Electrophiles thermal fragmentation

Nucleophilic Reactions. M,C)-Bis(trimethylsilyl)hydroxyl-amine is a protected, lipophilic form of hydroxylamine. It reacts with a variety of electrophiles predominantly by attack on the nitrogen nucleophilic center. Reaction with acid chlorides (1 equiv) in the presence of triethylamine gives M<9-bis(trimethylsilyl)-hydroxamic acids by iV-acylation. A related reagent, tris(tri-methylsilyl)hydroxylamine, gives the same product in high yields, also by iV-acylation. Hydrolysis gives the free hydroxamic acids, whereas thermal fragmentation affords isocyanates (eq 1). ... 

More recent studies have shown that monomeric metaphosphates such as 147 are just as unisolable as the metaphosphate ion 102, and are even more electrophilic. Generation of metaphosphates is accomplished mainly in two ways, i.e. by thermal or photochemical fragmentation reactions, on the one hand, and by decomposition of suitably activated phosphates on the other. 

Besides their thermal decompositions into carbonyl fragments, the chemistry of 1,2-dioxetanes is quite limited. Obviously one of the reasons for this is the great lability of the dioxetane ring system. However, a number of reactions with nucleophiles and electrophiles have been performed and will be briefly reviewed here. 

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