Involvement of an oxidation-reduction equilibrium in chromium-mediated enantioselective Nozaki-Hiyama reactions

Henri S. Schrekker, K. Micskei, Csongor Hajdu, T. Patonay, Martin W G De Bolster, Ludger A. Wessjohann

Research output: Contribution to journalArticle

13 Citations (Scopus)

Abstract

Ligand induced enantioselective versions of the chromium(II)-mediated Nozaki-Hiyama reaction to homoallyl alcohols proved to be very difficult to achieve, especially if any other nucleophile than the parent allylchromium(III) species was applied. Also, the reaction is frequently accompanied by the formation of oxidation side products, predominantly allyl ketones. This can be explained by an Oppenauer-(Meerwein-Ponndorf-Verley) type mechanism (OMPV reaction). The addition of an enantiopure ligand to racemic chromium homoallyl alcoholate intermediates produced enantiomerically enriched homoallyl alcohols with an enantiomeric excess of up to 32%. This observation not only supports that the proposed OMPV oxidation-reduction equilibrium plays a crucial role in Nozaki-Hiyama reactions, but also proves its involvement in enantioselective versions.

Original languageEnglish
Pages (from-to)731-736
Number of pages6
JournalAdvanced Synthesis and Catalysis
Volume346
Issue number7
DOIs
Publication statusPublished - Jul 2004

Fingerprint

Chromium
Alcohols
Ligands
Nucleophiles
Ketones
Oxidation
Oxidation-Reduction

Keywords

  • Chromium
  • Enantioselection
  • Meerwein-Ponndorf-Verley reduction
  • Nozaki-Hiyama reaction, Oppenauer oxidation
  • Thermodynamic deracemization

ASJC Scopus subject areas

  • Chemistry (miscellaneous)
  • Organic Chemistry
  • Catalysis

Cite this

Involvement of an oxidation-reduction equilibrium in chromium-mediated enantioselective Nozaki-Hiyama reactions. / Schrekker, Henri S.; Micskei, K.; Hajdu, Csongor; Patonay, T.; De Bolster, Martin W G; Wessjohann, Ludger A.

In: Advanced Synthesis and Catalysis, Vol. 346, No. 7, 07.2004, p. 731-736.

Research output: Contribution to journalArticle

Schrekker, Henri S. ; Micskei, K. ; Hajdu, Csongor ; Patonay, T. ; De Bolster, Martin W G ; Wessjohann, Ludger A. / Involvement of an oxidation-reduction equilibrium in chromium-mediated enantioselective Nozaki-Hiyama reactions. In: Advanced Synthesis and Catalysis. 2004 ; Vol. 346, No. 7. pp. 731-736.
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