Visible-Light-Induced Alkoxyl Radical Generation Enables Selective C(sp3)-C(sp3) Bond Cleavage and Functionalizations
Visible-Light-Induced Alkoxyl Radical Generation Enables Selective C(sp3)-C(sp3) Bond Cleavage and Functionalizations
复制标题
可见光诱导的烷氧基自由基生成实现选择性 C(sp(3))-C(sp(3)) 键断裂和官能化
DOI：
10.1021/jacs.5b13066
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发表时间：
2016-02-10
影响因子：
15
通讯作者：
Chen, Yiyun
中科院分区：
文献类型：
--
作者：
Jia, Kunfang;Zhang, Fuyuan;Chen, Yiyun
烷氧基自由基是一种重要的反应中间体在机理研究和有机合成;然而，它目前的生成从醇氧化严重依赖于过渡金属活化在强氧化条件下。本文首次报道了在温和的反应条件下，环碘（III）试剂催化下可见光诱导醇氧化生成烷氧基自由基。烷氧基自由基的β-断裂使得能够与各种应变环烷醇以及首次与直链醇进行选择性C（sp（3））-C（sp（3））键断裂和炔基化/烯基化反应。
The alkoxyl radical is an important reactive intermediate in mechanistic studies and organic synthesis; however, its current generation from alcohol oxidation heavily relies on transition metal activation under strong oxidative conditions. Here we report the first visible-light induced alcohol oxidation to generate alkoxyl radicals by cyclic iodine(III) reagent catalysis under mild reaction conditions. The beta-fragmentation of alkoxyl radicals enables selective C(sp(3))-C(sp(3)) bond cleavage and alkynylation/alkenylation reactions with various strained cycloalkanols, and for the first time with linear alcohols.