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A mechanistic study of the substituent‐dependent ring formations in RhIII‐catalyzed CH activation/cycloaddition of benzamide and diazo compounds was carried out by using DFT calculations. The results indicated that the decomposition of the diazo is facilitated upon the formation of the five‐membered rhodacycle, in which the RhIII center is more electrophilic. The insertion of carbenoid into RhC(phenyl)...
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