Abstract
AbstractTransition metal-catalyzed reductive difunctionalization of alkenes with alkyl halides is a powerful method for upgrading commodity chemicals into densely functionalized molecules. However, super stoichiometric amounts of metal reductant and the requirement of installing a directing group into alkenes to suppress the inherent β-H elimination bring great limitations to this type of reaction. We demonstrate herein that the difunctionalization of alkenes with two different alkyl halides is accessible via a radical-anion relay with Na2S2O4 as both reductant and sulfone-source. The Na2S2O4 together with the electron-shuttle catalyst is crucial to divert the mechanistic pathway toward the formation of alkyl sulfone anion instead of the previously reported alkylmetal intermediates. Mechanistic studies allow the identification of carbon-centered alkyl radical and sulfur-centered alkyl sulfone radical, which are in equilibrium via capture or extrusion of SO2 and could be converted to alkyl sulfone anion accelerated by iron electron-shuttle catalysis, leading to the observed high chemoselectivity.
Funder
National Natural Science Foundation of China
Publisher
Springer Science and Business Media LLC
Cited by
9 articles.
订阅此论文施引文献
订阅此论文施引文献,注册后可以免费订阅5篇论文的施引文献,订阅后可以查看论文全部施引文献