PreprintCC BYChemRxiv
Case Studies of Homemorphic Isomerization: Interconversion of In/Out Isomers of Bicyclo[6.5.1]tetradecane and Related Bicyclic Hydrocarbons
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.
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BibTeX
@misc{shafikov2026case,
title = {{Case Studies of Homemorphic Isomerization: Interconversion of In/Out Isomers of Bicyclo[6.5.1]tetradecane and Related Bicyclic Hydrocarbons}},
author = {Marsel Z. Shafikov and John A. Gladysz},
howpublished = {ChemRxiv},
year = {2026},
month = oct,
doi = {10.26434/chemrxiv.15010033/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010033/v1},
note = {CC BY},
}
RIS
TY - UNPB
TI - Case Studies of Homemorphic Isomerization: Interconversion of In/Out Isomers of Bicyclo[6.5.1]tetradecane and Related Bicyclic Hydrocarbons
AU - Marsel Z. Shafikov
AU - John A. Gladysz
PY - 2026
DA - 2026/10/07
PB - ChemRxiv
DO - 10.26434/chemrxiv.15010033/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010033/v1
AB - 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.
ER -