Desymmetrisation of a centrosymmetric molecule by carbon-carbon bond formation: asymmetric aldol reactions of a centrosymmetric dialdehyde.
The desymmetrisation of centrosymmetric molecules by enantioselective carbon-carbon bond formation has been reported for the first time. A bimetallic zinc catalyst developed by Trost was exploited in the desymmetrisation of a centrosymmetric dialdehyde. The approach was successful with a range of ketone nucleophiles and was uniformly highly diastereoselective (>98:<2). The yield and the enantioselectivity of the reaction varied as a function of the ketone used, and the desymmetrised products were obtained in up to 74 % yield and 97 % ee (ee=enantiomeric excess). The desymmetrisation of centrosymmetric molecules by enantioselective carbon-carbon bond formation is an efficient and convergent synthetic approach which is likely to find wide application in synthesis, particularly in the total synthesis of natural products with embedded centrosymmetric fragments.
Dodd
Karen
K
School of Chemistry, University of Leeds, Leeds, LS2 9JT, UK.
Morton
Daniel
D
Worden
Stephen
S
Narquizian
Robert
R
Nelson
Adam
A
D000447:Aldehydes / Q000737:chemistry*; D002244:Carbon / Q000737:chemistry*; D002384:Catalysis; D008968:Molecular Conformation; D015394:Molecular Structure; D013237:Stereoisomerism; D015032:Zinc / Q000737:chemistry
D000447:Aldehydes; D002244:Carbon; C116609:3-hydroxybutanal; D015032:Zinc