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Visible-Light-Driven Photocatalytic Kharasch-Type Addition of 1,6-Enynes

Fang-Zhou Geng, Shichao Wang, Kexian Song, Wen‐Juan Hao, Bo Jiang

2021Chinese Journal of Organic Chemistry15 citationsDOIOpen Access PDF

Abstract

A new visible-light-driven photocatalytic Kharasch-type addition of 1,6-enynes was reported. By using the characteristics of the in-situ-generation of trihalomethyl radicals from photocatalytic reduction of trichloromethane bromide and carbon tetrabromide, fac-Ir(ppy)3-catalyzed Kharasch-type addition of 1,6-enynes of these polyhalogenated hydrocarbon substrates at room temperature was conducted under visible-light irradiation, regioselectively affording 1-indanone derivatives with an exocyclic double bond and a quaternary carbon in moderate to good yields. Based on the experimental results and literature reports, a reasonable reaction mechanism was proposed, which involved the in-situ-generation of trihalomethyl radicals, radical-induced addition-cyclization and radical cross coupling. In addition, this protocol featured wide substrate scope, high functional group compatibility, 100% atomic utilization, and mild conditions as well as simple operation. It provides a green, mild, and efficient synthetic strategy for the construction of 1-indanone skeleton with potential application, which is consistent with the concept of green chemistry.

Topics & Concepts

ChemistryPhotocatalysisPhotochemistryVisible spectrumOrganic chemistryOptoelectronicsCatalysisPhysicsRadical Photochemical ReactionsOxidative Organic Chemistry ReactionsCatalytic C–H Functionalization Methods