TY - JOUR
T1 - Asymmetric autocatalysis
T2 - Novel structures, novel mechanism?
AU - Gridnev, Ilya D.
AU - Brown, John M.
N1 - Copyright:
Copyright 2008 Elsevier B.V., All rights reserved.
PY - 2004/4/20
Y1 - 2004/4/20
N2 - The amplifying asymmetric autocatalysis discovered by Soai and coworkers in 1995 does not fit easily into the extensively investigated framework of organozinc alkylation of aldehydes. In that case the catalyst is a monomeric Zn chelate that functions as both Lewis acid and Lewis base, permitting the simultaneous coordination of both dialkylzinc reagent and aldehyde reactant. By contrast, the Soai reactants are rigid γ-aminoaldehydes that cannot function as mononuclear chelates. Structural and computational evidence for a binuclear resting state is presented, and the energetics of mono-, di-, tri-, and tetrameric species accessible to the reacting system have been computed.
AB - The amplifying asymmetric autocatalysis discovered by Soai and coworkers in 1995 does not fit easily into the extensively investigated framework of organozinc alkylation of aldehydes. In that case the catalyst is a monomeric Zn chelate that functions as both Lewis acid and Lewis base, permitting the simultaneous coordination of both dialkylzinc reagent and aldehyde reactant. By contrast, the Soai reactants are rigid γ-aminoaldehydes that cannot function as mononuclear chelates. Structural and computational evidence for a binuclear resting state is presented, and the energetics of mono-, di-, tri-, and tetrameric species accessible to the reacting system have been computed.
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U2 - 10.1073/pnas.0308178101
DO - 10.1073/pnas.0308178101
M3 - Review article
C2 - 15060283
AN - SCOPUS:1942437586
VL - 101
SP - 5727
EP - 5731
JO - Proceedings of the National Academy of Sciences of the United States of America
JF - Proceedings of the National Academy of Sciences of the United States of America
SN - 0027-8424
IS - 16
ER -