18724-46-4Relevant academic research and scientific papers
Electrophilic Organobismuth Dication Catalyzes Carbonyl Hydrosilylation
Kannan, Ramkumar,Balasubramaniam, Selvakumar,Kumar, Sandeep,Chambenahalli, Raju,Jemmis, Eluvathingal D.,Venugopal, Ajay
, p. 12717 - 12721 (2020)
Bismuth compounds are gaining importance as potential alternatives to transition-metal complexes and electron deficient lighter p-block compounds in homogeneous catalysis. Computational analysis on the two-coordinate [(Me2NC6H4)Bi]2+ possessing three electrophilic sites is experimentally evidenced by the isolation of [{Me2NC6H4}Bi{OP(NMe2)3}3][B(3,5-C6H3Cl2)4]2. These observations led us to generate dicationic organobismuth catalyst, [(Me2NC6H4)Bi(L)3]2+ (L=aldehyde/ketone), evidenced by NMR spectroscopy in solution and by single-crystal X-ray diffraction in the solid state. It efficiently catalyzes hydrosilylation of aldehydes and ketones resulting in silyl ethers as the only products in high yields. Our investigations support a carbonyl activation mechanism at the bismuth center followed by Si?H addition.
A Versatile Iridium(III) Metallacycle Catalyst for the Effective Hydrosilylation of Carbonyl and Carboxylic Acid Derivatives
Corre, Yann,Rysak, Vincent,Trivelli, Xavier,Agbossou-Niedercorn, Francine,Michon, Christophe
supporting information, p. 4820 - 4826 (2017/09/07)
A versatile iridium(III) metallacycle catalysed rapidly and selectively the reduction of a large array of challenging esters and carboxylic acids as well as various ketones and aldehydes. The reactions proceeded in high yields at room temperature by hydrosilylation followed by desilylation. Although the reactions of various aldehydes and ketones resulted exclusively in alcohols, the hydrosilylation of esters led to alcohols or ethers, depending on the type of substrate. Regarding the carboxylic acids, again the nature of the reagent controlled the outcome of the hydrosilylation reaction, either alcohols or aldehydes being formed.
