The Photo-Enolization of β-Disubstituted αβ-Unsaturated Ketone

One-Pot Synthesis of β,β-Disubstituted α,β-Unsaturated Carbonyl Compounds.

TiCl4-promoted aldol reaction of ketones as aldol acceptors followed by elimination of the titanoxy group from the Ti-aldolates affords β,β-disubstituted α,β-unsaturated carbonyl compounds in a one-pot procedure. The use of additives, such as DMF, N,N,N',N'-tetramethylethylenediamine, and pyridine, in the elimination step was found to be important.

Organocatalytic asymmetric Michael-type reaction between β,γ-unsaturated α-keto ester and α-nitro ketone.

A Michael-type reaction of β,γ-unsaturated α-keto ester and α-nitro ketone was established. With a thiourea catalyst derived from cinchona alkaloid, the reactions afford products in 47-94% yields with 68-96% ee.

Ketone enolization by lithium hexamethyldisilazide: structural and rate studies of the accelerating effects of trialkylamines.

Mechanistic studies of the enolization of 2-methylcyclohexanone mediated by lithium hexamethyldisilazide (LiHMDS; TMS2NLi) in toluene and toluene/amine mixtures are described. NMR spectroscopic studies of LiHMDS/ketone mixtures in toluene reveal the ketone-complexed cyclic dimer (TMS2NLi)2(ketone). Rate studies using in situ IR spectroscopy show the enolization proceeds via a dimer-based transi...

Rhodium-Catalyzed Synthesis of 2,3-Disubstituted Indoles from β,β-Disubstituted Stryryl Azides**

Superparamagnetic Core-Shell-Type Fe3O4/Ru Nanoparticles as Catalysts for the Selective Hydrogenation of an Unconstrained α,β-Unsaturated Ketone

Selective hydrogenation of the carbon-oxygen bond in α,β-unsaturated carbonyl compounds is a synthetic challenge, since C=C bond reduction is thermodynamically more favorable (35 kJ mol–1) than C=O bond reduction.[1] This problem becomes even more complicated by the presence of an aromatic substituent in such systems because of possible ring hydrogenation.[2] Moreover, the transformation of uns...