title: Dual Palladium(II)/Tertiary Amine Catalysis for Asymmetric Regioselective Rearrangements of Allylic Carbamates.
abstract: 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.
authors.affiliation: Institut für Organische Chemie, Universität Stuttgart, Pfaffenwaldring 55, 70569, Stuttgart, Germany.
authors.forename: Johannes Moritz
authors.identifier: http://orcid.org/0000-0002-3945-999X
authors.initials: JM
authors.lastname: Bauer
authors.affiliation: Institut für Organische Chemie, Universität Stuttgart, Pfaffenwaldring 55, 70569, Stuttgart, Germany.
authors.forename: Wolfgang
authors.identifier: http://orcid.org/0000-0002-6522-4190
authors.initials: W
authors.lastname: Frey
authors.affiliation: Institut für Organische Chemie, Universität Stuttgart, Pfaffenwaldring 55, 70569, Stuttgart, Germany. rene.peters@oc.uni-stuttgart.de.
authors.forename: René
authors.identifier: http://orcid.org/0000-0002-6668-4017
authors.initials: R
authors.lastname: Peters
mesh_terms: D000588:Amines / Q000737:chemistry*; D000596:Amino Acids / Q000737:chemistry*; D002219:Carbamates / Q000737:chemistry*; D002384:Catalysis; D015394:Molecular Structure; D009570:Nitriles / Q000737:chemistry; D010165:Palladium / Q000737:chemistry*; D013237:Stereoisomerism; D014105:Tosyl Compounds / Q000737:chemistry
chemical_list: D000588:Amines; D000596:Amino Acids; D002219:Carbamates; C000610132:N-tosylisocyanate; D009570:Nitriles; D014105:Tosyl Compounds; D010165:Palladium; C034650:allyl carbamate
keywords: allylic compounds; domino reactions; enantioselectivity; palladium; regioselectivity