Copper-catalyzed methylenation reaction: total synthesis of (+)-desoxygaliellalactone.
The enantioselective total synthesis of (+)-desoxygaliellalactone was achieved in six steps starting from 4-tert-butyldimethylsilyloxybutanal. This synthesis featured a one-pot copper-catalyzed methylenation-Diels-Alder cyclization. The challenging methylenation of aldehyde 4 was studied under various reaction conditions. Whereas Wittig reaction conditions led to byproducts resulting from decomposition of the sensitive butenolide moiety, the mild copper-catalyzed methylenation reaction produced the desired triene in good yield.
Lebel
Hélène
H
Département de chimie, Université de Montréal, P.O. Box 6128, Station Downtown, Montréal, Québec, Canada H3C 3J7. helene.lebel@umontreal.ca
Parmentier
Michaël
M
D000447:Aldehydes / Q000138:chemical synthesis* / Q000737:chemistry; D000475:Alkenes / Q000737:chemistry*; D002384:Catalysis; D003300:Copper / Q000737:chemistry*; D004129:Dimethylpolysiloxanes / Q000138:chemical synthesis* / Q000737:chemistry; D007783:Lactones / Q000138:chemical synthesis* / Q000737:chemistry*; D015394:Molecular Structure; D013237:Stereoisomerism
C524018:4-tert-butyldimethylsilyloxybutanal; D000447:Aldehydes; D000475:Alkenes; D004129:Dimethylpolysiloxanes; D007783:Lactones; C524017:desoxygaliellalactone; C416043:galiellalactone; D003300:Copper