Palladium-Catalyzed Synthesis of 1-Alkylidene-2-dialkylaminomethyl Cyclobutane Derivatives via Pd-Catalyzed Alkene Difunctionalization Reactions: Influence of Nucleophile and Water on the Reaction Mechanism.

The Pd-catalyzed coupling of 1,5-diene-2-yl triflates with amine nucleophiles affords exomethylenecyclobutanes bearing dialkylaminomethyl groups at C2. The strained carbocyclic products are obtained in moderate to excellent yields, with regioselectivities of up to >95:5 for four-membered ring formation. The mechanism of these reactions, which provides products resulting from -addition to alkenes, differs from related reactions involving malonate nucleophiles that provide -addition products.

Regiodivergent Palladium-Catalyzed Alkene Difunctionalization Reactions for the Construction of Methylene Cyclobutanes and Methylene Cyclopentanes.

Regiodivergent palladium-catalyzed alkene difunctionalization reactions between diethyl malonate and 1,5-dienes bearing a triflate group at C2 are described. Use of tris(2,4-di--butylphenyl)phosphite as a ligand leads to 4--cyclization/functionalization to afford malonate-substituted methylene cyclobutanes. In contrast, the 1,2-bis(diphenylphosphino)benzene ligand provides methylene cyclopentanes via 5--cyclization/functionalization.