60199-02-2Relevant articles and documents
New Zinc Catalyst for Hydrosilylation of Carbonyl Compounds
Alshakova, Iryna D.,Nikonov, Georgii I.
, p. 3305 - 3312 (2019)
A new zinc complex was synthesized and applied in the catalytic hydrosilylation of carbonyl compounds. Optimization of the reaction conditions showed that the presence a substoichiometric amount of methanol accelerates the process significantly. The reaction can proceed at very low catalyst load (down to 0.1 molpercent) under mild reaction conditions. The reaction tolerates the presence of C=C bonds, and thus can be useful for the synthesis of allylic alcohols from α,β-unsaturated aldehydes and ketones.
Phosphido-bridged Ta/Rh bimetallic complex: Synthesis, structure, and catalytic hydrosilylation of acetophenone
Findlay, Andrea E.,Leelasubcharoen, Somying,Kuzmina, Lyudmila G.,Howard, Judith A. K.,Nikonov, Georgii I.
, p. 9264 - 9269 (2010)
Reaction of Cp2TaH3 (1) with ClPEt2 gives the insertion product [Cp2TaH2(PHEt2)]Cl (5), which upon deprotonation with LiN(SiMe3)2 affords the phosphido complex Cp
Homoleptic cobalt(II) phenoxyimine complexes for hydrosilylation of aldehydes and ketones without base activation of cobalt(II)
Hori, Momoko,Ishikawa, Ryuta,Koga, Yuji,Matsubara, Kouki,Mitsuyama, Tomoaki,Shin, Sayaka
supporting information, p. 1379 - 1387 (2021/05/29)
Air-stable, easy to prepare, homoleptic cobalt(II) complexes bearing pendant-modified phenoxyimine ligands were synthesized and determined. The complexes exhibited high catalytic performance for reducing aldehydes and ketones via catalytic hydrosilylation, where a hydrosilane and a catalytic amount of the cobalt(II) complex were added under base-free conditions. The reaction proceeded even in the presence of excess water, and excellent functional-group tolerance was observed. Subsequent hydrolysis gave the alcohol in high yields. Moreover, H2O had a critical role in activation of the Co(II) catalyst with hydrosilane. Several additional results also indicated that the cobalt(II) center acts as an active catalyst in the hydrosilylation of aldehydes and ketones.
A Masked Cuprous Hydride as a Catalyst for Carbonyl Hydrosilylation in Aqueous Solutions
Ritter, Florian,Mukherjee, Debabrata,Spaniol, Thomas P.,Hoffmann, Alexander,Okuda, Jun
supporting information, p. 1818 - 1822 (2019/01/09)
Redox-unstable cuprous hydridotriphenylborate was isolated as an N-heterocyclic carbene adduct [(IPr)Cu(HBPh3)] (IPr=1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) with good thermal stability. Although this compound displays a contact ion-pa
Hypercoordinate ketone adducts of electrophilic π3-H2SiRR′ ligands on ruthenium as key intermediates for efficient and robust catalytic hydrosilation
Lipke, Mark C.,Tilley, T. Don
, p. 16387 - 16398 (2015/02/05)
The electrophilic π3-H2SiRR′ σ-complexes [PhBPPh3]RuH(π3-H2SiRR′) (RR′ = MePh, 1a; Ph2, 1b; [PhBPPh3]- = [PhB(CH2PPh2)
A cationic zinc hydride cluster stabilized by an N-heterocyclic carbene: Synthesis, reactivity, and hydrosilylation catalysis
Rit, Arnab,Zanardi, Alessandro,Spaniol, Thomas P.,Maron, Laurent,Okuda, Jun
supporting information, p. 13273 - 13277 (2015/02/19)
The trinuclear cationic zinc hydride cluster [(IMes)3Zn3H4 (THF)](BPh4)2 (1) was obtained either by protonation of the neutral zinc dihydride [(IMes)ZnH2]2 with a Bronsted acid o
Highly efficient large bite angle diphosphine substituted molybdenum catalyst for hydrosilylation
Chakraborty, Subrata,Blacque, Olivier,Fox, Thomas,Berke, Heinz
, p. 2208 - 2217 (2013/10/22)
Treatment of the complex Mo(NO)Cl3(NCMe)2 with the large bite angle diphosphine, 2,2′-bis(diphenylphosphino)diphenylether (DPEphos) afforded the dinuclear species [Mo(NO)(PaP)Cl 2]2[μCl]2 (PaP = DPEph
Controlled hydrosilylation of carbonyls and imines catalyzed by a cationic aluminum alkyl complex
Koller, Juergen,Bergman, Robert G.
scheme or table, p. 2530 - 2533 (2012/06/04)
The synthesis, characterization, and unprecedented catalytic activity of cationic aluminum alkyl complexes toward hydrosilylation are described. X-ray crystallographic analysis of Tp*AlMe2 (1) and [Tp*AlMe][I3] (3) revealed the prefe
Nonhydride mechanism of metal-catalyzed hydrosilylation
Shirobokov, Oleg G.,Kuzmina, Lyudmila G.,Nikonov, Georgii I.
supporting information; experimental part, p. 6487 - 6489 (2011/06/23)
A 1:1:1 reaction between complex (Tp)(ArN=)Mo(H)(PMe3) (3), silane PhSiD3, and carbonyl substrate established that hydrosilylation catalyzed by 3 is not accompanied by deuterium incorporation into the hydride position of the catalyst, thus ruling out the conventional hydride mechanism based on carbonyl insertion into the M-H bond. An analogous result was observed for the catalysis by (O=)(PhMe2SiO)Re(PPh 3)2(I)(H) and (Ph3PCuH)6.
Designing the "Search pathway" in the development of a new class of highly efficient stereoselective hydrosilylation catalysts
Cesar, Vincent,Beliemin-Laponnaz, Stephane,Wadepohl, Hubert,Gade, Lutz H.
, p. 2862 - 2873 (2007/10/03)
A highly efficient class of N-heterocyclic carbene-based catalysts for the asymmetric hydrosilylation of prochiral ketones was discussed. The potential pitfalls associated with the nonlinearity in the behavior of an enantioselective catalyst in response to the variations of key reaction parameters were also described. The modular design of a new catalyst is based essentially on a single assembly step of its structural and functional subunits. It was observed that the direct coupling of oxazolines and N-heterocyclic carbenes leads to chelating C,N ancillary ligands for asymmetric catalysis that combines both an 'anchor' unit and a stereodirecting element.
