C-O hydrogenolysis catalyzed by Pd-PMHS nanoparticles in the company of chloroarenes.
Catalytic Pd(OAc)(2) and polymethylhydrosiloxane (PMHS), in conjunction with aqueous KF, and a catalytic amount of an aromatic chloride, effects the chemo-, regio-, and stereoselective deoxygenation of benzylic oxygenated substrates at room temperature in THF. Preliminary mechanistic experiments suggest the process to involve palladium-nanoparticle-catalyzed hydrosilylation followed by C-O reduction. The chloroarene additive appears to facilitate the hydrogenolysis process through the slow controlled release of HCl.
Department of Chemistry, Michigan State University, East Lansing, Michigan 48824, USA.
Ronald J
RJ
Rahaim
Robert E
RE
Maleczka
D002244:Carbon / Q000737:chemistry*; D002384:Catalysis; D020650:Combinatorial Chemistry Techniques; D006843:Hydrocarbons, Chlorinated / Q000737:chemistry; D006851:Hydrochloric Acid / Q000737:chemistry; D015394:Molecular Structure; D053758:Nanoparticles / Q000737:chemistry*; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*; D010165:Palladium / Q000737:chemistry*; D012833:Siloxanes / Q000737:chemistry*; D013237:Stereoisomerism
D006843:Hydrocarbons, Chlorinated; D012833:Siloxanes; C402373:poly(methylhydrosiloxane); D010165:Palladium; D002244:Carbon; D006851:Hydrochloric Acid; D010100:Oxygen
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