Regiospecific nucleophilic substitution in 2,3,4,5,6-pentafluorobiphenyl as model compound for supramolecular systems. Theoretical study of transition states and energy profiles, evidence for tetrahedral S(N)2 mechanism
Kvicala, J; Benes, M; Paleta, O; Kral, V
| HERO ID | 3859241 |
|---|---|
| In Press | No |
| Year | 2010 |
| Title | Regiospecific nucleophilic substitution in 2,3,4,5,6-pentafluorobiphenyl as model compound for supramolecular systems. Theoretical study of transition states and energy profiles, evidence for tetrahedral S(N)2 mechanism |
| Authors | Kvicala, J; Benes, M; Paleta, O; Kral, V |
| Journal | Journal of Fluorine Chemistry |
| Volume | 131 |
| Issue | 12 |
| Page Numbers | 1327-1337 |
| Abstract | 2,3,4,5,6-Pentafluorobiphenyl (PFBi) was modified by the nucleophilic substitution of one fluorine using a series of 0-, S- and N-nucleophiles, viz, alkaline salts of 2,2,2-trifluoro-ethanol, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctanol, 1,2:3,4-di-O-isopropylidenexylitol, allylsulfane, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctane-1-thiol, 3-aminopropan-1-ol (7), and tert-butyl N-(3-aminopropyl)carbamate (8). All the substitutions took place exclusively at the position para to the phenyl group. (3-Amino-propyl)amino derivative of PFBi (15) was further modified at the terminal amino group by acylation or fluoroalkylation. The reaction of 8 was applied to meso-5,10,15,20-tetrakis-(pentafluorophenyl)porphyrin (20) to afford tris- (21) and tetrakis-substituted (22) products with complete para-regioselectivity. Theoretical studies of the reaction pathways of PFBi with ammonia, microsolvated lithium fluoride or lithium hydroxide revealed that no Meisenheimer-type intermediates are formed in the course of the simulated reactions: instead, tetrahedral S(N)2 mechanism was found. Significant regioselectivity of the nucleophilic aromatic substitution, leading to 4-substituted products, was predicted based on relative transition state energies in agreement with the observed experimental results. (C) 2010 Elsevier BM. All rights reserved. |
| Doi | 10.1016/j.jfluchem.2010.09.003 |
| Wosid | WOS:000285899700008 |
| Is Certified Translation | No |
| Dupe Override | No |
| Comments | Scopus URL: https://www.scopus.com/inward/record.uri?eid=2-s2.0-78649630220&doi=10.1016%2fj.jfluchem.2010.09.003&partnerID=40&md5=990aae1bc1757a9266cfd5c5e838fdfc |
| Is Public | Yes |
| Language Text | English |
| Keyword | 2,3,4,5,6-Pentafluorobiphenyl; meso-5,10,15,20-Tetrakis-(pentafluorophenyl)-porphyrin; Nucleophilic substitution; Computational chemistry; Meisenheimer complex; Tetrahedral S(N)2 mechanism |