chiral Rhodium Catalyst
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2017-06-06 , DOI: 10.1021/jacs.7b01786
Brandon Tutkowski ₁ , Eric Meggers ₂ , Olaf Wiest _{1,

3}

Affiliation

The surprising acceleration of the addition of electron-rich radicals to α,β-unsaturated 2-acyl imidazoles by a chiral-at-metal rhodium catalyst is investigated. M06/Lanl2DZ (Rh),6-31G(d) calculations reproduce the observed rate acceleration and shed light on a catalyst design where a rigid chiral pocket with a steric interaction >5 Å from the chiral metal center leads to the observed high stereoinduction. Analysis of the molecular orbitals of two key addition transition states emphasize the role of the catalyst as a Lewis acid without significant charge transfer.

中文翻译：

了解手性铑催化剂介导的不对称 Giese 反应的速率加速和立体感应

研究了通过手性金属铑催化剂向 α,β-不饱和 2-酰基咪唑中添加富电子自由基的惊人加速。M06/Lanl2DZ (Rh),6-31G(d) 计算再现了观察到的速率加速并阐明了催化剂设计，其中具有距手性金属中心的空间相互作用 > 5 Å 的刚性手性袋导致观察到的高立体感应。对两个关键加成过渡态的分子轨道的分析强调了催化剂作为路易斯酸的作用，而没有显着的电荷转移。

更新日期：2017-06-06

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