Mark A. Forman

The Thermal Rearrangement of Endo-7-Methyl-exo-7-vinylbicyclo[3.2.0]Hept-2-ene

Abstract Gas-phase thermolysis of the title compound in the temperature range of 150°–166°C yields predominantly cis -6-methyl-4,7,8,9-tetrahydroindene by tandem [1,3]–[3,3) sigmatropic shifts: however, we cannot exclude some direct conversion by an alternative [1,3] sigmatropic migration.

Structures and Rotational Barriers of a Diiodobinorsnoutane: Energetic Preference for Gauche Conformation

The diiodobinorsnoutane, bi(5-iodopentacyclo[4.3.0.0(2,4).0(3,8).0(5,7)]non-4-yl) (5), exists in a sterically hindered gauche conformation rather than an anti or an averaged (freely rotating) C2v structure. Density functional theory (DFT) predictions place the gauche conformation 11 kcal/mol more stable than the anti conformation with a barrier of 17 kcal/mol connecting the minima. These are consistent with variable-temperature NMR (17.1 ± 0.8 kcal/mol) estimates and X-ray analysis. Predictions of the torsional profiles of the yet-unsynthesized bromo-, chloro-, and fluoro- analogues show a progressive lowering of the barriers.