Carbocations heteroatom-containing

A few observations of the isolation of carbocation-carbanion salt containing heteroatoms, such as oxygen and nitrogen, have been reported. Over 30 years ago LeGoff and LaCount (1963) reported the formation of a... 

When a simple alkene reacts with an electrophilic, lone-pair-bearing heteroatom, a carbocation is not formed. Instead, both C atoms of the it bond form new bonds to the electrophilic atom to give a product containing a three-membered ring. The four electrons required for the two new cr bonds come from the it bond and one lone pair of the heteroatom. The reaction is stereospecifically syn (i.e., the two new bonds form on the same side of the double bond). For example, epoxides are formed in the... 

The introduction of an arylthio (ArS) group at an ot-position of a heteroatom compound containing N or O causes a significant decrease in the oxidation potential, because the energy level of the S p-orbital is usually much higher than that of N and O p-orbital. In other words, the S p-orbital becomes the HOMO of the compound. One electron oxidation of such compounds leads to the formation of the radical cation, in which the C-S bond is cleaved selectively to generate a carbocation adjacent to the heteroatom Eq. 2. Therefore,... 

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