Use of Theoretical Chemistry To Explain Baeyer-Villiger Oxidations of Methoxybenzaldehydes
N. Anoune, H. Hannachi, P. Lantéri, R. Longeray, and C. Arnaud
J. Chem. Educ. 75, 1290-1291 (1998) (https://www.thevespiary.org/rhodium/Rhodium/pdf/baeyer-villiger.anisaldehyde.pdf)
(https://www.thevespiary.org/rhodium/Rhodium/pdf/baeyer-villiger.anisaldehyde.pdf)
Abstract
Part 1: A study of the Baeyer-Villiger reaction on Anisaldehyde. This portion of the study is intended to show advanced students the feasibility of using this reaction on an aromatic aldehyde. The use of monopersuccinic acid (PSA) constitutes an interesting alternative to the classical m-chloroperoxybenzoic acid (mCPBA).
Part 2: The experiment is extended to various polymethoxybenzaldehydes and theoretical calculations are used to explain their particular behaviors. In acid medium at 55°C the first step of reaction on dimethoxybenzaldehydes is rate determining. This is a special feature, as the rearrangement that constitutes the second step is usually rate determining.