Case Studies of Homemorphic Isomerization: Interconversion of In/Out Isomers of Bicyclo[6.5.1]tetradecane and Related Bicyclic Hydrocarbons
Year: 2026
Type: preprint
Abstract: Homeomorphic isomerization is equivalent to turning a molecule inside out in the same manner as a reversible article of clothing. Manifestations include the interconversion of (a) in,in and out,out isomers, or (b) in,out and out,in isomers of bicyclic molecules, but without inverting the configurations of the bridgehead atoms. In this preprint, this topological process is probed computationally for the title molecules. For the in,in/out,out manifold, the CH 2 tether is able to transit through the CH(CH 2 ) 6 CH tether with a barrier of ~26 kcal/mol, in good agreement with an experimental measurement. The geometries of the ground and transition states are analyzed in detail and the process of isomerization is visualized in animations.
Source: ChemRxiv
Authors: Marsel Z. Shafikov, John A. Gladysz
Language: English
Subfield: Physical and Theoretical Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: green
OpenAlex ID: W7220833489