Cyclic peroxides using oxygen

Autoxidation140 of suitable olefins, particularly 1,3-dienes, leads to cyclic peroxides (though mostly in low yields) as well as polymeric peroxides. These autoxidations occur when the olefins are aerated with oxygen, and does not usually require exposure to light or the use of sensitizers. Only a few papers have been published in this field, and these are mostly due to Hock et al.147-183... 

The cyclic peroxide natural product (+)-chondrillin was prepared by P.H. Dussault and co-workers using a singlet oxygenation/radicai rearrangement sequence as the key step. The first stereocenter was introduced via the Midland reduction of an ynone substrate. 

Figure 6. Schematic of the state correlation diagram for the concerted addition of molecular oxygen to a diene. The electronic configurations for states of the (O2 + diene) complex are indicated on the left (state of O2 in the complex given in brackets). States of the cyclic peroxides with their appropriate electronic configurations are on the right in order of increasing energy. Dashed curves indicate the primitive correlations obtained by straightforward application of symmetry and spin restrictions. Solid curves indicate final correlations obtained by using the additional information contained in the orbital correlation...

Reaction of trans, trara-conjugated dienes with singlet oxygen and subsequent dehydration of cyclic peroxide to cyclic ether with iron (II) sulfate. This has been used to convert the 8,10- and 9,11-dienes to the corresponding furanoid... 

Bis(iluoroformyl) peroxide, prepared from carbon monoxide, oxygen, and fluorine at 55 cyclizes to the cyclic peroxide (77) when left in contact with potassium fluoride at — 80 °C, presumably via a mechanism of the type proposed for fluoride-initiated conversion of the bis(acyi) fluoride CKCFjCOF) into perfluoro-j3-oxa-8-valerolactone (see Vol. 1, p. 76) use of caesium fluoride at -40 °C gives a mixture of the acyclic peroxides (CFs-0-0)sC0 and CFj-O-O COF, possibly via attack of F on the CF group of (77). The 1,2-dioxolan (78) can be obtained by direct fluorination of the copper chelate of l,l,l,5,5,5-hexafluoropraitane-2,4-dione at —20... 

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