Asymmetric autocatalysis: Novel structures, novel mechanism?
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Edited by Jack Halpern, University of Chicago, Chicago, IL, and approved February 7, 2004 (received for review December 10, 2003)
Abstract
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.
Footnotes
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↵ ‡ To whom correspondence may be addressed. E-mail: igridnev{at}mail.tains.tohoku.ac.jp or john.brown{at}chem.ox.ac.uk.
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↵ † Present address: Department of Chemistry, Graduate School of Science, Tohoku University, Sendai 980-8578, Japan.
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This paper was submitted directly (Track II) to the PNAS office.
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Abbreviation: ee, enantiomer excess.
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↵ § Defined as catalysis by organic compounds lacking any metallic or metalloid component.
- Copyright © 2004, The National Academy of Sciences
