R. Curci, M. Fiorentino, C. Fusco
Dec 5, 1992
Citations
0
Influential Citations
36
Citations
Journal
Tetrahedron Letters
Abstract
Abstract In situ generated or isolated dimethyldioxirane (1a) and methyl(trifluoromethyl)dioxirane (1b) efficiently afford oxidation of alkynes, most likely via oxirene intermediates, which rearrange into ketene or α,γ-unsaturated carbonyls, or else are further oxidized to α,β-dicarbonyls. Diphenylacetylene and phenylacetylene yield mostly ketene derived products, whereas 8-hexadecyne (an internal dialkyl alkyne) gives 9-hexadecen-8-one (both trans and cis) as the main product. Reaction of cyclodecyne (a conformationally rigid cycloalkyne) with isolated 1b affords cis-bicyclo[5.3.0]decan-2-one (15) and cis-bicyclo[4.4.0]decan-2-one (16), which derive from the oxirene by stereoselective 1.5- and 1,6-transanular insertion, respectively.