Cycloaddition 1.2- dioxetanes

Characteristic reactions of singlet oxygen lead to 1,2-dioxetane (addition to olefins), hydroperoxides (reaction with aHyhc hydrogen atom), and endoperoxides (Diels-Alder "4 -H 2" cycloaddition). Many specific examples of these spectrally sensitized reactions are found iu reviews (45—48), earlier texts (15), and elsewhere iu the Engchpedia. 

Another interesting cycloaddition, the detailed mechanism of which is still under investigation, is the addition of singlet oxygen to alkenes producing 1,2-dioxetanes (Section 5.15.3.3.2). 

Cycloaddition reactions can occur with retention of configuration in the pseudoexcitation band (Sect 1.1) whereas [2jt H-2jtJ reactions are symmetry-forbidden in the delocalization band. Experimental evidence is available for the stereospecific [2-1-2] cycloaddition reactions between A and olefins with retention of configuration (Scheme 14) [82]. A perepoxide intermediate was reported to be trapped in the epoxide form [83] in the reaction of adamantylideneadamantane with singlet oxygen affording dioxetane derivatives [84]. 

The reaction mechanism for the aerobic oxidation of the pz to seco-pz can be attributed to a formal 2 + 2 cycloaddition of singlet oxygen to one of the pyrrole rings, followed by cleavage (retro 2 + 2) of the dioxetane intermediate to produce the corresponding seco-pz (160). This mechanism is shown in Scheme 29 for an unsymmetrical bis(dimethylamino)pz. Further photophysical studies show that the full reaction mechanism of the photoperoxidation involves attack on the reactant by singlet oxygen that has been sensitized by the triplet state of the product, 159. As a consequence, the kinetics of the process is shown to be autocatalytic where the reactant is removed at a rate that increases with the amount of product formed. 

In a thorough study on photooxidation of 2,5-dimethyl-2,4-hexadiene (455) it was found that 1,2-dioxene 456, 1,2-dioxetane 457, hydroperoxy dienes 458 and 459 and, when methanol was used as solvent, also hydroperoxy(methoxy)octene 460 are formed (Scheme 124) . Product distribution was found to be highly solvent dependent. These results led investigators to postulate a mechanism involving the intermediacy of perepoxide 461 and zwitterion 462 (Scheme 124). Accordingly, the product of [4-1-21-cycloaddition 456, the product of [2 + 2]-cycloaddition 457, as well as the products 458 and 459 deriving from ene-addition would originate from polar intermediates 461 and... 

As already hinted at above, chiral dioxetanes, obtained through the highly stereoselective [2 + 2] cycloaddition of singlet oxygen to the chiral enecarbamate, provide a convenient preparation of optically active 1,2 diols as building blocks for asymmetric synthesis (Scheme 5) . Reduction of the dioxetane 2c by L-methionine, followed by release of the oxazolidinone auxiliary by NaBH4/DBU reduction, affords the enantiomerically pure like-5 diol (for additional cases, see Table 4 in Reference 19e). 

In contrast, the a-peroxy lactones, also members of the dioxetane family, display a higher reactivity toward nucleophiles, in view of the inherent polarization of the peroxide bond by the carbonyl functionality. Consequently, the nucleophilic attack is expected to take place at the more sterically hindered but more electrophilic alkoxy-type oxygen atom of the peroxide bond. A recent detailed study of the oxidation of various di-, tri-and tetrasubstituted alkenes 6 with dimethyl a-peroxy lactone (7) revealed, however, much complexity, as illustrated in Scheme 7 for R = CH3, since cycloaddition (8), ene-reaction (9 and 10) and epoxidation (11) products were observed. In the presence of methanol, additionally the trapping products 12 and 13 were obtained, at the expense of the polyester 14. The preferred reaction mode is a sensitive function of the steric demand imposed by the attacking alkene nucleophile. 

With electron rich olefins 1,2 cycloaddition forms relatively unstable dioxetanes which cleave to give carbonyl fragments ... 

Certain hindered alkenes display exceptional behavior. They readily undergo cycloaddition to yield 1,2-dioxetanes despite the presence of allylic hydrogen. The oxidation of 2,2 -biadamantylidene was the first successful synthesis of the dioxetane of an unactivated alkene 400,401... 

Cycloheptatriene represents a challenging substrate for cycloaddition. It can react either in a [2 + 4 ]- or [2 + 6]-cycloaddition to yield isomeric endoperoxides 53 and 54, respectively (Scheme 9.8). Moreover, it may give a 1,2-dioxetane (55) in a [2 + 2] process. Norcaradiene, its valence isomer, may also yield a [2 + 4] adduct (56). All four products were detected in the transformation of the nonsubstituted molecule.421,422... 

---