Hybrid Phosphine/Amino-Acid Ligands Built on Phenyl and Ferrocenyl Platforms: Application in the Suzuki Coupling of o-Dibromobenzene with Fluorophenylboronic Acid.

We describe the synthesis and characterization of two classes of hybrid phosphino ligands functionalized with amino ester or amino acid groups. These compounds are built either on a rigid planar phenyl platform or on a functionalized - conformationally controlled - rotational ferrocene backbone. Modifications at the -PR phosphino groups (R=aryl and alkyl, with various steric bulk, Ph, Mes, i-Pr, Cy) and at the amino acid/amino ester functions are reported, showing a valuable high modularity.

Transition-Metal-Free α-Vinylation of Enolizable Ketones with β-Bromostyrenes.

An α-vinylation of enolizable ketones has been developed by using β-bromostyrenes and a KO tBu/NMP system. β,γ-Unsaturated ketones of E configuration were obtained in excellent yield and selectivity. Further synthetic possibilities are highlighted by one-pot functionalization via trapping of intermediate dienolates with alkyl, allyl, benzyl, and propargyl halides to generate quaternary centers.

Synthesis of 3,3'-Disubstituted Indolenines Utilizing the Lewis Acid Catalyzed Alkylation of 2,3-Disubstituted Indoles with Trichloroacetimidates.

Trichloroacetimidates function as effective electrophiles for the selective C3-alkylation of 2,3-disubstituted indoles to provide 3,3'-disubstituted indolenines. These indolenines are common synthetic intermediates that are often utilized in the synthesis of complex molecules. Effective reaction conditions utilizing Lewis acid catalysts have been determined, and the scope of the reaction with respect to indole and imidate reaction partner has been investigated.