Catalytic α‑Monoallylation of Aryl Acetonitriles

α-Cyano aldehydes undergo selective transition-metal-catalyzed monoallylation to provide α-allylated nitriles. The transformation leads to linear substitution products with palladium catalysts or branched allylated nitriles using an iridium catalyst. Facile TBD-catalyzed retro-Claisen cleavage is leveraged to attain selective monoallylation

Catalytic α‑Monoallylation of Aryl Acetonitriles

α-Cyano aldehydes undergo selective transition-metal-catalyzed monoallylation to provide α-allylated nitriles. The transformation leads to linear substitution products with palladium catalysts or branched allylated nitriles using an iridium catalyst. Facile TBD-catalyzed retro-Claisen cleavage is leveraged to attain selective monoallylation

Palladium-Catalyzed Double-Decarboxylative Addition to Pyrones: Synthesis of Conjugated Dienoic Esters

An interceptive decarboxylative allylation protocol has been developed utilizing pyrone as a C4 synthon. This palladium-catalyzed transformation difunctionalizes the pyrone moiety by <i>in situ</i> generation and activation of both the electrophile and nucleophile via a double decarboxylation pathway. Ultimately, allyl carbonates react smoothly with 2-carboxypyrone under mild reaction conditions to generate synthetically useful acyclic dienoic esters, forming carbon dioxide as the sole byproduct

Synthesis of Spirooxindoles via the <i>tert</i>-Amino Effect

A new method is developed for the synthesis of spirooxindoles from amines and isatins via C–H functionalization. The reaction leverages the <i>tert</i>-amino effect to form an enolate–iminium intermediate via [1,5]-hydride shift followed by cyclization. Interestingly the hydride migrates to the N atom of a CN, which is atypical for hydride additions to imines

Development of Asymmetric Deacylative Allylation

Herein we present the development of asymmetric deacylative allylation of ketone enolates. The reaction directly couples readily available ketone pronucleophiles with allylic alcohols using facile retro-Claisen cleavage to form reactive intermediates in situ. The simplicity and robustness of the reaction conditions is demonstrated by the preparation of >6 g of an allylated tetralone from commercially available materials. Furthermore, use of nonracemic PHOX ligands allows intermolecular formation of quaternary stereocenters directly from allylic alcohols