title: Synthesis of optically active 2-alkoxy-2H-pyran-3(6H)-ones. Their use as dienophiles in Diels-Alder cycloadditions.
abstract: Optically active 2-alkoxy-2H-pyran-3(6H)-ones (4a-d) were synthesized in one step by the tin(IV) chloride-promoted glycosylation and rearrangement of the 2-acetoxy-3,4-di-O-acetyl-D-xylal (3) prepared from D-xylose (1). The absolute configuration of the new stereocenter at C-2 was determined by chemical transformation of the dihydropyranones 4a and 4b into the known alkyl pentopyranosides (7a and 7b, respectively). Also, from (1)H NMR experiments using a chiral ytterbium shift reagent, the enantiomeric excesses for 4a (>86%) and 4b (>77%) were established. Enantiomerically pure 4c and 4d were obtained by reaction of 3 with chiral 2-octanol (R and S, respectively). Dihydropyranones 4a-d were employed as dienophiles in Diels-Alder cycloadditions with 2,3-dimethylbutadiene and butadiene. Under thermal conditions, only moderate yields (approximately 50%) of cycloadducts 9a-c and 10a were respectively obtained with good diastereofacial selectivity (>80%). Optimized Lewis acid promoted cycloadditions led to 9a-d and 10a,c in higher yields (approximately 80%) and with higher diastereoselectivities (>94%). The major products were formed by approach of the dienes from the less hindered face of the dihydropyranones, and the minor products (such as 11a) were formed by addition from the opposite side. Furthermore, cycloadduct 9a was stable in an alkaline solution, whereas 11a underwent epimerization under the same conditions.
authors.affiliation: CIHIDECAR-CONICET, Departamento de Química Orgánica, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Ciudad Universitaria, Pabellón 2, 1428, Buenos Aires, Argentina.
authors.forename: C A
authors.initials: CA
authors.lastname: Capaccio
authors.forename: O
authors.initials: O
authors.lastname: Varela
mesh_terms: D000107:Acetylation; D003500:Cyclization; D007202:Indicators and Reagents; D009682:Magnetic Resonance Spectroscopy; D011714:Pyrans / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D007202:Indicators and Reagents; D011714:Pyrans