Tetrahedron Letters p. 7929 - 7932 (1992)
Update date:2022-08-17
Topics:
Curci, Ruggero
Fiorentino, Michele
Fusco, Caterina
Mello, Rossella
Ballistreri, Francesco
et al.
In situ generated or isolated dimethyldioxirane (1a) and methyltrifluoromethyldioxirane (1b) efficiently afford oxidation of alkynes, most likely via oxirene intermediates, which rearrange into ketene or α,β-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. Key Words - Dioxiranes, Oxygen transfer, Alkynes, Oxidation, Oxirenes, ketenes, α,β-Unsaturated Carbonyls.
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