Radical-induced cyclopentannulation of Henry (nitroaldol)-derived intermediates.
Tributyltin hydride-mediated cyclizations of 1-nitro-2-acetoxy-5-hexenes 7a-g having multiple substitutions on carbons 1 and 6 result in 2,3-substituted-1-acetoxycyclopentanes 1a-g. The substrates were prepared by nitroaldol reactions of silyloxyaldehydes followed by acetylation, desilylation, and oxidation to the acetoxynitroaldehydes 6a-e. Wittig olefination of aldehydes 6a-e then afforded substrates for the radical cyclizations. The overall scheme gave a diverse array of cyclopentanes, including gem-disubstituted cyclopentanes having substitution on three contiguous carbons.
Luzzio
Frederick A
FA
Department of Chemistry, University of Louisville, 2320 South Brook Street, Louisville, Kentucky 40292, USA. faluzz01@gwise.louisville.edu
Ott
Joel P
JP
Duveau
Damien Y
DY
D000475:Alkenes / Q000737:chemistry; D003500:Cyclization; D003517:Cyclopentanes / Q000138:chemical synthesis* / Q000737:chemistry; D005609:Free Radicals / Q000737:chemistry; D015394:Molecular Structure; D009574:Nitro Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism; D014220:Trialkyltin Compounds / Q000737:chemistry
D000475:Alkenes; D003517:Cyclopentanes; D005609:Free Radicals; D009574:Nitro Compounds; D014220:Trialkyltin Compounds; C011559:tributyltin