title: Dihydroxylation-based approach for the asymmetric syntheses of hydroxy-γ-butyrolactones.
abstract: A method of preparing enantiopure hydroxy-γ-butyrolactones containing multiple contiguous stereocenters in high yield with good diastereoselectivity has been developed. Osmium tetroxide mediated dihydroxylation of a range of β-alkenyl-β-hydroxy-N-acyloxazolidin-2-ones results in formation of triols that undergo spontaneous intramolecular 5-exo-trig cyclization reactions to provide hydroxy-γ-butyrolactones. The stereochemistry of these hydroxy-γ-butyrolactones has been established using NOE spectroscopy, which revealed that 1-substituted, 1,1-disubstituted, (E)-1,2-disubstituted, (Z)-1,2-disubstituted, and 1,1,2-trisubstituted alkenes undergo dihydroxylation with anti-diastereoselectivity, while 1,2,2-trisubstituted systems afford syn-diastereoisomers. The synthetic utility of this methodology has been demonstrated for the asymmetric synthesis of the natural product 2-deoxy-D-ribonolactone.
authors.affiliation: Department of Chemistry, University of Bath, Claverton Down, Bath, BA2 7AY, United Kingdom.
authors.forename: Jennifer
authors.initials: J
authors.lastname: Peed
authors.forename: Iwan R
authors.initials: IR
authors.lastname: Davies
authors.forename: Lucy R
authors.initials: LR
authors.lastname: Peacock
authors.forename: James E
authors.initials: JE
authors.lastname: Taylor
authors.forename: Gabriele
authors.initials: G
authors.lastname: Kociok-Köhn
authors.forename: Steven D
authors.initials: SD
authors.lastname: Bull
mesh_terms: D015107:4-Butyrolactone / Q000138:chemical synthesis* / Q000737:chemistry*; D000475:Alkenes / Q000737:chemistry*; D002384:Catalysis; D003500:Cyclization; D015394:Molecular Structure; D013237:Stereoisomerism
chemical_list: D000475:Alkenes; D015107:4-Butyrolactone