13735-82-5Relevant academic research and scientific papers
Base-free dehydrogenative coupling of enolizable carbonyl compounds with silanes
Koenigs, C. David F.,Klare, Hendrik F. T.,Ohki, Yasuhiro,Tatsumi, Kazuyuki,Oestreich, Martin
supporting information; experimental part, p. 2842 - 2845 (2012/08/07)
A dehydrogenative coupling between enolizable carbonyl compounds and equimolar amounts of triorganosilanes catalyzed by a tethered ruthenium complex with a Ru-S bond is reported. The complex is assumed to fulfill a dual role by activating the Si-H bond to release a silicon electrophile and by abstracting an α-proton from the intermediate silylcarboxonium ion, only liberating dihydrogen as the sole byproduct. Reaction rates are exceedingly high at room temperature with very low loadings of the ruthenium catalyst.
Analysis of the enantioselectivities and initial rates of the hydrosilylation of acetophenone catalyzed by [Rh(cod)Cl]2/(chiral diphosphine). The quantitative analysis of ligand effects
Reyes, Clementina,Prock, Alfred,Giering, Warren P.
, p. 13 - 26 (2007/10/03)
Through the application of the quantitative analysis of ligand effects (QALE) method to the study of the hydrosilylation of acetophenone, we have shown, for the first time, that the initial rate and enantioselectivity of a complicated catalytic system responds in a rational manner to the variations in the stereoelectronic properties of the silane. The reactions (in benzene-d6 at 63 °C) were catalyzed by [Rh(cod)Cl]2/(chiral diphosphine) (chiral diphosphine=(R)-BINAP [(R)-(+)-2,2′-bis(diphenylphosphino)- 1,1′binaphthyl], (R,R)-tolyl-BINAP [(R)-(+)-2,2′-bis (di-p-tolylphosphino)-1,1′-binaphthyl], (R,R)-Me-DUPHOS [(R,R )-(-)-1,2-Bis-2,5-dimethylphospholano)benzene], (R,R)-DIOP [(R,R)-(-)-2,3-O-isopropylidine-2,3-dihydroxy-1,4-bis(diphenylphosphino) butane], and (R)-QUINAP [(R)-(+)-1-(2-diphenylphosphino-1-naphthyl) isoquinoline]. The ee's (R) of the hydrosilylation products (CH3CH(OSiR3)Ph) range between - 9 and 53% with the (R)-QUINAP giving the poorest enantioselectivity. The QALE analyses of log( R/S) for (R)-BINAP, (R)-tolyl-BINAP, (R,R)-Me-DUPHOS, and (R,R)-DIOP reveal that the steric effects associated with the silanes are not monotonic.
