Asymmetric Trapping of Siloxyketenes In Situ Generated from [1,3]-Silyl Migration of α-Ketoacylsilanes: A Visible-Light-Driven Palladium-Catalyzed [4 + 2] Cycloaddition

IF 13.1 1区化学 Q1 CHEMISTRY, PHYSICAL ACS Catalysis Pub Date : 2025-03-25 DOI:10.1021/acscatal.5c01239

Lingyun Yao, Xinlan Zou, Jian Zhang, Yang-Zi Liu, Quannan Wang, Hanliang Zheng, Xusheng Shao, Wei-Ping Deng

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Abstract

The transition metal-catalyzed asymmetric [n + 2] cycloaddition reaction with oxy-substituted ketene intermediates remains a synthetic challenge due to the limited availability of suitable ketene precursors. Herein, we report a visible-light-driven, palladium-catalyzed asymmetric [4 + 2] cycloaddition of vinyl benzoxazinanones with siloxyketene intermediates, generating structurally diverse chiral quinolinone derivatives with satisfactory diastereo- and enantioselectivities. The transient generation of siloxyketenes from α-ketoacylsilylanes through visible-light-induced Brook rearrangement is important for the success of the present cycloaddition. The ¹³C-labeling experiments reveal a Brook rearrangement pathway involving a [1,3]-silyl migration process. The side arm effects of BOX ligand and silyl steric hindrance of α-ketoacylsilanes play crucial roles in the stereoselectivity control, and theoretical calculations provide crucial insights into the stereochemical outcome in the reaction.

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α-酮酰基硅烷[1,3]-硅基迁移原位生成硅氧酮的不对称捕获：可见光驱动钯催化的[4 + 2]环加成

由于合适的烯酮前体的可用性有限，过渡金属催化的与氧取代的烯酮中间体的不对称[n + 2]环加成反应仍然是一个合成挑战。在此，我们报道了一种可见光驱动，钯催化的不对称[4 + 2]环加成乙烯基苯并恶嗪酮与硅氧酮中间体，生成了结构多样的手性喹啉酮衍生物，具有令人满意的非映对和对映选择性。α-酮酰基硅烷在可见光诱导下的布鲁克重排反应对环加成反应的成功与否至关重要。13c标记实验揭示了Brook重排途径涉及[1,3]-硅基迁移过程。BOX配体的副作用和α-酮酰硅烷的硅基位阻在立体选择性控制中起着至关重要的作用，理论计算为反应的立体化学结果提供了重要的见解。

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来源期刊

ACS Catalysis CHEMISTRY, PHYSICAL-

CiteScore

20.80

自引率

6.20%

发文量

1253

审稿时长

1.5 months

期刊介绍： ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels. The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.