Qi Cui, Pan Zhang, Bing-Wen Li, Yi Jin, Qianwei Zhang, Hong-Xi Bai, Zhi-Xiang Yu
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引用次数: 0
Abstract
Developing reactions to synthesize challenging eight-membered carbocycles is a research frontier of organic synthesis. Reported here is the development of Rh-catalyzed [5 + 1 + 2] cycloaddition of yne-3-acyloxy-1,4-enynes (Yne-ACEs, shortened as YACEs) and CO, in which sequentially five-carbon (generated from 3-acyloxy-1,4-enynes), one-carbon (CO), and two-carbon (alkynes) units are assembled into the final 5/8 scaffold containing a cyclooctatrienone structure. This reaction has a broad scope and can be carried out under mild conditions. Keys to the success of the present [5 + 1 + 2] reaction, discovered and supported by experiments and ab initio calculations, include using terminal alkyne in the 3-acyloxy-1,4-enyne moiety of the substrates so that 1,2-acyloxy migration (instead of 1,3-acyloxy migration, a step required for a competing [4 + 2 + 1] reaction) can be realized and applying an electron-rich aryl group (here, it is p-dimethylamino phenyl) in the acyloxy group to make a [5 + 1] pathway disfavored. Quantum chemical calculations have also been used to answer why this reaction is [5 + 1 + 2] but not [5 + 2 + 1] (where alkyne insertion is ahead of CO insertion) and to find the factors disfavoring the competitive [5 + 2], [5 + 1], and [4 + 2 + 1] reactions.
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.