Guo Hong-Mei, Wu Xuesong
Hubei Key Laboratory of Bioinorganic Chemistry & Materia Medica, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan, China.
Nat Commun. 2021 Sep 10;12(1):5365. doi: 10.1038/s41467-021-25702-4.
The delivery of alkyl radicals through photocatalytic deoxygenation of primary alcohols under mild conditions is a so far unmet challenge. In this report, we present a one-pot strategy for deoxygenative Giese reaction of alcohols with electron-deficient alkenes, by using xanthate salts as alcohol-activating groups for radical generation under visible-light photoredox conditions in the presence of triphenylphosphine. The convenient generation of xanthate salts and high reactivity of sequential C-S/C-O bond homolytic cleavage enable efficient deoxygenation of primary, secondary and tertiary alcohols with diverse functionality and structure to generate the corresponding alkyl radicals, including methyl radical. Moreover, chemoselective radical monodeoxygenation of diols is achieved via selective formation of xanthate salts.
在温和条件下通过光催化伯醇脱氧来传递烷基自由基是迄今为止尚未解决的挑战。在本报告中，我们提出了一种醇与缺电子烯烃的脱氧吉泽反应的一锅法策略，该方法使用黄原酸盐作为醇的活化基团，在可见光光氧化还原条件下，在三苯基膦存在下生成自由基。黄原酸盐的便捷生成以及连续的C-S/C-O键均裂的高反应活性，能够使具有不同官能团和结构的伯醇、仲醇和叔醇高效脱氧，生成相应的烷基自由基，包括甲基自由基。此外，通过选择性形成黄原酸盐，实现了二醇的化学选择性自由基单脱氧。
