使用镍光氧化还原催化从链烷烃直接形成 C-C 键。
Direct C-C Bond Formation from Alkanes Using Ni-Photoredox Catalysis.
机构信息
Department of Chemistry , Princeton University , Princeton , New Jersey 08544 , United States.
出版信息
J Am Chem Soc. 2018 Oct 31;140(43):14059-14063. doi: 10.1021/jacs.8b09191. Epub 2018 Oct 16.
Abstract
A method for direct cross coupling between unactivated C(sp)-H bonds and chloroformates has been accomplished via nickel and photoredox catalysis. A diverse range of feedstock chemicals, such as (a)cyclic alkanes and toluenes, along with late-stage intermediates, undergo intermolecular C-C bond formation to afford esters under mild conditions using only 3 equiv of the C-H partner. Site selectivity is predictable according to bond strength and polarity trends that are consistent with the intermediacy of a chlorine radical as the hydrogen atom-abstracting species.
摘要
通过镍和光氧化还原催化，实现了未活化的 C(sp)-H 键和氯甲酸酯之间的直接交叉偶联。通过镍和光氧化还原催化，实现了未活化的 C(sp)-H 键和氯甲酸酯之间的直接交叉偶联。通过镍和光氧化还原催化，实现了未活化的 C(sp)-H 键和氯甲酸酯之间的直接交叉偶联。一种通过镍和光氧化还原催化实现的未活化 C(sp)-H 键与氯甲酸酯直接交叉偶联的方法。通过镍和光氧化还原催化，实现了未活化的 C(sp)-H 键和氯甲酸酯之间的直接交叉偶联。通过镍和光氧化还原催化，实现了未活化的 C(sp)-H 键和氯甲酸酯之间的直接交叉偶联。通过镍和光氧化还原催化，实现了未活化的 C(sp)-H 键和氯甲酸酯之间的直接交叉偶联。多种原料化学品，如（a）环烷烃和甲苯，以及晚期中间体，通过分子间 C-C 键形成，在温和条件下仅使用 3 当量的 C-H 配体，得到酯。根据键强度和极性趋势，可以预测出位点选择性，这些趋势与氯自由基作为氢原子提取物种的中间体一致。
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