Enantioselective olefin epoxidation using homologous amine and iminium catalysts-a direct comparison

Tetrahedron Letters

Volumn 47, Issue 30, 2006, Pages 5297-5301

  Gonçalves, Maria Héléna ^a   Martinez, Alexandre ^a   Grass, Stéphane ^a   Page, Philip C Bulman ^b   Lacour, Jérôme ^a  

^a UNIVERSITY OF GENEVA   (Switzerland)

^b LOUGHBOROUGH UNIVERSITY   (United Kingdom)

Author keywords

[No Author keywords available]

Indexed keywords

ALKENE; AMINE; IMINE;

ARTICLE; CATALYST; CHEMICAL STRUCTURE; CHIRALITY; COMPARATIVE STUDY; DIASTEREOISOMER; ENANTIOSELECTIVITY; EPOXIDATION; OLEFINATION; STRUCTURAL HOMOLOGY; STRUCTURE ANALYSIS;

EID: 33746875652     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.tetlet.2006.05.132     Document Type: Article

References (40)

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36. Appropriate pyrrolidine and carbonyl moieties can react together to generate iminium species. Unfortunately, most of these species, in particular the most hindered ones, are prone to solvolysis in the reaction conditions: see Ref. 8.
37. TRISPHAT is chiral. However, it was shown (see Ref. 10b) that its configuration plays no role in the enantioselective epoxidation reaction. For ease of synthesis and better chemical yields in ion pair exchange metathesis, enantiopure [cinchonidinium][Δ-TRISPHAT] was used as a source of hexacoordinated phosphate anion.
38. In view of the previous results by the group of Yang (Ref. 17), one can reason that the presence of two electron-withdrawing oxygen atoms at β-position relative to the amino group in l-acetonamine activates the catalytic activity of the amine/ammonium salt.
39. These results confirm the previous observations that higher values are obtained for both conversions and enantiomeric excesses using more polar solvent conditions and amines as catalysts, see Refs. 15 and 17.
40. It is remarkable that the amines and iminium salts leads to such similar enantiomeric excess values. Although it is reasonable to consider a single mechanistic pathway for the two processes, we have no evidence for it. Under conditions A or B, no products of oxidation of amines 1a-3a could be characterized or, for that matter, could iminium cations 1i-3i be recovered at the end of the reactions.