Premium
Reevaluation of the Mechanism of the Baylis–Hillman Reaction: Implications for Asymmetric Catalysis
Author(s) -
Aggarwal Varinder K.,
Fulford Sarah Y.,
LloydJones Guy C.
Publication year - 2005
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.200462462
Subject(s) - allylic rearrangement , baylis–hillman reaction , alkene , chemistry , catalysis , limiting , aldehyde , amine gas treating , hydride , reaction mechanism , medicinal chemistry , organic chemistry , mechanical engineering , engineering , hydrogen
One step beyond : Proton transfer (step 3, see scheme), not CC bond formation (step 2) as previously thought, is the rate‐limiting step (RLS) in the initial stage of the Baylis–Hillman reaction, which involves the amine‐catalyzed addition of an aldehyde to an activated alkene to generate an allylic alcohol. This finding has considerable implications for asymmetric catalysis of the reaction.