1.2- Dioxetanes chemical transformations

Nevertheless, there are two highly efficient CL systems which are believed to involve the CIEEL mechanism in the chemiexcitation step, i.e. the peroxyoxalate reaction and the electron transfer initiated decomposition of properly substituted 1,2-dioxetanes (Table 1)17,26 We have recently confirmed the high quantum yields of the peroxyoxalate system and obtained experimental evidence for the validity of the CIEEL hypothesis as the excitation mechanism in this reaction. The catalyzed decomposition of protected phenoxyl-substituted 1,2-dioxetanes is believed to be initiated by an intramolecular electron transfer, analogously to the intermolecular CIEEL mechanism. Therefore, these two highly efficient systems demonstrate the feasibility of efficient excited-state formation by subsequent electron transfer, chemical transformation (cleavage) and back-electron transfer steps, as proposed in the CIEEL hypothesis. 

One of the earliest chemical transformations of 1,2-dioxetanes was their reaction with phosphines (Eq. 72). It was shown that the trivalent phosphorus first inserts into the peroxide bond to afford a relatively stable phosphorane. On warming the phosphorane eliminates phosphine oxide to yield the epoxide product. In this elimination, there is inversion of the stereochemistry at one of the carbon centers. 

Endoperoxides (also 1,2-dioxetanes) are versatile starting materials for further transformations. In view of the weak 0-0 bond, these peroxides are thermally sensitive to homolytic cleavage, a feature that makes most of them ha2aidous. Ring opening opens up attractive opportunities for selective transformations that include reductions (diols), oxidations (dicarbonyl products), rearrangements (hydroxy carbonyl compounds, epoxy carbonyl compounds, fo/s-epoxides, ene diones, etc.) and additions (polycycKc dioxanes or trioxanes, some of which display antimalarial activity). The synthesis and the subsequent reactions of the 2,3-dioxabicyclo[2.2.2]oct-7-en-5-one skeleton have been studied by Adam etak An impressive number of chemical transformations and examples for applications in organic synthesis have been collected in several reviews. 

Adam, W., Ahrweiler, M., and Sauter, M., Photosensitized oxygenation of a keto furan isolation of the first furan dioxetane by rearrangement of its endoperoxide and selected chemical transformations, Angew. Chem., 105, 104, 1993. 

Chemiluminescence is defined as the production of light by chemical reactions. This light is cold , which means that it is not caused by vibrations of atoms and/or molecules involved in the reaction but by direct transformation of chemical into electronic energy. For earlier discussions of this problem, see 7 9h Recent approaches towards a general theory of chemiluminescence are based on the relatively simple electron-transfer reactions occurring in aromatic radical-ion chemiluminescence reactions 10> and on considerations of molecular orbital symmetry as applied to 1.2-dioxetane derivatives, which very probably play a key role in a large number of organic chemiluminescence reactions 11>. 

The intramolecular chemical titration is conceptually and experimentally simple and convenient, but it requires that a particular dioxetane must be made that chemi-energizes the photochemically active carbonyl product K. This is usually a formidable and challenging synthetic problem. Representative intramolecularly chemienergized photochemical transformations include Norrish Type I cleavage (Eq. 44), Norrish Type II (Eq. 45a, b, c) cleavages, cyclohexadienone rearrangement (Eq. 46), and cyclopentenyl ketone rearrangement (Eq. 47). 

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