AI Article Synopsis
- - The study focuses on the selective radical chlorination of a specific compound, 2,2-difluorobicyclo[1.1.1]pentane-1,3-dicarboxylic acid, resulting in the creation of four new bicyclo[1.1.1]pentane compounds with varying chlorine and fluorine atom placements.
- - The positions of the halogen atoms in these new compounds have been accurately determined through X-ray diffraction analysis.
- - The acidity constants of the new derivatives were measured using capillary electrophoresis and compared with predictions made by density functional theory (DFT), with calculations also explaining the selective formation of certain isomers and their relative strain energies.
Article Abstract
Herein we report the highly selective radical chlorination of 2,2-difluorobicyclo[1.1.1]pentane-1,3-dicarboxylic acid. Together with radical hydrodechlorination by TMSSiH, four new bicyclo[1.1.1]pentane cages carrying two fluorine and one to three chlorine atoms in bridge positions have been obtained. The exact positions of all halogen atoms have been confirmed by X-ray diffraction. The acidity constants (p) for all new derivatives have been determined by capillary electrophoresis, and these experimental values show excellent agreement with ps predicted by DFT methods. Extensive DFT calculations have been used to rationalize the selective formation of four out of nine possible FCl isomers of bridge-halogenated bicyclo[1.1.1]pentanes and to obtain relative strain energies for all possible isomers.
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| http://dx.doi.org/10.1021/acs.joc.1c01020 | DOI Listing |
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