Photoinduced Pd-Catalyzed Formal Asymmetric Allylic Substitution of Piperidine Scaffolds

IF 11.3 1区化学 Q1 CHEMISTRY, PHYSICAL

ACS Catalysis Pub Date : 2025-02-26 DOI:10.1021/acscatal.4c0786910.1021/acscatal.4c07869

Wei-Dong Lu, Zhi-Lin Liu, Zi-Hao Liao, Zi-Yi Gao, Kai Chen*, Hao-Yue Xiang* and Hua Yang*,

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Abstract

Transition-metal-catalyzed asymmetric allylic substitution (AAS) reaction is one of the most synthetically useful and powerful reactions for the assembly of carbon–carbon and carbon–heteroatom bonds in an asymmetric fashion. Herein, we accomplished a photoinduced, palladium-catalyzed formal AAS reaction without preinstalling the allylic structural unit, which rationally integrates photocatalytic desaturation and asymmetric allylic substitution. A series of sterically congested optically pure 2-alkyltetrahydropyridine scaffolds were facilely prepared from inexpensive and readily available piperidine derivatives with carbon-centered nucleophiles, with excellent compatibility (51 examples), high efficiency (up to 96% yield), excellent regioselectivity (only α-product), and outstanding enantioselectivities (up to 95.5:4.5 er). Comprehensive computational studies rationalized the compatibility of photoinduced radical chemistry and transition-metal-catalyzed AAS reaction and disclosed the origin of regioselectivity and enantioselectivity.

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过渡金属催化的不对称烯丙基取代（AAS）反应是以不对称方式组装碳-碳键和碳-异原子键的最有用、最强大的合成反应之一。在这里，我们完成了一种光诱导、钯催化的正式烯丙基取代反应，无需预先安装烯丙基结构单元，合理地整合了光催化脱饱和与不对称烯丙基取代。利用价格低廉、易于获得的哌啶衍生物与碳中心亲核物轻松制备了一系列立体拥挤的光学纯 2-烷基四氢吡啶支架，这些支架具有极佳的兼容性（51 个实例）、高效率（收率高达 96%）、优异的区域选择性（只有 α 产物）和出色的对映选择性（高达 95.5:4.5 er）。综合计算研究合理地解释了光诱导自由基化学和过渡金属催化 AAS 反应的兼容性，并揭示了区域选择性和对映体选择性的来源。

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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.