A chiral hydrogen atom abstraction catalyst for the enantioselective epimerization of meso-diols

被引：6

作者：

Lahdenpera, Antti S. K. ^{[1
]}

Dhankhar, Jyoti ^{[1
]}

Davies, Daniel J. ^{[1
]}

Lam, Nelson Y. S. ^{[1
]}

Bacos, P. David ^{[1
]}

de la Vega-hernandez, Karen ^{[1
]}

Phipps, Robert J. ^{[1
]}

机构：

[1] Univ Cambridge, Yusuf Hamied Dept Chem, Cambridge CB2 1EW, England

来源：

SCIENCE | 2024年 / 386卷 / 6717期

基金：

瑞士国家科学基金会; 英国工程与自然科学研究理事会; 欧盟地平线“2020”;

关键词：

AMINE-BORYL RADICALS; POT ENZYMATIC-SYNTHESIS; CYCLIC VICINAL DIOLS; KINETIC RESOLUTION; HOMOLYTIC REACTIONS; LIGATED BORANES; CARBON-CARBON; TRANSFER HAT; DESYMMETRIZATION; REACTIVITY;

D O I：

10.1126/science.adq8029

中图分类号：

O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];

学科分类号：

07 ; 0710 ; 09 ;

摘要：

Hydrogen atom abstraction is an important elementary chemical process but is very difficult to carry out enantioselectively. We have developed catalysts, readily derived from the Cinchona alkaloid family of natural products, which can achieve this by virtue of their chiral amine structure. The catalyst, following single-electron oxidation, desymmetrizes meso-diols by selectively abstracting a hydrogen atom from one carbon center, which then regains a hydrogen atom by abstraction from a thiol. This results in an enantioselective epimerization process, forming the chiral diastereomer with high enantiomeric excess. Cyclic and acyclic 1,2-diols are compatible, as are acyclic 1,3-diols. Additionally, we demonstrate the viability of combining our approach with carbon-carbon bond formation in Giese addition. Given the increasing number of synthetic methods involving hydrogen atom transfer steps, we anticipate that this work will have a broad impact in the field of enantioselective radical chemistry.

引用

页码：42 / 49

页数：8

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