Unusual Allylpalladium Carboxylate Complexes: Identification of the Resting State of Catalytic Enantioselective Decarboxylative Ketone Allylic Alkylation Reactions**

Unusual allylpalladium carboxylate complexes: identification of the resting state of catalytic enantioselective decarboxylative allylic alkylation reactions of ketones.

Enantioselective Synthesis of α-Quaternary Mannich Adducts by Palladium-Catalyzed Allylic Alkylation: Total Synthesis of (+)-Sibirinine

A catalytic enantioselective method for the synthesis of α-quaternary Mannich-type products is reported. The two-step sequence of (1) Mannich reaction followed by (2) decarboxylative enantioselective allylic alkylation serves as a novel strategy to in effect access asymmetric Mannich-type products of "thermodynamic" enolates of substrates possessing additional enolizable positions and acidic pr...

Catalytic asymmetric reactions via p-allylpalladium complexes coordinated with chiral monophosphine ligands

Chiral monophosphines (MOPs), whose chirality is due to biaryl axial chirality, are prepared from enantiometrically pure 2,2%-dihydroxy-1,1%-binaphthyl and 3,3%-dihydroxy-4,4%-biphenanthryl. The representatives are 2-(diphenylphosphino)-2%-methoxy1,1%-binaphthyl (MeO–MOP and 3-(diphenylphosphino)-3%-methoxy-4,4%-biphenanthryl (MOP–phen). The palladium complexes coordinated with the MOP ligands ...

Enantioselective Pd-Catalyzed Decarboxylative Allylic Alkylation of Thiopyranones. Access to Acyclic, Stereogenic α-Quaternary Ketones.

A catalytic, enantioselective decarboxylative allylic alkylation of 4-thiopyranones is reported. The α-quaternary 4-thiopyranones produced are challenging to access by standard enolate alkylation owing to facile ring-opening β-sulfur elimination. In addition, reduction of the carbon-sulfur bonds provides access to elusive acyclic α-quaternary ketones. The alkylated products are obtained in up t...

Diastereo- and Enantioselective Iridium-Catalyzed Allylation of Cyclic Ketone Enolates: Synergetic Effect of Ligands and Barium Enolates

We report asymmetric allylic alkylation of barium enolates of cyclic ketones catalyzed by a metallacyclic iridium complex containing a phosphoramidite ligand derived from (R)-1-(2-naphthyl)ethylamine. The reaction products contain adjacent quaternary and tertiary stereocenters. This process demonstrates that unstabilized cyclic ketone enolates can undergo diastereo- and enantioselective Ir-cata...