可见光诱导的酰基硅烷与丙酮酸酯亲电试剂的咔嗒反应

IF 7.4 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chemical Science Pub Date : 2025-10-08 DOI:10.1039/d5sc06269a

Rowan L Pilkington, Rosa Kössler, Jesse Molloy, Stefan Bräse, Daniel L Priebbenow

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引用次数: 0

摘要

在可见光照射下，酰基硅烷诱导的硅氧卡宾中间体与丙酮酸衍生物发生了高效的苯甲酸类咔嗒反应。该过程不需要除可见光以外的任何试剂，进行效率高，并且可以耐受各种官能团。丙酮酸酯、硫酯、酰胺、腈和膦酸盐都被认为是合适的亲电试剂，包括那些连接在复杂药物或生物分子支架上的亲电试剂。可见光诱导碳-碳键形成过程具有批量和流动两种方法的可扩展性，并对相应的加成产物进行了多样化的研究。DFT分析还获得了硅氧烷反应性的机理见解。

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Visible-Light Induced Click Reactions of Acylsilanes with Pyruvate Electrophiles

Siloxycarbene intermediates induced via the visible light irradiation of acylsilanes undergo highly efficient benzoin-type click reactions with pyruvate derivatives. This process requires no reagents other than visible light, proceeds with high efficiency and is tolerant of a wide range of functional groups. Pyruvate esters, thioesters, amides, nitriles and phosphonates were all identified as suitable electrophiles including those tethered to complex drug or biomolecule scaffolds. The visible-light induced carbon-carbon bond forming process was scalable using both batch and flow methodologies, accompanied by diversification studies on the corresponding addition products. Mechanistic insights into siloxycarbene reactivity were also obtained by DFT analysis.

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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.