Thermal Isomerizations of 2-d-1-(E)-Propenylcyclobutanes to 4-d-3-Methylcyclohexenes
- 7 April 2006
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 128 (17) , 5608-5609
- https://doi.org/10.1021/ja0586586
Abstract
Racemic trans-2-d-1-(E)-propenylcyclobutane at 276 °C in the gas phase fragments to give ethylenes and pentadienes, equilibrates with its cis isomer, and rearranges to mixtures of 4-d- and 6-d-3-methylcyclohexenes through [1,3] carbon shifts. The time-dependent distributions of deuterium-labeled isomers of propenylcyclobutanes and 3-methylcyclohexenes reveal a significant secondary deuterium kinetic isotope effect favoring C1−C4 over C1−C2 bond breaking (kH/kD = 1.16 ± 0.02) and a 72:28 preference for structural isomerizations giving (si + ar) rather than (sr + ai) products through conformationally flexible short-lived diradical intermediates.Keywords
This publication has 18 references indexed in Scilit:
- Thermal Stereomutations and Stereochemically Elucidated [1,3]-Carbon Sigmatropic Shifts of 1-(E)-Propenyl-2-methylcyclobutanes Giving 3,4-DimethylcyclohexenesJournal of the American Chemical Society, 2003
- Dynamics of the biradical mediating vinylcyclopropane–cyclopentene rearrangementPhysical Chemistry Chemical Physics, 2002
- Mechanism of the Vinylcyclopropane−Cyclopentene Rearrangement Studied by Quasiclassical Direct DynamicsThe Journal of Physical Chemistry A, 2001
- Quantum dynamics of the trimethylene biradical Stereomutation of cyclopropane and unimolecular decayFaraday Discussions, 1998
- Direct Dynamics Simulation of the Lifetime of TrimethyleneJournal of the American Chemical Society, 1996
- Thermal Stereomutations of Cyclopropane and of Isotopically Labeled Cyclopropanes Assessed through ab Initio Computational Methods and Kinetic Isotope Effect CalculationsThe Journal of Physical Chemistry, 1994
- Stereomutation of cyclopropane revisited. An ab initio investigation of the potential surface and calculation of secondary isotope effectsJournal of the American Chemical Society, 1992
- Facile product isolation from organostannane reductions of organic halidesThe Journal of Organic Chemistry, 1979
- Thermal rearrangements of bicyclo[3.1.0]hex-2-ene. Degenerate rearrangementsJournal of the American Chemical Society, 1974
- Synthesis of cis-2-aza-3-oxo-4-oxabicyclo[4.2.0]octane and cis-2-aza-3-oxo-4-oxabicyclo[4.1.0]heptaneThe Journal of Organic Chemistry, 1971