93823-14-4Relevant articles and documents
Hexacarbonylmolybdenum(0)-Catalyzed Reaction of Allylic Carbonates with Arylsulfonyl-Stabilized Carbanions
Masuyama, Yoshiro,Hirai, Hidenori,Kurusu, Yasuhiko,Segawa, Koh-ichi
, p. 1525 - 1526 (1987)
p-Tolylsulfonylacetonitrile reacted with allylic carbonates in the presence of a catalytic amount of hexacarbonylmolybdenum(0) to give monoallylated derivatives.Using sodium hydride as a base, methyl p-tolylsulfonylacetate reacted with those to give mixtu
N- Allyl- N- sulfonyl ynamides as synthetic precursors to amidines and vinylogous amidines. An unexpected N-to-C 1,3-sulfonyl shift in nitrile synthesis
Dekorver, Kyle A.,Johnson, Whitney L.,Zhang, Yu,Hsung, Richard P.,Dai, Huifang,Deng, Jun,Lohse, Andrew G.,Zhang, Yan-Shi
supporting information; experimental part, p. 5092 - 5103 (2011/08/06)
A detailed study of amidine synthesis from N-allyl-N-sulfonyl ynamides is described here. Mechanistically, this is a fascinating reaction consisting of diverging pathways that could lead to deallylation or allyl transfer depending upon the oxidation state of palladium catalysts, the nucleophilicity of amines, and the nature of the ligands. It essentially constitutes a Pd(0)-catalyzed aza-Claisen rearrangement of N-allyl ynamides, which can also be accomplished thermally. An observation of N-to-C 1,3-sulfonyl shift was made when examining these aza-Claisen rearrangements thermally. This represents a useful approach to nitrile synthesis. While attempts to render this 1,3-sulfonyl shift stereoselective failed, we uncovered another set of tandem sigmatropic rearrangements, leading to vinyl imidate formation. Collectively, this work showcases the rich array of chemistry one can discover using these ynamides.
A divergent mechanistic course of Pd(0)-catalyzed aza-claisen rearrangement and aza-rautenstrauch-type cyclization of N -allyl ynamides
Dekorver, Kyle A.,Hsung, Richard P.,Lohse, Andrew G.,Zhang, Yu
supporting information; experimental part, p. 1840 - 1843 (2010/10/03)
A fascinating mechanistic study of ynamido-palladium-allyl complexes is described that features isolation of a unique silyl ketenimine via aza-Claisen rearrangement, which can be accompanied by an unusual thermal N-to-C 1,3-Ts shift in the formation of tertiary nitriles and a novel cyclopentenimine formation via a palladium-catalyzed aza-Rautenstrauch-type cyclization pathway.
ALLYLIC ALKYLATION CATALYZED BY THE COUPLE PALLADIUM COMPLEXES-ALUMINA
Ferroud, D.,Genet, J.P.,Muzart, J.
, p. 4379 - 4382 (2007/10/02)
Using both palladium complexes and alumina, nucleophilic substitutions of allyl acetate by various nucleophiles (pKa=5-13) are realized with good yields at room temperature without preformation of the corresponding carbanions.
