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Visible Light-Induced Coupling Cyclization Reaction of α-Diazosulfonium Triflates with α-Oxocarboxylic Acids or Alkynes

Xue‐Cen Xu, Dan‐Ni Wu, Yong‐Xin Liang, Ming Yang, Haiyan Yuan, Yu‐Long Zhao

2022The Journal of Organic Chemistry34 citationsDOI

Abstract

A photocatalyst-free radical cleavage of α-diazo sulfonium salts has been developed for the first time. The reaction provides an efficient method for the generation of diazomethyl radicals from α-diazosulfonium triflates under photochemical conditions. Utilizing the in situ generated diazomethyl radicals as key intermediate, the coupling cyclization reaction of α-diazosulfonium triflates with α-oxocarboxylic acids or alkynes has been achieved. The method affords a diverse set of important 2,5-disubstituted 1,3,4-oxadiazoles and 3,5-disubstituted-1H-pyrazoles with excellent regioselectivity in a single step. A reaction mechanism involving a radical pathway was further supported by control experiments and DFT calculations.

Topics & Concepts

RegioselectivitySulfoniumRadicalChemistryDiazoPhotochemistryCleavage (geology)Combinatorial chemistryPhotocatalysisMedicinal chemistryOrganic chemistryCatalysisSalt (chemistry)Materials scienceComposite materialFracture (geology)Cyclopropane Reaction MechanismsCatalytic C–H Functionalization MethodsSulfur-Based Synthesis Techniques