Mechanistic study on the conversion of primary alcohols and butadiene into branched ketones using a rhodium catalyst
This work investigates the mechanism of a Rh(I)-catalyzed transformation of primary alcohols and butadiene into saturated branched ketones, without premetalated intermediates or external hydrogen sources. DFT calculations reveal a four-step pathway involving alcohol oxidation, butadiene hydrogenation, carbonyl addition, and intramolecular hydrogen transfer. The rate-determining step is the sterically hindered carbonyl addition, which also explains why …