First study of rhodium(I) complexes with chiral sulfur-containing terpenoids as catalytic systems for ketone hydrosilylation |
| |
| Authors: | Vladimir M Uvarov Dimitry A de Vekki |
| |
| Institution: | 1. Department of Chemical Technology of Polymers, St. Petersburg State Institute of Technology, St. Petersburg, Russiavladi.uvarov@gmail.com;3. Department of Chemical Technology of Polymers, St. Petersburg State Institute of Technology, St. Petersburg, Russia |
| |
| Abstract: | AbstractUsing 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. |
| |
| Keywords: | Hydrosilylation sulfides thiols rhodium terpenoids terpenes |
|
|
