吡啶- n -氧化物催化磺胺酰化不对称脱对称反应

IF 7.6 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chemical Science Pub Date : 2025-04-08 DOI:10.1039/d5sc01270h

Cui-Mei Guo, Fang-Yuan Zhang, Yin Tian, Ming-Sheng Xie, Hai-Ming Guo

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引用次数: 0

摘要

以手性4-芳基吡啶- n -氧化物为催化剂，对氯甲酸酯进行了磺胺酰化脱对称反应，得到了具有硫（VI）立体中心的n -酰化磺胺酰化脱对称产物，收率高，对映选择性好。实验和DFT计算支持酰基转移机制，而磺酰咪胺亲核取代o-酰基氧基吡啶阳离子中间体是该反应的对映体决定步骤。该反应的特点是羧基的可变性和与水分的相容性。

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Pyridine-N-oxide Catalyzed Asymmetric N-Acylative Desymmetrization of Sulfonimidamides

A highly efficient enantioselective N-acylative desymmetrization of sulfonimidamides with chloroformates was reported using chiral 4-arylpyridine-N-oxide as the catalyst, affording N-acylative sulfonimidamides with sulfur(VI)-stereocenters in high yields and excellent enantioselectivities. Experiments and DFT calculations support an acyl transfer mechanism, and the nucleophilic substitution of sulfonimidamide to O-acyloxypyridinium cation intermediate is the enantio-determining step of the reaction. The reaction is featured with variability for acyloxy groups and compatibility with moisture.

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来源期刊

Chemical Science CHEMISTRY, MULTIDISCIPLINARY-

CiteScore

14.40

自引率

4.80%

发文量

1352

审稿时长

2.1 months

期刊介绍： Chemical Science is a journal that encompasses various disciplines within the chemical sciences. Its scope includes publishing ground-breaking research with significant implications for its respective field, as well as appealing to a wider audience in related areas. To be considered for publication, articles must showcase innovative and original advances in their field of study and be presented in a manner that is understandable to scientists from diverse backgrounds. However, the journal generally does not publish highly specialized research.