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Synlett 1997; 1997(SI): 518-520
DOI: 10.1055/s-1997-6119
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Energetics of Cation-Olefin Addition in the Gas Phase and in Solution

Corky Jenson, William L. Jorgensen*
  • *Department of Chemistry, Yale University, New Haven, Connecticut 06520-8107, USA
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Publication Date:
31 December 2000 (online)

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The cation-olefin addition of 2-methyl-2-propyl cation and 2-methylpropene has been investigated in the gas phase and in solution with ab initio calculations and Monte Carlo statistical mechanics simulations. The reaction is exothermic by ca. 20 kcal/mol and proceeds without activation energy in the gas phase. However, solvation introduces a 3-4 kcal/mol barrier at a C-C separation near 5 Å in methylene chloride, THF, and methanol. An intermediate in a shallow energy well is found near 3-Å separation. Implications for sterol biosynthesis are discussed.

cation-olefin addition - tertiary carbenium ion - solvent effects - Monte Carlo