Identifying the Intermediate in the Dioxygen Transfer from 4a-Hydroperoxyflavin Anion to Phenolate and Indole Anions

Facile Epoxidation of α,β-Unsaturated Ketones with trans-3,5-Dihydroperoxy-3,5-dimethyl-1,2-dioxolane as an Efficient Oxidant

“…Also, it should be mentioned that in all the reactions acetylacetone was recovered in high yield after the reaction as evidenced by the spectral analysis. The structures of the products 3a-q were fully established by analysis of their spectral ( 1 H NMR, 13 C NMR, IR) and physical data and compared with those reported. 45,56 Scheme 2…”

“…In contrast to H 2 O 2 , gem-dihydroperoxides act more efficiently as high-oxygen-content oxidants for transferring oxygen to sulfides, a,b-unsaturated ketones, amines, and other substrates. [12][13][14][15][16][17][18][19] Anomeric hydroperoxides derived from 3,4,6-tri-O-benzyl-galactose and glucose were used for enantioselective epoxidation of naphthoquinone, chalcones, (E)-1,2-dibenzoyl ethylene, and (E)-iso-butyrylphenyl ethylene. 20 Most recently, we reported a novel use of trans-3,5-dihydroperoxy-3,5-dimethyl-1,2-dioxolane in selective sulfoxidation of sulfides.…”

Regioselective and Facile Oxidative Thiocyanation of Anilines and Indoles With Trans-3,5‐dihydroperoxy‐3,5‐dimethyl‐1,2‐dioxolane

“…Therefore, development of more effective and benign approaches for thiocyanation of different organic compounds including anilines and related compounds such as indoles appears as important experimental challenge. Recently, gem-dihydroperoxides have received considerable interest as high potent oxidants for various organic transformations [23][24][25][26][27][28][29][30]. Following our ongoing research on the synthesis of gem-dihydroperoxides [31][32][33][34], and their applications in a variety of organic conversions including oxidation of alcohols to ketones [35], selective sulfoxidation of sufides [36], selective halogenation of aromatic compounds [37], epoxidation of α,β-unsaturated ketones [38], oxidative conversion of aldehydes, amines, alcohols and halides to nitriles [39], ultrasound-accelerated selective oxidation of primary aromatic amines to azoxy derivatives [40], and synthesis of benzimidazoles and benzothiazoles [41], herein, we were encouraged to study the oxidative potential of trans-3,5-dihydroperoxy-3,5-dimethyl-1,2-dioxolane (DHPDMDO) for thiocyanation of anilines and their related heterocyclic compounds such as indoles.…”

Theoretical investigation of the [1,2]-sigmatropic hydrogen migration in the mechanism of oxidation of 2-aminobenzoyl-CoA by 2-aminobenzoyl-CoA monooxygenase/reductase

“…It was determined that the monooxygen transfer involving 4a-hydroperoxyflavins does not occur from a carbonyl oxide formed on ring opening of the isoalloxazine ring between C4 and C4a (13, 14), as originally proposed (1), but by nucleophilic attack on the terminal oxygen of the flavin 4a-hydroperoxide (15). Dioxygen transfer from the oxygen anion 4a-FlEt-OO Ϫ is known in model reactions (3,(16)(17)(18)(19)(20), but there is no evidence for the existence of a flavin dioxygenase enzyme.The flavoenzyme mixed-function oxygenase 2-aminobenzoylCoA monooxygenase͞reductase (ACMR) (EC 1.13.14.40) from Azoarcus evansii catalyzes both the oxygenation and hydrogenation reactions provided in Eqs. 1 and 2.…”