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在具有相邻杂原子的碳中心自由基上的羰基化反应。

Carbonylation Reactions at Carbon-Centered Radicals with an Adjacent Heteroatom.

作者信息

Wang Le-Cheng, Wu Xiao-Feng

机构信息

Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 116023, Dalian, Liaoning, China.

Leibniz-Institut für Katalyse e. V., 18059, Rostock, Germany.

出版信息

Angew Chem Int Ed Engl. 2024 Dec 16;63(51):e202413374. doi: 10.1002/anie.202413374. Epub 2024 Oct 29.

Abstract

Heteroatoms are essential to living organisms and present in almost all molecules with medicinal usage. The catalytic functionalization at the carbon-centered radical with an adjacent heteroatom provides an effective way to value added moiety while retaining the unique physicochemical and pharmacological properties of heteroatoms, which can promote the development of pharmaceutical and fine chemical production. Carbonylative transformation was discovered nearly a century ago which is an efficient method for the synthesis of carbonyl-containing molecules with potent applications in both industry and academia. Despite numerous advances in new reaction development, carbonylative transformation involving adjacent heteroatom carbon radical remain a subject that deserves to be discussed. In this minireview, we systematically summarized and discussed the recent advances in carbonylative transformations involving carbon-centered radicals with an adjacent heteroatom, including oxygen (O), nitrogen (N), phosphorus (P), silicon (Si), sulfur (S), boron (B), fluorine (F), and chlorine (Cl). The related reaction mechanism was also discussed.

摘要

杂原子对生物有机体至关重要,几乎存在于所有具有药用价值的分子中。在具有相邻杂原子的碳中心自由基上进行催化官能团化,为引入增值部分提供了一种有效方法,同时保留了杂原子独特的物理化学和药理性质,这有助于促进制药和精细化工生产的发展。羰基化转化近一个世纪前就已被发现,它是一种合成含羰基分子的有效方法,在工业和学术界都有重要应用。尽管在新反应开发方面取得了诸多进展,但涉及相邻杂原子碳自由基的羰基化转化仍是一个值得探讨的课题。在本综述中,我们系统地总结并讨论了涉及具有相邻杂原子(包括氧(O)、氮(N)、磷(P)、硅(Si)、硫(S)、硼(B)、氟(F)和氯(Cl))的碳中心自由基的羰基化转化的最新进展。同时也讨论了相关的反应机理。

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