Harnessing the Silicon Effect for Copper-Catalyzed Linear-E-Selective Reductive Coupling of Ketones with Allenylsilanes

IF 4.7 1区化学 Q1 CHEMISTRY, ORGANIC

Organic Letters Pub Date : 2026-10-16 Epub Date: 2026-10-07 DOI:10.1021/acs.orglett.6c03882

Qingbin Lu, Weixiang Ye, Yixiao Li, Baihui Gong, Shixin Zhang, Xuanyi Li, Aijun Lin, Shang Gao

引用次数: 0

Abstract

We report a copper-catalyzed reductive coupling of ketones with allenylsilanes that delivers γ-silyl homoallylic alcohols with exceptional linear E-selectivities. Mechanistic investigations indicate that the silyl substituent functions as a directing element for regioselectivity control. DFT calculations further reveal that the allyl addition is the regio-determining step, where the branched allylcopper species shows a markedly lower activation barrier. The vinylsilane products serve as versatile platforms for downstream functionalization, enabling efficient carbon-chain elongation.

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利用铜催化酮与烯基硅烷线性选择性还原偶联的硅效应

摘要：我们报道了一种铜催化的酮与烯基硅烷的还原偶联反应，该反应产生了具有特殊线性e选择性的γ-硅基同丙烯醇。机理研究表明，硅基取代基在区域选择性控制中起着指导作用。DFT计算进一步表明，烯丙基加成是区域决定步骤，其中支化的烯丙基铜表现出明显较低的激活势垒。乙烯基硅烷产品作为下游功能化的通用平台，实现高效的碳链延伸。

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

Organic Letters 化学-有机化学

CiteScore

9.30

自引率

11.50%

发文量

1607

审稿时长

1.5 months

期刊介绍： Organic Letters invites original reports of fundamental research in all branches of the theory and practice of organic, physical organic, organometallic,medicinal, and bioorganic chemistry. Organic Letters provides rapid disclosure of the key elements of significant studies that are of interest to a large portion of the organic community. In selecting manuscripts for publication, the Editors place emphasis on the originality, quality and wide interest of the work. Authors should provide enough background information to place the new disclosure in context and to justify the rapid publication format. Back-to-back Letters will be considered. Full details should be reserved for an Article, which should appear in due course.