First study of rhodium(I) complexes with chiral sulfur-containing terpenoids as catalytic systems for ketone hydrosilylation

Abstract

Using a “chiral pool” approach, a number of chiral thiolate and sulfide ligands based on natural terpenes and terpenoids have been synthesized in a few simple steps. Two new Rh-thiolate complexes with the formula [Rh(CO)₂(μ-SR)]₂ were obtained. The influence of these complexes and catalytic systems formed by combining the synthesized ligands with [Rh(CO)₂(μ-Cl)]₂ and [Rh(cod)(μ-Cl)]₂, on the reaction rate, chemoselectivity, stereoselectivity and formation of tetraphenyldisiloxane in Rh-catalyzed asymmetric hydrosilylation of acetophenone as a model reaction have been studied. Mechanistic aspects of formation of silyl enol ether as a side product in the presence of S-containing ligands are presented.

Graphical Abstract

Keywords:

• Hydrosilylation
• sulfides
• thiols
• rhodium
• terpenoids
• terpenes