Mechanism of endoperoxide formation. 3. Utilization of the Young and Carlsson kinetic techniques

Synthesis, Chemistry and Applications of 5‐Hydroxymethyl‐furfural and Its Derivatives

“…Clennan et al 171 reported results of their work on the chemical behaviour of FDC in the photochemical oxidation with oxygen. They performed 1 H, 13 C and 17 O NMR studies on products of the reaction.…”

Biomimetic Total Synthesis of Litseaverticillols A, C, D, F, and G: Singlet‐Oxygen‐Initiated Cascades

“…A detailed mechanistic rationale for this tandem sequence transforming sesquirosefuran (10) to litseaverticillols A (1) and C (3) is given in Scheme 4. The first step involves the [4+2] cycloaddition of singlet oxygen to the furan moiety [13] of 10 and is followed by regio-and diastereoselective [14] nucleophilic opening of endoperoxide 16 by MeOH. Reduction of the resulting hydroperoxide 15 to the fleeting anomeric hemiacetals 17 leads to the achiral keto aldehyde 9, after elimination of MeOH.…”

Singlet Oxygen as a Reagent in Organic Synthesis

“…Singlet oxygen reactions have been conducted with many cyclopentadiene and cyclohexadiene compounds as a means of generating bicyclic endoperoxides [72]. The synthesis of an endoperoxide from the parent cyclopentadiene in O 2 -purged CHCl 3 -CCl 4 (1 : 4) at À20 C has been reported in 93% yield, in which the photosensitizer was a ROMP-sphere-supported seco-porphyrazine [55].…”

“…The formation of ozonide 67 resulted from the TPP-sensitized photooxygenation of 2,5-dimethylfuran (57) in CH 2 Cl 2 at À78 C [72]. Low-temperature NMR spectra were recorded, and the reaction can presumably be taken to 100% yield, although the endoperoxide was not isolated.…”