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N-Ammonium Ylide Mediators for Electrochemical C–H Oxidation
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2021-05-13 , DOI: 10.1021/jacs.1c03780 Masato Saito 1 , Yu Kawamata 1 , Michael Meanwell 1 , Rafael Navratil 1 , Debora Chiodi 1 , Ethan Carlson 1 , Pengfei Hu 1 , Longrui Chen 1 , Sagar Udyavara 2 , Cian Kingston 3 , Mayank Tanwar 2 , Sameer Tyagi 4 , Bruce P McKillican 4 , Moses G Gichinga 4 , Michael A Schmidt 5 , Martin D Eastgate 5 , Massimiliano Lamberto 6 , Chi He 1 , Tianhua Tang 3 , Christian A Malapit 3 , Matthew S Sigman 3 , Shelley D Minteer 3 , Matthew Neurock 2 , Phil S Baran 1
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2021-05-13 , DOI: 10.1021/jacs.1c03780 Masato Saito 1 , Yu Kawamata 1 , Michael Meanwell 1 , Rafael Navratil 1 , Debora Chiodi 1 , Ethan Carlson 1 , Pengfei Hu 1 , Longrui Chen 1 , Sagar Udyavara 2 , Cian Kingston 3 , Mayank Tanwar 2 , Sameer Tyagi 4 , Bruce P McKillican 4 , Moses G Gichinga 4 , Michael A Schmidt 5 , Martin D Eastgate 5 , Massimiliano Lamberto 6 , Chi He 1 , Tianhua Tang 3 , Christian A Malapit 3 , Matthew S Sigman 3 , Shelley D Minteer 3 , Matthew Neurock 2 , Phil S Baran 1
Affiliation
The site-specific oxidation of strong C(sp3)–H bonds is of uncontested utility in organic synthesis. From simplifying access to metabolites and late-stage diversification of lead compounds to truncating retrosynthetic plans, there is a growing need for new reagents and methods for achieving such a transformation in both academic and industrial circles. One main drawback of current chemical reagents is the lack of diversity with regard to structure and reactivity that prevents a combinatorial approach for rapid screening to be employed. In that regard, directed evolution still holds the greatest promise for achieving complex C–H oxidations in a variety of complex settings. Herein we present a rationally designed platform that provides a step toward this challenge using N-ammonium ylides as electrochemically driven oxidants for site-specific, chemoselective C(sp3)–H oxidation. By taking a first-principles approach guided by computation, these new mediators were identified and rapidly expanded into a library using ubiquitous building blocks and trivial synthesis techniques. The ylide-based approach to C–H oxidation exhibits tunable selectivity that is often exclusive to this class of oxidants and can be applied to real-world problems in the agricultural and pharmaceutical sectors.
中文翻译:
用于电化学 C-H 氧化的 N-铵叶立德介体
强 C(sp 3 )-H 键的位点特异性氧化在有机合成中具有无可争议的效用。从简化对代谢物的获取和先导化合物的后期多样化到截断逆合成计划,学术界和工业界都越来越需要新的试剂和方法来实现这种转变。当前化学试剂的一个主要缺点是在结构和反应性方面缺乏多样性,这阻碍了用于快速筛选的组合方法的使用。在这方面,定向进化仍然最有希望在各种复杂环境中实现复杂的 C-H 氧化。在此,我们提出了一个设计合理的平台,该平台使用N-铵叶立德作为电化学驱动的氧化剂,用于位点特异性、化学选择性 C(sp 3 )-H 氧化。通过采用以计算为指导的第一性原理方法,这些新的介质被识别出来,并使用无处不在的构建块和简单的合成技术迅速扩展到一个库中。基于叶立德的 C-H 氧化方法表现出可调的选择性,这通常是此类氧化剂独有的,可应用于农业和制药领域的实际问题。
更新日期:2021-05-26
中文翻译:
用于电化学 C-H 氧化的 N-铵叶立德介体
强 C(sp 3 )-H 键的位点特异性氧化在有机合成中具有无可争议的效用。从简化对代谢物的获取和先导化合物的后期多样化到截断逆合成计划,学术界和工业界都越来越需要新的试剂和方法来实现这种转变。当前化学试剂的一个主要缺点是在结构和反应性方面缺乏多样性,这阻碍了用于快速筛选的组合方法的使用。在这方面,定向进化仍然最有希望在各种复杂环境中实现复杂的 C-H 氧化。在此,我们提出了一个设计合理的平台,该平台使用N-铵叶立德作为电化学驱动的氧化剂,用于位点特异性、化学选择性 C(sp 3 )-H 氧化。通过采用以计算为指导的第一性原理方法,这些新的介质被识别出来,并使用无处不在的构建块和简单的合成技术迅速扩展到一个库中。基于叶立德的 C-H 氧化方法表现出可调的选择性,这通常是此类氧化剂独有的,可应用于农业和制药领域的实际问题。