Polyhalogenated Bicyclo[1.1.1]pentane-1,3-dicarboxylic Acids

Autor:	Martin Dračínský, Jiří Kaleta, Thi Phuong Le, Ivana Císařová, Igor Rončević, Veronika Šolínová, Václav Kašička
Rok vydání:	2021
Předmět:	Pentane chemistry.chemical_compound Capillary electrophoresis Relative strain Bicyclic molecule chemistry Computational chemistry Organic Chemistry Halogen Fluorine chemistry.chemical_element Pentanes Acid dissociation constant
Zdroj:	The Journal of Organic Chemistry. 86:10303-10319
ISSN:	1520-6904 0022-3263
DOI:	10.1021/acs.joc.1c01020
Popis:	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 TMS3SiH, 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 (pKa) for all new derivatives have been determined by capillary electrophoresis, and these experimental values show excellent agreement with pKas predicted by DFT methods. Extensive DFT calculations have been used to rationalize the selective formation of four out of nine possible F2Cl1-4 isomers of bridge-halogenated bicyclo[1.1.1]pentanes and to obtain relative strain energies for all possible isomers.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_dedup___::565b0bfa1ecc7c9bd390a753a968ba2b https://doi.org/10.1021/acs.joc.1c01020 Zobrazit plný text záznamu