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

IF 44.7 1区综合性期刊 Q1 MULTIDISCIPLINARY SCIENCES

Science Pub Date : 2024-10-04 Epub Date: 2024-10-03 DOI:10.1126/science.adq8029

Antti S K Lahdenperä, Jyoti Dhankhar, Daniel J Davies, Nelson Y S Lam, P David Bacoş, Karen de la Vega-Hernández, Robert J Phipps

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Abstract

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.

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一种用于介二元醇对映选择性环化的手性氢原子抽取催化剂。

氢原子抽取是一种重要的基本化学过程，但很难实现对映选择性。我们从金鸡纳生物碱家族的天然产品中开发出了催化剂，凭借其手性胺结构可以实现这一目标。催化剂在进行单电子氧化后，通过选择性地从一个碳中心抽取一个氢原子来使中二元醇非对称，然后通过从一个硫醇中抽取氢原子来重新获得氢原子。这就产生了对映体选择性外嵌合过程，形成对映体过量的手性非对映异构体。环状和非环状 1,2-二醇以及非环状 1,3-二醇是兼容的。此外，我们还证明了在吉斯加成法中将我们的方法与碳-碳键形成相结合的可行性。鉴于涉及氢原子转移步骤的合成方法越来越多，我们预计这项工作将在对映体选择性自由基化学领域产生广泛影响。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Science 综合性期刊-综合性期刊

CiteScore

61.10

自引率

0.90%

发文量

审稿时长

2.1 months

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