An unprecedented N-heterocyclic carbene (NHC) catalyzed Morita-Baylis-Hillman (MBH) reaction of β-substituted nitroalkenes and azodicarboxylates has been developed. Both β-aryl and β-alkyl nitroalkenes worked well for the reaction using 5 mol% of NHC catalyst, giving the desired α-hydrazino-α,β-unsaturated nitroalkenes in good to excellent yields.

Aza-Michael addition of amines, including aromatic and aliphatic amines, with α, β-unsaturated ketones was realized employing N-Heterocyclic Carbene (NHC) as organocatalyst, yielding β-amino ketones with up to 98% yield.

A novel conjugate hydrofluoroalkylation of α,β-unsaturated acyl-oxazolidinones is described. Using this method, enantiomerically pure β-trifluoromethylated amino acids were prepared. Trifluorovaline and trifluoroisoleucine were incorporated into peptides and found to show extremely low α-helix propensities.

A method for the palladium-catalyzed arylation of α,β-unsaturated valerolactams is reported. This new protocol provides arylation products in yields up to 95% and is applicable to a wide array of aryl and heteroaryl bromides. The optimization, scope and limitations are described.

Catalytic addition of silylacetylenes to α,β-unsaturated ketones proceeded in the presence of a cobalt complex coordinated with a bisphosphine ligand to give high yields of β-alkynylketones.

The sp3 C–H acetoxylation at the β-position of α,α-disubstituted α-amino acids proceeds smoothly under palladium catalysis in presence PhI(OAc)2. This reaction provides a straightforward synthetic route to non-natural β-acetoxy-α-amino acids. α-aminocyclopropanecarboxylic acid takes place via ring-opening selectively afford an acyclic γ-acetoxy-α,β-unsaturated amino acid.

Alkylation reactions of the nucleoside guanosine (Guo) by the α,β-unsaturated compounds (α,β-UC) acrylonitrile (AN), acrylamide (AM), acrylic acid (AA) and acrolein (AC), which can act as alkylating agents of DNA, were investigated kinetically. The following conclusions were drawn: i) The Guo alkylation mechanism by AC is different from those brought about the other α,β-UC; ii) for the first th...

An easy to operate method of catalytic hydroboration of unsaturated compounds has been developed with wide substrate scope. Reactions of various aldimines, ketimines, α,β-unsaturated carbonyl compounds, and alkynes were successfully executed with bis(pinacolato)diboron and N-heterocyclic carbenes in methanol without requiring a transition metal or inert atmosphere.

A synthetic equivalent of the Nazarov reagent, the silyl derivative 2, able to undergo base-catalyzed double Michael addition reactions with α,β-unsaturated carbonyl compounds has been developed. The new reagent satisfactorily reacts with unsaturated indolo[2,3-a]quinolizidine lactams to give pentacyclic yohimbinone-type derivatives.