Mechanistic Insight into the Diastereoselective Rhodium‐Catalyzed Pauson–Khand Reaction: Role of Coordination Number in Stereocontrol

Abstract

How much CO? Theoretical analysis of the origin of diastereocontrol in the rhodium-catalyzed Pauson–Khand reaction (see scheme) provides two mechanistic scenarios in which optimum selectivity can be attributed to a five- rather than a four-coordinate organorhodium complex. The relative population of these complexes is related to carbon monoxide concentration, a finding which is in contrast to phosphine-containing rhodium(I) complexes.