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Asymmetric γ‐Allylation of α,β‐Unsaturated Aldehydes by Combined Organocatalysis and Transition‐Metal Catalysis
Author(s) -
Næsborg Line,
Halskov Kim Søholm,
Tur Fernando,
Mønsted Sofie M. N.,
Jørgensen Karl Anker
Publication year - 2015
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201504749
Subject(s) - chemistry , catalysis , organocatalysis , transition metal , diastereomer , iridium , enantioselective synthesis , palladium , synergistic catalysis , organic chemistry , transition state , combinatorial chemistry , ligand (biochemistry) , biochemistry , receptor
The first asymmetric regio‐ and diastereodivergent γ‐allylation of cyclic α,β‐unsaturated aldehydes based on combined organocatalysis and transition‐metal catalysis is disclosed. By combining an aminocatalyst with an iridium catalyst, both diastereomers of branched allylated products can be achieved in moderate to good yields and excellent regio‐ and stereoselectivities. Furthermore, by replacing the iridium catalyst with a palladium catalyst, the linear allylated products are formed in good yields and excellent regio‐ and enantioselectivities. The developed method thus provides selective access to all six isomers of the γ‐allylated product in a divergent fashion by choosing the appropriate combination of organocatalyst, transition‐metal catalyst, and ligand.