The phenylcarbene rearrangement revisited

Peter P. Gaspar, Jong Pyng Hsu, Sarangan Chari, Maitland Jones

Research output: Contribution to journalArticlepeer-review

79 Scopus citations


The evolution of mechanistic ideas about the phenylcarbene rearrangement has been reviewed, and three closely linked problems have been identified toward whose solution this research has been aimed: 1. Why do the ratios of the stable end products from the rearrangements of o-, m- and p-tolylmethylene differ when all three reactions have been throught to pass through a common intermediate? 2. Why does the rearrangement of 2-methylcycloheptatrienylidene lead to exclusive formation of styrene? 3. What is the mechanism of styrene formation from o-tolylmethylene? New mechanisms have been proposed in which m- and p-tolylmethylene can rearrange to styrene without necessarily being converted to o-tolylmethylene. The formation of a small amount of 2,6-dimethylstyrene from the rearrangement of 3,4,5-trimethylphenylmethylene is viewed as evidence for such a mechanism, and a set of interconverting norcaradienylidenes are believed to be the crucial intermediates. Other alternatives are considered and rejected on the basis of the rearrangement products of 3,5-dimethyl- and 3,4,5-trimethylphenylmethylene.

Original languageEnglish (US)
Pages (from-to)1479-1507
Number of pages29
Issue number8
StatePublished - 1985
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Biochemistry
  • Drug Discovery
  • Organic Chemistry


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