Linear free energy correlation analysis on the electronic effects of Rh(II) carbene O-H insertion.

The relative rate constants for the Rh(II)-catalyzed insertion of diazoacetone into the O-H bond have been measured through intermolecular competitions. The kinetic data were subjected to Hammett correlation analysis, and mechanistic implication of the results with respect to a stepwise vs a concerted O-H insertion pathway is discussed.