Computational studies with ωB97X-D density functional theory of the mechanisms of the steps in Trauner's biomimetic synthesis of preuisolactone A have elaborated and refined mechanisms of several unique processes. An ambimodal transition state has been identified for the cycloaddition between an
Quantitative knowledge of the fluorinating strength of electrophilic N-F reagents is of crucial importance for rational design and optimization of novel reagents and new reactions. Herein, we report the first systematic computation of fluorinating potentials of 130 electrophilic N-F reagents in two commonly used solvents dichloromethane and acetonitrile in terms of the N-F bond heterolysis energies as expressed by the fluorine plus detachment (FPD) values. The calculated FPD scales of 130 N-F reagents cover a range from 112.3 to 290.4 kcal mol(-1) and 110.9 to 278.4 kcal mol(-1) in dichloromethane and acetonitrile, respectively. This comprehensive FPD database provides a valuable quantitative guide for studying the influence of structural variation on the fluorinating strength of the N-F reagents, opening a door to the rational design of novel reagents with appropriate fluorinating strength for specific purposes. It is demonstrated that the FPD values can reproduce the reactivity order for electrophilic N-F reagents better than other parameters.
An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.
The preparation of the first nitrogen- or phosphine-ligated trifluoromethoxylated Pd( ii ) complexes [(L)Pd(4-CF 3 Ph)(OCF 3 )] (L = TMEDA, 4-mepyridine or t Bu-BrettPhos, BrettPhos, RuPhos and CPhos) was described.
Comprehensive Summary Five‐coordinate neutral Cu(III) complexes have long been considered as the key intermediates in copper‐mediated/catalyzed arene trifluoromethylative reactions, but the identity of these complexes remains elusive. Herein, we reported, for the first time, the preparation and characterization of these putative complexes [(bpy)Cu(CF 3 ) 2 (C 6 F 4 R)] and investigation of their C(sp 2 )‐CF 3 bond‐forming reductive elimination. Our mechanistic studies including kinetic studies, the effect of temperature and solvents, the effect of the para ‐substitution of the ligand as well as DFT calculations suggest that C(sp 2 )‐CF 3 reductive elimination process proceeds via synchronous bond‐breaking/bond‐forming process.
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