Selective oxidation of acetylenic 1,4-diols with dioxiranes in comparison with the methyltrioxorhenium-hydrogen peroxide oxidant

Dimethyldioxirane (1a) and its trifluoro analog (1b) were employed to achieve selectively the direct transformation of hex-3-yne-2,5-diol 3a and 1,4-diphenyl-but-2yne-1,4-diol 3b (two representative acetylenic 1,4-diols) into the corresponding carbonyls, leaving the carbon-carbon triple bond moiety untouched. The results are compared with those recorded in the analogous oxidation using the methyltrioxorhenium (MTO)/85% H₂O₂ homogeneous system. The powerful methyl(trifluoromethyl)dioxirane (1b) is the reagent of choice to achieve optimum yields of the target alkyne-1,4-diones, which are extremely versatile synthons.