Quantitative analysis of the chiral amplification in the amino alcohol- promoted asymmetric alkylation of aldehydes with dialkylzincs

Masato Kitamura, Seiji Suga, Hiromasa Oka, Ryoji Noyori

Research output: Contribution to journalArticle

229 Citations (Scopus)

Abstract

Asymmetric reaction of dimethylzinc and benzaldehyde in the presence of (2S)-3-exo-(dimethyl-amino)isoborneol [(2S)-DAIB] exhibits unusual nonlinear phenomena. The enantiomeric purity of the product is much higher than that of the chiral source, DAIB, while the rate of the enantioselective catalysis decreases considerably as the enantiomeric excess (ee) of DAIB is lowered. Such effects originate from the reversible homochiral and heterochiral interaction of the coexistent enantiomeric zinc amino alkoxide catalysts which are formed from dimethylzinc and (2S)- and (2R)-DAIB. The thermodynamics of the five-component equilibration between the two monomers and three dimers, when coupled with the kinetics of the alkylation, strongly affects the extent of enantioselectivity and the reaction rate of the alkylation reaction. The overall profile of the nonlinear effects has been clarified mathematically using experimentally available parameters, viz., the equilibrium constants of the dimer/monomer conversion and the association of the monomeric catalyst with the organozinc and aldehyde, the rate constant of alkyl transfer from the catalyst/dimethylzinc/aldehyde mixed complex, the ee of DAIB, and the concentrations of DAIB, dimethylzinc, and aldehyde. 3D graphics are presented for the correlation of the enantiomeric purity of the product with DAIB ee and the concentrations of dimethylzinc and aldehyde and for the relationship between the reaction rate, DAIB ee, and the concentrations of the organozinc and aldehyde. The computer simulation is in good agreement with the experimental results, confirming thai the nonlinear effects result from the competition of two enantiomorphic catalytic cycles involving the monomeric chiral zinc catalysts rather than the diastereomorphic catalytic cycles with dinuclear zinc catalysts. Furthermore, this study indicates that the degree of nonlinear effects in asymmetric catalysis could be affected not only by the catalyst ee but also by various reaction parameters, particularly the concentrations of the catalyst, reagent, and substrate as well as the extent of conversion.

Original languageEnglish
Pages (from-to)9800-9809
Number of pages10
JournalJournal of the American Chemical Society
Volume120
Issue number38
DOIs
Publication statusPublished - Sep 30 1998
Externally publishedYes

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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