Transition-metal-catalyzed activation of inert C−H bonds and subsequent C−C bond formation have emerged as powerful synthetic tools for the synthesis of elaborate cyclic molecules. In this report, we introduce an efficient synthetic method of 3,4-unsubstituted isocoumarins adopting an electron-deficient Cp E Rh complex as the catalyst. The use of vinylene carbonate as a vinylene transfer reagent enables the direct construction of isocoumarins from readily available benzoic acids, without any external oxidants as well as bases. The reaction mechanism is evaluated by computational analysis to find an unprecedented "rhodium shift" event within the catalytic cycle.

A Rh­(III)-catalyzed annulative coupling of 3,5-diarylisothiazoles and alkynes is reported. The N–S bond in the isothiazole ring acts as an internal oxidant to regenerate the Rh­(III) species in combination with an external Cu­(II) oxidant, and the corresponding 1:2 coupling products are obtained. The remarkable difference in the reaction outcome between isothiazoles and the relevant isoxazoles has been investigated by DFT calculations, revealing that the relative stability of the enolate intermediates dictates the product selectivity.

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