Degenerate thermal isomerizations of bicyclo [3.1.1]hept-2-ene: strategy and analysis

作者：Baldwin John E^*; Hudson Bruce S

来源：Journal of Physical Organic Chemistry, 2014, 27(3): 213-217.

DOI：10.1002/poc.3268

• C-13 deuterium shifts
• bicyclo[3
• 1
• 1]hept-2-ene
• deuterium labels
• epimers
• thermal [1
• 3] carbon shifts

Bicyclo[3.1.1]hept-2-ene was first prepared and well identified in 1972. In 1974, the degenerate thermal isomerization involving 1-d- and 3-d-bicyclo[3.1.1]hept-2-ene was approached successfully, as one of the two deuterium-labeled structures was selected, heated, and equilibrated. There has been no further study of this degenerate isomerization. Here, a detailed outline of reaction trajectories for d(2)-labeled bicyclo[3.1.1]hept-2-enes is given that will establish the four independent kinetic parameters needed for 20 linking paths between six d(2)-species. The use of racemates, eliminating chiral separations and dissections, provides degenerate isomerization paths providing this method with general utility.

• 出版日期2014-3