Zr(OBut)4 as an effective promoter for the Meerwein-Ponndorf-Verley alkynylation and cyanation of aldehydes: Development of new asymmetric cyanohydrin synthesis

Takashi Ooi, Tomoya Miura, Keisuke Takaya, Hayato Ichikawa, Keiji Maruoka

Research output: Contribution to journalArticlepeer-review

68 Citations (Scopus)

Abstract

Zr(OBut)4 can serve as an effective promoter for the Meerwein-Ponndorf-Verley alkynylation of aldehydes and also facilitate MPV type cyanide transfer to aldehyde carbonyls with commercially available acetone cyanohydrin under mild conditions. Based on this finding, a new procedure for asymmetric cyanohydrin synthesis has been developed employing (4R,5R)-2,2-dimethyl-α,α,α′,α′-tetraph enyl-1,3-dioxolane-4,5-dimethanol (TADDOL, 6) as a chiral ligand. For instance, sequential treatment of CH2Cl2 solution of 6 (1 equiv.) with Zr(OBut)4 (1 equiv.) and acetone cyanohydrin (2 equiv.) at room temperature for 1 h, and subsequent reaction with 3-phenylpropanal at -40°C for 7.5 h resulted in formation of the corresponding cyanohydrin 5g [R=Ph(CH2)2] in 63% isolated yield with 85% ee. The scope and limitations of this method have been clarified with various aldehydes as substrates.

Original languageEnglish
Pages (from-to)867-873
Number of pages7
JournalTetrahedron
Volume57
Issue number5
DOIs
Publication statusPublished - Jan 28 2001
Externally publishedYes

Keywords

  • Alkynylation
  • Cyanation
  • Cyanohydrin

ASJC Scopus subject areas

  • Biochemistry
  • Drug Discovery
  • Organic Chemistry

Fingerprint

Dive into the research topics of 'Zr(OBu<sup>t</sup>)<sub>4</sub> as an effective promoter for the Meerwein-Ponndorf-Verley alkynylation and cyanation of aldehydes: Development of new asymmetric cyanohydrin synthesis'. Together they form a unique fingerprint.

Cite this