A rhodium-catalyzed oxidative annulation of benzimidates with elemental sulfur for the direct construction of isothiazole rings is reported. The proposed reaction mechanism involving Rh(I)/Rh(III) redox is supported by a stoichiometric reaction of metallacycle species as well as DFT calculations. This method is also applicable to selenium cyclization to produce isoselenazole derivatives. The alkoxy substituent at C3 can be used for further functionalization of the azole core.
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