10.1002/ejoc.201700970
This research aims to improve the efficiency of radiofluorination reactions for the synthesis of PET radiotracers. The study explores the use of quinuclidine and DABCO as additives to enhance the nucleophilic substitution of [18F]fluoride ion in 5-substituted 2-halopyridines, which are challenging precursors due to the presence of a good leaving group. The researchers found that quinuclidine and DABCO significantly increased the yields of [18F]2-fluoropyridines to practically useful levels (>15%) by likely promoting radiofluorination through the reversible formation of quaternary ammonium intermediates. The study also demonstrated that these additives tolerated free aryl amino groups in the precursors and were effective in various 5-substituted 2-halopyridines. The findings suggest that quinuclidine and DABCO can facilitate the rapid screening of homologous candidate PET radiotracers by improving the radiosyntheses of [18F]2-fluoropyridines directly from more readily accessible 2-halopyridyl precursors.
10.1002/hlca.19870700303
The research focuses on the study of bimolecular nucleophilic substitution at the boron atom in complexes of 2,2’,2”-nitrilotriphenol. The purpose of the study was to investigate the coordination of boron(III) complexes with electronegative ligand atoms and their reactivity towards N-nucleophiles, comparing it to the coordination behavior of carbon and silicon in the same row and diagonally related in the periodic table. The researchers synthesized and studied the reactivity of the boron complex 111, which forms with the ligand 2,2’,2”-nitrilotriphenol, and its subsequent reactions with nitrogen bases like pyridine, quinuclidine, and others. Through temperature-dependent NMR spectroscopy, they found that the reaction is a bimolecular nucleophilic substitution (SN2). The chemicals used in the process included trimethyl borate, 2,2’,2”-nitrilotriphenol, pyridine, quinuclidine, diazabicyclooctane (DABCO), 4-(dimethylamino)pyridine (Me2NPy), and other N-donors, as well as solvents like chloroform (CHCl3), acetonitrile (MeCN), and tetrahydrofuran (THF). The study concluded that the complex 111 is considerably strained and that the reaction entropy is found almost completely on the bimolecular side of the reaction profile, indicating an associative transition state, i.e., an SN2-type mechanism for the nucleophilic substitution.