Hydrosilylation of Aldehydes and Ketones Catalyzed by an N-Heterocyclic Carbene-Nickel Hydride Complex
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of this family of complexes and development an
asymmetric version of this reduction is currently
under investigation.[26]
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Experimental Section
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Typical Procedure for the Hydrosilylation of
Aldehydes
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A 10-mL oven-dried Schlenk tube containing a stirring bar
was loaded with 1 (4.6 mg, 1·10À5 mol) and 4 mL of THF.
The resulting purple solution was stirred for 5 min. A solu-
tion of NaHBEt3 in THF (20 mL, 1M in THF, Acros,
2·10À5 mol) was added dropwise, and the solution stirred
until the colour turned to deep red. The aldehyde
(1·10À3 mol) and Ph2SiH2 (186 mL, 1·10À3 mol) were then
added, in this order, and the reaction mixture was stirred in
a preheated oil bath at 258C for 1 or 17 h (see Table 2). The
reaction mixture was then quenched by the addition of
methanol (2 mL) and 2M NaOH (2 mL) and stirred for 2 h.
After the addition of water (5 mL), the product was extract-
ed with diethyl ether (3ꢅ10 mL). The combined organic
layers were dried over anhydrous MgSO4, filtered and con-
centrated under vacuum. The conversion was determined by
1H NMR, and the product purified by silica gel column
chromatography using a petroleum ether/diethyl ether mix-
ture.
[12] For representative reviews about iron-catalyzed hydro-
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[14] For very interesting studies concerning the hydrogena-
tion of ketones catalyzed by a closely related Cp*Ru-
NHC complex with a tethered primary amine donor,
see: a) W. W. N. O, A. J. Lough, R. H. Morris, Chem.
Commun. 2010, 46, 8240–8242; b) W. W. N. O, A. J.
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W. D. Jones, Inorg. Chem. 2011, 50, 9443–9453.
[16] For general reviews about hydrosilylation, see: a) Com-
prehensive Handbook on Hydrosilylation, (Ed.: B. Mar-
ciniec), Pergamon Press, Oxford, 1992; b) Hydrosilyla-
tion: A Comprehensive Review on Recent Advances,
(Ed.: B. Marciniec), Springer, Heidelberg, 2009.
[17] a) R. A. Kelly III, N. M. Scott, S. Dꢆez-Gonzꢇlez, E. D.
Stevens, S. P. Nolan, Organometallics 2005, 24, 3442–
3447; b) W. Buchowicz, A. Koziol, L. B. Jerzykiewicz,
T. Lis, S. Pasynkiewicz, A. Pecherzewska, A. Pietrzy-
Acknowledgements
JBS and CD are grateful to the Universitꢀ de Rennes 1, the
CNRS, Rennes Mꢀtropole, and the Ministꢁre de l’Enseigne-
ment Supꢀrieur et de la Recherche for financial support. VR
and MJC are grateful to the Universitꢀ de Strasbourg and the
CNRS for their financial help. The Agence Nationale de la
Recherche is also acknowledged for its support to VR and the
doctoral fellowship of MH (ANR 2010 JCJC 716 1; SBA-15-
NHC-NiCat).
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Adv. Synth. Catal. 2012, 354, 2619 – 2624
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2623