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The [1,3]-hydrogen shift in cyclopropene. Does it exist?

✍ Scribed by Frank Jensen

Publisher
Elsevier Science
Year
1989
Tongue
English
Weight
615 KB
Volume
161
Category
Article
ISSN
0009-2614

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✦ Synopsis

The [ 1,3]-hydrogen shift in cyclopropene has been investigated by ab initio calculations. At Hartree-Fock and Moller-Plesset levels of theory the Woodward-Hoffmann forbidden suprafacial hydrogen migration is calculated to be a concerted reaction, although the energy of the transition structure at levels including electron correlation is very close to the dissociation limit, cyclopropenyl radical and a hydrogen atom. Sufficiently high-level MCSCF calculations concur with these results, predicting that a concerted [ 1,3]-hydrogen shift should be a few kcal/mol lower in energy than the dissociation process.

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