Data di Pubblicazione:
2020
Citazione:
Divergent, Stereospecific Mono- and Difluoromethylation of Boronic Esters / V. Fasano, N. Winter, A. Noble, V.K. Aggarwal. - In: ANGEWANDTE CHEMIE. INTERNATIONAL EDITION. - ISSN 1433-7851. - 59:22(2020 May 25), pp. 8502-8506. [10.1002/anie.202002246]
Abstract:
There is considerable interest in incorporating fluorine into agrochemicals and pharmaceuticals to improve their biological properties. Whilst a number of methods have been reported for installing CH2F and CHF2 groups, they are mainly limited to radical reactions, which are invariably racemic. Herein, we report the divergent, stereospecific reaction of fluoroiodomethyllithium with boronic esters to give α-fluoro-boronic esters. These unique intermediates can be readily transformed into the corresponding mono- or difluoromethylated compounds through proto- or fluorodeboronation, respectively. The use of the highly unstable fluoroiodomethyllithium was key to allowing rapid 1,2-migration over competing decomposition of the carbanion. DFT calculations informed and supported the experimental findings.
Tipologia IRIS:
01 - Articolo su periodico
Keywords:
1,2-migration; boronic esters; fluorocarbanions; fluoromethylation; stereospecificity
Elenco autori:
V. Fasano, N. Winter, A. Noble, V.K. Aggarwal
Link alla scheda completa: