1404456-94-5Relevant academic research and scientific papers
Dual Palladium(II)/Tertiary Amine Catalysis for Asymmetric Regioselective Rearrangements of Allylic Carbamates
Bauer, Johannes Moritz,Frey, Wolfgang,Peters, René
, p. 5767 - 5777 (2016)
The streamlined catalytic access to enantiopure allylic amines as valuable precursors towards chiral β- and γ-aminoalcohols as well as α- and β-aminoacids is desirable for industrial purposes. In this article an enantioselective method is described that transforms achiral allylic alcohols and N-tosylisocyanate in a single step into highly enantioenriched N-tosyl protected allylic amines via an allylic carbamate intermediate. The latter is likely to undergo a cyclisation-induced [3,3]-rearrangement catalysed by a planar chiral pentaphenylferrocene palladacycle in cooperation with a tertiary amine base. The otherwise often indispensable activation of palladacycle catalysts by a silver salt is not required in the present case and there is also no need for an inert gas atmosphere. To further improve the synthetic value, the rearrangement was used to form dimethylaminosulfonyl-protected allylic amines, which can be deprotected under non-reductive conditions.
Catalytic enantioselective allylic amination of unactivated terminal olefins via an Ene reaction/[2,3]-rearrangement
Bao, Hongli,Tambar, Uttam K.
, p. 18495 - 18498 (2013/01/15)
The enantioselective allylic amination of unactivated terminal olefins represents a direct and attractive strategy for the synthesis of enantioenriched amines. We have developed the first use of a nitrogen-containing reagent and a chiral palladium catalyst to convert unfunctionalized olefins into enantioenriched allylic amines via an ene reaction/[2,3]-rearrangement.
