Synthetic aspects of stereoselective hydroformylation.

The hydroformylation of olefins is well known as one of the industrially most important processes which rely on homogeneous catalysis. Additionally, the hydroformylation represents an ideal atom economic C/C-bond forming reaction with unique opportunities for application in target-oriented organic synthesis, provided that selectivity and in particular stereoselectivity in the course of this metal-catalyzed addition reaction can be controlled. This Account describes recent developments on new and efficient concepts making use of substrate-direction to control stereoselectivity throughout the course of the hydroformylation reaction. Emphasis is given to the concept of substrate-bound catalyst-directing groups which allow for high levels of acyclic stereocontrol. Applications of these new stereoselective variants of the hydroformylation reaction in the context of organic synthesis are discussed. Additionally, recent applications of stereoselective hydroformylation as part of Domino-type processes are covered.