1446096-65-6Relevant articles and documents
Carbenylative Amination and Alkylation of Vinyl Iodides via Palladium Alkylidene Intermediates
Premachandra, Ilandari Dewage Udara Anulal,Nguyen, Thi A.,Shen, Chengtian,Gutman, Eugene S.,Van Vranken, David L.
, p. 5464 - 5467 (2015)
Most palladium-catalyzed reactions involving insertion of alkylidenes with α-hydrogens undergo β-hydride elimination from alkylpalladium(II) intermediates to form alkenes. Vinyl iodides were shown to generate η3-allylpalladium intermediates that resist β-hydride elimination, preserving the sp3 center adjacent to the carbene moiety. Acyclic stereocontrol (syn/anti) for carbenylative amination and alkylation reactions was low, suggesting a lack of control in the migratory insertion step. Highly hindered carbene precursors inexplicably led to formation of Z-alkenes with high levels of stereocontrol.
Pd-catalyzed bis-cyclization/dimerization reactions of ω-aminovinyl halides
Khanna, Avinash,Premachandra, Ilandari Dewage Udara Anulal,Sung, Paul D.,Van Vranken, David L.
, p. 3694 - 3697 (2013/08/15)
Palladium is shown to catalyze the dimerization and cyclization of vinyl halides to generate pyrrolidine and piperidine dimers connected by a trans-ethylene bridge. The reaction tolerates a variety of N-alkyl substituents, including adamantyl. This remarkable dimerization reaction generates the skeleton of the alkaloid hyalbidone in a single step. A crossover experiment with a vinyl halide and a vinyl bromide is consistent with a Michael-type addition to a vinylpalladium cation to generate a Pd(0) alkylidene intermediate.
