13545-04-5Relevant articles and documents
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Cason,J.,Schmitz,F.J.
, p. 555 - 561 (1963)
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Campbell,P.H. et al.
, p. 6404 - 6410 (1969)
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Rosenthal et al.
, p. 3050,3052 (1958)
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Hydrogen-free homogeneous catalytic reduction of olefins in aqueous solutions
Gaviglio, Carina,Doctorovich, Fabio
, p. 5379 - 5384 (2008/12/20)
(Chemical Equation Presented) Herein we report a study involving the homogeneous catalytic reduction of unsaturated substrates in aqueous solutions or water-organic solvent mixtures. The reduction of olefins has been carried out in the presence of catalytic amounts of [Fe(CN)5NH3] 3- and excess of NH2OH, which under mild reaction conditions can be used to reduce carbon-carbon unsaturations without affecting carbonyl functionalities and aromatic rings. To explore the scope of the catalytic reduction, a wide variety of representative unsaturated substrates have been examined. The steric effects of the substituents on the carbon-carbon multiple bond as well as the regioselectivity and stereoselectivity of the catalyst have been studied. The deuterium kinetic isotope effect on the catalytic reduction of double bonds in olefins has been analyzed, and no significant kinetic isotope effect was found. Among the great advantages of this novel procedure for catalytic reduction are that hydrogen and high pressures are not needed, the catalyst is inexpensive and easily prepared, and water as well as water-organic solvent mixtures can be used as reaction media.
Stereoselective homogeneous hydrogenation. The basis of preferential anti-isomer formation in acyclic systems
Brown, John M.,Cutting, Ian,James, Alun P.
, p. 211 - 217 (2007/10/02)
Directed homogeneous hydrogenation of olefins derived from methyl acrylate proceeds with high selectivity.The reactant must possess a polar substituent at a chiral centre situated in the α'-position; this may be -OH, CO2R or NHCOR.The catalyst should be a cationic chelating rhodium biphosphine complex.In all cases high anti-stereoselectivity is observed in the reduced product, and this can be rationalised by a simple and general model.With an optically active catalyst, efficient kinetic resolution occurs, providing a means of access to optically active acrylates.Experimental details of typical hydrogenation reactions are provided.
