- POCN Ni(ii) pincer complexes: Synthesis, characterization and evaluation of catalytic hydrosilylation and hydroboration activities
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A series of iminophosphinite POCN pincer Ni(ii) complexes, (POCN)NiMe and (POCN)NiLn(BX4) (L = CH3CN, n = 0, 1; X = F, Ph, C6F5), have been developed and subjected to catalytic hydrosilylation of alkenes, aldehydes and ketones and hydroboration of carbonyl compounds. The stoichiometric reactivity of (POCN)NiMe and (POCN)Ni(BF4) with PhSiH3 and HBPin suggests that catalytic reactions proceed via the hydride intermediate (POCN)NiH. With regard to reactions with HBPin, efficient and mild hydroboration of a variety of carbonyl compounds, including highly chemoselective hydroboration of benzaldehyde in the presence of other common potent reductive functional groups, such as alkenes, alkynes, esters, amides, nitriles, nitro compounds and even ketones, and the first example of base metal catalyzed hydroboration of amides, including mild direct hydroborative reduction of primary and secondary amides to borylated amines were demonstrated for (POCN)NiMe.
- Gudun, Kristina A.,Segizbayev, Medet,Adamov, Assyl,Balanay, Mannix P.,Khalimon, Andrey Y.,Plessow, Philipp N.,Lyssenko, Konstantin A.
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supporting information
p. 1732 - 1746
(2019/03/07)
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- Selective synthesis of halosilanes from hydrosilanes and utilization for organic synthesis
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Selective synthesis of halosilanes has been examined. Various types of halosilanes and halohydrosilanes, such as R3SiX, R2SiHX, R2SiX2, RSiH2X, RSiHX2 (X=Cl, Br, F), were obtained by the reactions of the corresponding hydrosilanes with Cu(II)-based reagents selectively in high yields. This method could be also applied to the synthesis of chlorofluorosilanes and chlorohydrogermanes. On the other hand, iodo- and bromosilanes and germanes were obtained by Pd- or Ni-catalyzed hydride-halogen exchange reactions of hydrosilanes with alkyl or allyl halides. Their synthetic applications have been demonstrated by using iodo- and bromosilanes and chlorofluorosilanes.
- Kunai, Atsutaka,Ohshita, Joji
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- Catalytic asymmetric hydrosilylation of 1,3-dienes with difluoro( phenyl) silane
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A palladium complex with an optically active ligand catalyzes asymmetric hydrosilylation of 1,3-dienes using difluoro(phenyl)silane to give optically active allyl difluoro(phenyl)silanes in good enantiomeric excess.Keywords: Chirality; Fluorine; Silane; Ferrocene; Silicon; Palladium
- Ohmura, Hideaki,Matsuhashi, Hayao,Tanaka, Makoto,Kuroboshi, Manabu,Hiyama, Tamejiro,et al.
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p. 167 - 172
(2007/10/02)
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