1,2-Dioxetanes with phosphines

Baumstark, A.L. and Vasquez, P.C. (1984) Reaction of tetramethyl-1,2- dioxetane with phosphines deuterium isotope effects. Journal of Organic Chemistry, 49 (5), 793-798. 

There have been extensive studies on the reaction of dioxetanes and dioxetanones with nucleophiles (C, N, P, and S) and the reader is directed to CHEC-II(1996) for an exhaustive list up to 1996. The most common reactions of dioxetanes have been with phosphorus nucleophiles. The phosphines and phosphites first insert into the 0-0 bond. The phosphorane intermediate then collapses to afford phosphine oxide or the trialkylphosphate and the corresponding epoxide (Scheme 6). The same is true for the treatment of a-peroxy lactones with phosphines and phosphites except that the so-formed a-lactone intermediate undergoes decarboxylation and ultimately furnishes a ketone <1997JOC1623>. 

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. 

Dioxetanes can also be transformed into 1,2-diols by reduction with LiAlH4 or into epoxides by treatment with phosphines in the dark.1421... 

At low temperatures dioxetane adducts with trivalent phosphorus have been isolated by Bartlett and coworkers. These cyclic phosphoranes gradually decompose to give the corresponding epoxide and phosphine oxide (Scheme 39) (73JA6486). Aryl-substituted phosphines... 

Peroxides and Related Compounds.— Triphenylphosphine has been shown to react with the dioxetan (61) to give the quinquecovalent compound (62). This decomposes to give an epoxide on heating. Several peroxides and polyperoxides react with alkyl- and aryl-phosphines in the presence of water. Alcohols are... 

Cyclic Phosphoranes - The reaction of dioxetanes (28a-c) with ylides (29a-d) gave phosphonium alkoxides (30a-f) in equilibrium with the pentacoordinate dioxa-2,5-phosphorinanes (31a-f).16 Hydrolysis via the hydroxyphosphoranes (32a-f) gave the phosphine oxides (33a-f). 

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