Unprecedented Direct Oxygen Atom Transfer from Hypervalent Oxido-λ³-iodanes to α,β-Unsaturated Carbonyl Compounds:  Synthesis of α,β-Epoxy Carbonyl Compounds

Abstract

Tetra-n-butylammonium oxido-lambda(3)-iodane, prepared from 1-hydroxy-1,2-benziodoxol-3(1H)-one by reaction with tetra-n-butylammonium fluoride, directly undergoes oxygen atom transfer to alpha,beta-unsaturated carbonyl compounds, yielding epoxides.

Tetrafluoro‐IBA and‐IBX: Hypervalent Iodine Reagents

“…Reactions with IBA (1) are much less common in organic synthesis owing to its low reactivity. [40] FIBA (6), however, can be used advantageously. The diphenyl diselenide catalyzed cyclization of 16 to the butenolide 17 can be achieved with FIBA (6) (Scheme 3), [41] while IBA (1) is not reactive in this system.…”

7.07 α-Oxygenation of Carbonyl Compounds

“…Ochiai The tetrabutylammonium oxido-l 3 -iodane reagent contains an oxyanion that attacks the electron-deficient alkene, followed by ring-closure to the epoxide and reductive elimination of the iodoarene (Scheme 58(a)). 160 PIFA was employed in a chemo-and stereoselective epoxidation in the total synthesis of epoxysorbicillinol, demonstrating the mild and selective features of many hypervalent iodine-mediated transformations (Scheme 58(b)). 161 Epoxidation of enones can also be achieved by sequential addition of IBX À I 2 and 10% NaOH, and proceeds by initial iodohydroxylation followed by cyclization.…”

α-Functionalization of Carbonyl Compounds Using Hypervalent Iodine Reagents

“…The reagent, tetrabutylammonium oxido-λ 3 -iodane, contains an oxyanion that can attack the electron-deficient olefin, followed by ring-closure to form the epoxide and expel the iodoarene. [142] Scheme 74 Epoxidation of enones.…”