Domino Self-Sensitized Photooxygenation of Conjugated Dienones for the Synthesis of 1,2,4-Trioxanes

Abstract

The photochemical behavior of several dienones was studied under aerobic conditions. 2-Allylidene-1,3-cycloalkanediones prepared via Knoevenagel-type condensation between simple readily available 1,3-dicarbonyl substrates and α,β-unsaturated aldehydes afforded 1,2,4-trioxane derivatives upon UVA irradiation in the presence of oxygen. This domino self-sensitized photooxygenation cascade of conjugated carbonyl systems proceeds stereoselectively and involves the formation of two new oxa-cycles, three new bonds (two C–O), and three stereocenters.

Marriage of Peroxides and Nitrogen Heterocycles: Selective Three-Component Assembly, Peroxide-Preserving Rearrangement, and Stereoelectronic Source of Unusual Stability of Bridged Azaozonides

“…The dramatic expansion of medicinal chemistry of organic peroxides was inspired by >100 known peroxide-containing natural products. − The variety of natural examples lessened concerns associated with the perceived peroxide instability and led to research efforts aimed at the development of synthetic approaches to varied classes of cyclic peroxides including 1,2-dioxolanes, − 1,2,4-trioxolanes (ozonides), ,− 1,2-dioxanes, − 1,2,4-trioxanes, − 1,2,4,5-tetraoxanes, − cyclic triperoxides, and tricyclic mono- and bisperoxides. − …”

Self-Sensitized Photooxidation of Naphthols to Naphthoquinones and the Use of Naphthoquinones as Visible Light Photocatalysts in Batch and Continuous Flow Reactors

“…Very few and specific examples have been described to generate 1 O 2 via self-sensitization under visible light activation. These are mostly related to large polyaromatic compounds such as bilirubin, fullerenes, − or dimethyldihydropyrene derivatives, , while examples of the self-sensitization of smaller molecules remain very limited. − …”

Inverse α-Effect as the Ariadne’s Thread on the Way to Tricyclic Aminoperoxides: Avoiding Thermodynamic Traps in the Labyrinth of Possibilities

“…As a result, synthetic approaches have been developed for the synthesis of various classes of cyclic peroxides such as 1,2-dioxanes, − 1,2-dioxolanes, − 1,2,4-trioxanes, − 1,2,4-trioxolanes (ozonides), − bisperoxides, − and triperoxides. , Such peroxides display antiparasitic, ,− anticancer, ,− antifungal, ,, antitubercular, − and antiviral − activities. Synthetic peroxide OZ277 (“arterolane”) is used for the treatment of malaria.…”