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Dual Palladium(II)/Tertiary Amine Catalysis for Asymmetric Regioselective Rearrangements of Allylic Carbamates
Author(s) -
Bauer Johannes Moritz,
Frey Wolfgang,
Peters René
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201600138
Subject(s) - allylic rearrangement , enantiopure drug , chemistry , enantioselective synthesis , palladium , catalysis , amine gas treating , combinatorial chemistry , regioselectivity , carbamate , organic chemistry , medicinal chemistry
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.