A Barbier reaction-Heck arylation sequence from α-bromomethylbutenolide to fused tri and tetracyclic lactones has been developed. The first step involving a Barbier reaction enabled installing ortho-bromoaromatics in α-ylidene γ-lactones. The latter substrates were subjected to intramolecular Heck reaction conditions which selectively afforded 6,5,5 or 6,6,5 fused ring systems depending on the ...

Aza-Heck cyclizations initiated by oxidative addition of Pd(0) -catalysts into the N-O bond of N-(pentafluoro-benzoyloxy)sulfonamides are described. These studies, which encompass only the second class of aza-Heck reaction developed to date, provide direct access to diverse N-heterocyclic ring systems.

A palladium (Pd)-catalyzed endo-selective Heck reaction of iodomethylsilyl ethers of phenols and aliphatic alkenols has been developed. Mechanistic studies reveal that this silyl methyl Heck reaction operates via a hybrid Pd-radical process and that the silicon atom is crucial for the observed endo selectivity. The obtained allylic silyloxycycles were further oxidized into (Z)-alkenyldiols.

An efficient enantioselective intramolecular Heck reaction of cyclohexadienones, using readily available and modular TADDOL-based mono- and bidentate phosphoramidites as chiral ligands and not requiring any additives, has been developed. Excellent enantioselectivities up to 96% ee are reached for the first time in a Heck reaction with monodentate ligands.

The syntheses of N,N'-dibenzyl-2,4-diaminopyrimidine-2'-deoxyribonucleoside and 1-methyl-2'-deoxypseudoisocytidine via Heck coupling are described. A survey of the attempts to use the Heck coupling to synthesize N,N'-dibenzyl-2,4-diaminopyrimidine-2'-deoxyribonucleoside is provided, indicating a remarkable diversity in outcome depending on the specific heterocyclic partner used.

A new fluorous PCP pincer ligand has been coordinated to Ni(II), Pd(II) and Pt(II). The air stable palladium complex, which promotes Heck reactions between methyl acrylate and either aryl bromides or iodides, can be recovered intact by fluorous solid-phase extraction and was reused four times in the Heck reaction between methyl acrylate and 4-bromoacetophenone without loss in catalytic activity.

Palladium-catalyzed tandem multifunctional reactions leading to the synthesis of substituted biaryl molecules have been developed including tandem Heck-direct arylation and tandem-sequential Heck-direct arylation-hydrogenation. These reactions occur in good yield and have been employed in the synthesis of a cytotoxic biaryl compound.