Enantioselective alkylation of carbonyl compounds. From stoichiometric to catalytic asymmetric induction

R. Noyori, Seiji Suga, K. Kawai, S. Okada, M. Kitamura

Research output: Contribution to journalArticle

158 Citations (Scopus)

Abstract

Multinuclear organometallic species play a significant role in alkylation of carbonyl compounds. Enantioselective alkylation of aldehydes using a 1:1 reagent/substrate stoichiometry is achievable by chirally modified lithium/magnesium binary organometallic reagents. For example, diethylmagnesium treated with di-O-lithio-(S)-2,2' ‘-dihydroxy-1,1’-binaphthyl reacts with benzaldehyde in a THF—dimethoxyethane mixture at-100 °C to give (S)-1-phenyl-1-propanol in 92% ee. In the presence of a catalytic quantity of (-)-3-exo-(dimethylamino)isoborneol (DAIB), reaction of dialkylzincs and aldehydes in nonpolar media is accelerated greatly to lead to the corresponding S alcohols in very high enantiomeric excesses (up to 99% ee). The enantioselective catalysis involves fluxional organozinc species and the product-forming dinuclear intermediate possesses DAIB auxiliary, an aldehyde ligand, and three alkyl groups, where it is the bridging alkyl group, rather than the terminal alkyls, that migrates from zinc to the carbonyl carbon.

Original languageEnglish
Pages (from-to)1597-1606
Number of pages10
JournalPure and Applied Chemistry
Volume60
Issue number11
DOIs
Publication statusPublished - Jan 1 1988
Externally publishedYes

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Carbonyl compounds
Alkylation
Aldehydes
Organometallics
Propanol
Lithium
Stoichiometry
Magnesium
Catalysis
Zinc
Alcohols
Carbon
Ligands
Substrates
isoborneol

ASJC Scopus subject areas

  • Chemical Engineering(all)
  • Chemistry(all)

Cite this

Enantioselective alkylation of carbonyl compounds. From stoichiometric to catalytic asymmetric induction. / Noyori, R.; Suga, Seiji; Kawai, K.; Okada, S.; Kitamura, M.

In: Pure and Applied Chemistry, Vol. 60, No. 11, 01.01.1988, p. 1597-1606.

Research output: Contribution to journalArticle

Noyori, R. ; Suga, Seiji ; Kawai, K. ; Okada, S. ; Kitamura, M. / Enantioselective alkylation of carbonyl compounds. From stoichiometric to catalytic asymmetric induction. In: Pure and Applied Chemistry. 1988 ; Vol. 60, No. 11. pp. 1597-1606.
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