Phenylcarbene rearrangement

Also interesting is the autoxidation of incarcerated CHTE in aerated solution. Under these conditions, oxygen diffuses into the hemicarcerand and adds to the central aUene C to produce a spirocychc dioxirane 86. The latter 86 rapidly decarboxylates to benzene at room temperature. 

This example illustrates nicely how kinetic experiments in confined space allow mapping of potential energy surfaces of important organic chemical processes involving highly reactive intermediates, which is difficult to achieve with other techniques such as laser flash photolysis, CID or matrix isolation. 

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Although the situation is complicated by the well-known phenylcarbene rearrangement that interconverts 51 and 53, the use of labeled carbon allows an... 

Gas-phase pyrolysis of phenyldiazomethane releases phenylcarbene, which undergoes the phenylcarbene rearrangement. Phenylcarbene cyclizes to form a... 

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