A novel probe for free radicals featuring epoxide cleavage

Abstract

This paper describes the identification of carbon-arbon bond cleavage within a defined range of epoxides as being a reaction type which is specifically diagnostic of free radicals adjacent to the epoxide. The speed of the epoxide cleavage is greater than that of hex-5-enyl radical cyclisation, and hence the reaction is kinetically competent to act as a new and discriminating type of probe for free radicals in solution.

Decomposition of vinyl ethers by alkalide K−, K+(15-crown-5)2 via organopotassium intermediates

“…MS; m/z (%): 134 (M þ , 4), 116 (7), 105 (11), 91 (100), 77 (7), 65 (30), 51 (9), 39 (11). MS data were also presented in [24], and 1 H and 13 C NMR (CDCl 3 ) spectra in [25].…”

The Epoxy‐Ramberg–Bäcklund Reaction (ERBR): A Sulfone‐Based Method for the Synthesis of Allylic Alcohols

“…Filtration and solvent removal in vacuo gave the crude product, which was purified by column chromatography (PE/EtOAc, 4:1) to yield the allylic alcohol 5a (62 mg, 63 %) as a viscous yellow oil (E:Z, 65:35) whose data was consistent to that reported. [51] (b) A solution of 4a (52 mg, 0.189 mmol, 1 equiv.) in dry DMSO (5 mL) was treated at 25°C with LiOtBu in THF (0.38 mL, 1.0 , 0.38 mmol, 2 equiv.).…”

10.1007/s11178-008-2001-z

“…Although in the most cases the C-O bond suffered homolysis, in certain studies homolytic rupture of C-C bond was proved and this was even suggested as a test on the formation of radical intermediates [122,123]. In [123] vinyl ether 141 was obtained by this procedure (Scheme 68).…”