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Asymmetric autocatalysis and its application to chiral discrimination
Author(s) -
Soai Kenso,
Sato Itaru
Publication year - 2002
Publication title -
chirality
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.43
H-Index - 77
eISSN - 1520-636X
pISSN - 0899-0042
DOI - 10.1002/chir.10081
Subject(s) - autocatalysis , chemistry , chirality (physics) , enantioselective synthesis , enantiomeric excess , homochirality , stereochemistry , enantiomer , chiral ligand , combinatorial chemistry , organic chemistry , catalysis , chiral symmetry breaking , nambu–jona lasinio model , quark , physics , quantum mechanics
Chiral pyrimidyl, quinolyl, and pyridyl alkanols act as asymmetric autocatalysts with significant amplification of enantiomeric excess (ee) in the enantioselective addition of diisopropylzinc to pyrimidine‐5‐, quinoline‐3‐, and pyridine‐3‐carbaldehydes, respectively. 2‐Alkynyl‐5‐pyrimidyl alkanol with as low as 0.6% ee automultiplies during the consecutive asymmetric autocatalysis with increasing ee to as high as >99.5%. Asymmetric autocatalysis is applied to chiral discrimination of organic compounds. In the presence of methyl mandelate or 2‐butanol with very low ee's (0.05–0.1%) as chiral initiators, the reaction between pyrimidine‐5‐carbaldehyde and diisopropylzinc affords pyrimidyl alkanol with higher ee's with the correlated absolute configurations to those of the chiral initiators. Chirality of amino acids (such as leucine) and helicenes with very low ee's are also discriminated by asymmetric autocatalysis, affording pyrimidyl alkanol with very high ee's. Asymmetric autocatalysis also discriminates the chirality of primary alcohols‐α‐ d , monosubstituted [2.2]paracyclophanes and octahedral cobalt complex with achiral ligands of which the chirality is due to the topology of coordination of the achiral ligand. Even the chirality of inorganic crystals such as quartz and sodium chlorate is discriminated by asymmetric autocatalysis of pyrimidyl alkanol. Thus, asymmetric autocatalysis provides a unique method for the discrimination of chiral compounds and crystals. Chirality 14:548–554, 2002. © 2002 Wiley‐Liss, Inc.