Selective Metalation and Functionalization of Fluorinated Nitriles Using 2,2,6,6-Tetramethylpiperidyl Bases.

Thiago Dos SantosHenrique P OrenhaValter E MurieRicardo VessecchiGiuliano Cesar Clososki

Published in: Organic letters (2021)

We have accomplished regioselective deprotometalation of aromatic and heteroaromatic nitriles via (TMP)2Zn·2MgCl2·2LiCl and TMPMgCl·LiCl (TMP = 2,2,6,6-tetramethylpiperidyl) with the exploration of new and scarcely investigated metalation positions. Regioselectivity was rationalized by DFT calculations. The quenching of the generated organozinc and organomagnesium intermediates with various electrophiles gave access to 47 highly functionalized nitriles with yields up to 95%. Additionally, we report a difunctionalization strategy and the use of functionalized nitriles as building blocks to construct relevant heterocycles.

Keyphrases

density functional theory
quantum dots
molecularly imprinted
molecular dynamics simulations
molecular docking
heavy metals
atomic force microscopy
risk assessment
simultaneous determination