Synthesis of a lactone diastereomer of the cembranolide uprolide D.
A convergent stereoselective synthesis of a C1/C14 bis-epimer of uprolide D is described in which an intramolecular Barbier-type reaction was employed for macrocyclization with concomitant introduction of the C1 and C14 stereocenters of a fused α-methylene lactone ring through an anti-Felkin-Anh transition state. Unlike previous examples of allyl chromium additions, none of the Felkin-Anh derived adduct could be detected.
Marshall
James A
JA
Department of Chemistry, University of Virginia, Charlottesville, Virginia 22904, USA. jam5x@virginia.edu
Griot
Céline A
CA
Chobanian
Harry R
HR
Myers
William H
WH
D001952:Bridged-Ring Compounds / Q000138:chemical synthesis*; D002614:Chelating Agents / Q000737:chemistry; D007783:Lactones / Q000138:chemical synthesis*; D015394:Molecular Structure; D009930:Organic Chemicals / Q000138:chemical synthesis*; D013237:Stereoisomerism
D001952:Bridged-Ring Compounds; D002614:Chelating Agents; D007783:Lactones; D009930:Organic Chemicals; C554303:uprolide D