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Rhodium‐Catalyzed Asymmetric Allylation of Malononitriles as Masked Acyl Cyanide with Allenes: Efficient Access to β,γ‐Unsaturated Carbonyls
Author(s) -
Grugel Christian P.,
Breit Bernhard
Publication year - 2018
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.201804150
Subject(s) - chemistry , rhodium , enantioselective synthesis , cyanide , catalysis , adduct , intermolecular force , medicinal chemistry , combinatorial chemistry , organic chemistry , molecule
A rhodium‐catalyzed regio‐ and enantioselective intermolecular allylation of malononitriles as masked acyl cyanides (MAC) with terminal and symmetrical internal allenes is reported. A Rh I /Josiphos catalytic system combined with subsequent oxidative degradation of the primary adducts enables a straightforward access to α‐branched, β,γ‐unsaturated carbonyl compounds. The present protocol exhibits perfect atom economy in the allylation step and is characterized by a great functional group compatibility. Furthermore, the use of α‐substituted malononitriles allowed for the construction of all‐carbon quaternary centers.