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Rhodium‐, copper‐ and iridium‐catalyzed reactions of the 13C‐labelled diazo carbonyl substrates 18* and 19* were performed. Results obtained from copper‐ and iridium‐catalyzed reactions of the 13C‐labelled α‐diazo β‐keto ester 19* indicate that either or both of these reactions do not proceed via a free oxonium ylide but instead follow a competing non‐ylide route that delivers apparent [2,3]‐sigmatropic...