Regiospecific decarboxylative allylation of nitriles.
Palladium-catalyzed decarboxylative alpha-allylation of nitriles readily occurs with use of Pd(2)(dba)(3) and rac-BINAP. This catalyst mixture also allows the highly regiospecific alpha-allylation of nitriles in the presence of much more acidic alpha-protons. Thus, the reported method provides access to compounds that are not readily available via base-mediated allylation chemistries. Lastly, mechanistic investigations indicate that there is a competition between C- and N-allylation of an intermediate nitrile-stabilized anion and that N-allylation is followed by a rapid [3,3]-sigmatropic rearrangement.
Recio
Antonio
A
Department of Chemistry, The University of Kansas, Lawrence, Kansas 66045, USA.
Tunge
Jon A
JA
D000498:Allyl Compounds / Q000737:chemistry*; D002384:Catalysis; D020650:Combinatorial Chemistry Techniques; D015394:Molecular Structure; D009570:Nitriles / Q000138:chemical synthesis* / Q000737:chemistry*; D010165:Palladium / Q000737:chemistry*
D000498:Allyl Compounds; D009570:Nitriles; D010165:Palladium