Search

The present article summarizes the development of two novel and complementary catalytic methods to access alpha-chiral aldehydes. A C1-symmetric chiral (P,N) ligand with a structure derived from the ubiquitous binepine scaffold has been specifically designed for the Pd-catalyzed alpha-arylation of aldehydes to access indane derivatives with a well-defined quaternary stereocenter in high yields and excellent enantioselectivities. In addition, a dinuclear palladium hydride catalyst has been synthesized for the isomerization of terminal and trisubstituted epoxides into aldehydes and ketones respectively. Combined experimental and theoretical investigations pointed to an unprecedented 'epoxide-opening/hydride-transfer' sequence. The mechanism also features two distinct enantio-determining steps in the kinetic resolution of racemic epoxides.

The present article describes the recent catalytic asymmetric methods developed in our group to access enantioenriched chiral aldehydes. We are generally aiming at developing complementary strategies based on either homogeneous organometallic catalysts or amino-catalysts and sometimes on a combination of both. Recent successes comprise a perfectly redox-economical iridium-catalyzed asymmetric isomerization of primary allylic alcohols under very mild conditions and the development of a transition metal-catalyzed anti-Markovnikov asymmetric hydroboration of 1,1-disubstituted olefins. The developments of these two processes along with preliminary mechanistic investigations are presented herein.

This article describes the situation of Department of Organic Chemistry in the year of the 450th anniversary of the University of Geneva.