Sc(III)-Catalyzed Carbonyl-Yne Reaction for the Diastereoselective Allene Synthesis: A Concerted Asynchronous Mechanism.

IF 5 1区化学 Q1 CHEMISTRY, ORGANIC

Organic Letters Pub Date : 2025-09-30 DOI:10.1021/acs.orglett.5c03172

Xinya Yuan,Jiashen Yang,Shaozhong Wang

引用次数: 0

Abstract

The carbonyl-yne reaction, involving propargylic C-H bond cleavage for carbon-carbon bond formation, is significantly less developed than the classical Alder-ene reaction due to the linear geometry and relatively weak nucleophilicity of alkynes compared to alkenes. Herein, we report a Sc(OTf)3-catalyzed carbonyl-yne reaction enabling the diastereoselective synthesis of multisubstituted allenes from α-ketoamide-tethered alkynes with 100% atom economy and excellent diastereoselectivity (up to 20/1 dr). DFT calculations support a concerted, asynchronous mechanism involving C-C bond formation and propargylic C-H cleavage. Theoretical analysis suggests that the observed stereoselectivity arises from an interplay of electronic and entropic effects in the transition states.

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Sc（III）催化羰基-炔反应合成非对映选择性烯：协同异步机制。

羰基炔反应涉及丙炔C-H键的裂解以形成碳-碳键，由于线性几何结构和相对于烯烃的亲核性较弱，羰基炔反应明显不如经典的醛烯反应发达。本文报道了Sc(OTf)3催化羰基炔反应，使α-酮酰胺系链炔具有100%的原子经济性和优异的非对映选择性（高达20/1 dr）合成多取代烯。DFT计算支持一个协调的、异步的机制，包括碳碳键的形成和丙炔碳氢键的裂解。理论分析表明，观察到的立体选择性是由过渡态中的电子效应和熵效应相互作用引起的。

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.