Phenoxymethyl cation

Olah and co-workers602 603 have obtained primary carboxonium ions such as methoxymethyl and phenoxymethyl cations and their halogenated derivatives (304-307). 

The essential step is believed to be the escape of the electron from the coulomb-valence force potential well. A subsequent proton transfer from the radical cation to the solvent should depend on its acidity. For example, the transient spectra in Table II show that proton transfer takes place for phenol and anisole, in which cases the radicals were identified as neutral phenoxyl and phenoxymethyl, respectively. On the other hand, irradiating aniline gave both the neutral and protonated... 

When exo-cf die carbon atom of 1 is attacked by oxirane the product with ether-carbonate group 2 is formed (reaction pathway a). On the other hand as a result of oxirane attack on endo-cydic carbon atom of 1 both the ether group 3 and cyclic carbonate are formed (pathway b). The intramolecular reaction between the carbocation and an oxygen atom of linear ether leads to spiroorthocarbonate 4 (pathway c). It was shown that the reaction proceeded partially according to pathway a in the case of using cyclic carbonates bearing phenoxymethyl and chloromethyl substituents, but for other five-membered cyclic carbonates the reaction pathway b dominated. Due to higher stability of the trialkoxycarbenium cation the polymerization rate is slower than that of oxirane homopolymerization. 

A Claisen protocol has been reported for the synthesis of substituted allyl-silanes using a cationic Ir(I) catalyst followed by a thermal Claisen rearrangement to provide the allylsilanes with high diastereoselectivities (Scheme 25). ( )-(Phenoxymethyl)arylpropenoates have been reported to undergo regioselective... 

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