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 11.3 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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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.