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[structure: see text] A new transition state of the addition step in the Baeyer-Villiger reaction was found. The role of proton acceptor is played by the carbonyl oxygen atom, and the free energy barrier is 12.7 kcal/mol lower than that previously reported. This finding changes the mechanism for the acid catalysis and could be of interest for similar reactions in which it is known that such catalysis occurs, especially in nonpolar solvents.

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