Total synthesis of natural (+)- [corrected] and ent-(-)-4-desacetoxy-6,7-dihydrovindorosine [corrected] and natural and ent-minovine: oxadiazole tandem intramolecular Diels-Alder/1,3-dipolar cycloaddition reaction.
Efficient and unusually concise total syntheses of both enantiomers of the Aspidosperma alkaloids 4-desacetoxy-6,7-dihydrovindorosine (12) and minovine (1) are detailed. A tandem intramolecular Diels-Alder/1,3-dipolar cycloaddition reaction of the 1,3,4-oxadiazole 8, in which three new rings, four new C-C bonds, and five stereocenters are formed, is a key step in the sequence. The availability of optically active material permitted an assessment of the enantiomeric integrity of minovine and the source of its reported unusual optical rotation. [Reaction: see text]
Yuan
Zhong Qing
ZQ
Department of Chemistry and The Skaggs Institute for Chemical Biology, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, CA 92037, USA.
Ishikawa
Hayato
H
Boger
Dale L
DL
D000470:Alkaloids / Q000138:chemical synthesis* / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D015394:Molecular Structure; D010069:Oxadiazoles; D014748:Vinca Alkaloids / Q000138:chemical synthesis* / Q000737:chemistry
D000470:Alkaloids; D010069:Oxadiazoles; D014748:Vinca Alkaloids; C511649:ent-4-desacetoxy-6,7-dihydrovindorosine; C008532:minovine