通过受阻自由基对获取烷氧基自由基：叔醇的多种氧化官能团化反应
Accessing Alkoxy Radicals via Frustrated Radical Pairs: Diverse Oxidative Functionalizations of Tertiary Alcohols.
作者信息
Ju Minsoo, Lee Sukwoo, Marvich Halle M, Lin Song
机构信息
Department of Chemistry and Chemical Biology, Cornell University, Ithaca, New York 14853, United States.
出版信息
J Am Chem Soc. 2024 Jul 24;146(29):19696-19703. doi: 10.1021/jacs.4c07125. Epub 2024 Jul 16.
Abstract
Alkoxy radicals are versatile reactive intermediates in organic synthesis. Here, we leverage the principle of frustrated radical pair to provide convenient access to these highly reactive species directly from tertiary alcohols via oxoammonium-mediated oxidation of the corresponding alkoxides. This approach enabled various synthetically useful transformations including β-scission, radical cyclization, and remote C-H functionalization, giving rise to versatile alkoxyamines that can be further elaborated to various functionalities.
摘要
烷氧基自由基是有机合成中用途广泛的反应中间体。在此，我们利用受挫自由基对的原理，通过氧鎓介导的相应醇盐氧化反应，直接从叔醇方便地获得这些高活性物种。这种方法实现了各种具有合成价值的转化，包括β-断裂、自由基环化和远程C-H官能化，生成了多种用途广泛的烷氧基胺，这些烷氧基胺可进一步转化为各种官能团。
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