From cyclic (alkyl)(amino)carbene (CAAC) precursors to fluorinating reagents. Experimental and theoretical study

Addition of anhydrous HF to the hydrochloride [ Me CAACH][Cl(HCl) 0.5 ] resulted in the formation of salts with high HF content. By stepwise removal of HF in vacuo , we selectively prepared [ Me CAACH][F(HF) 2 ] ( 3 ) and [ Me CAACH][F(HF) 3 ] ( 4 ). We also characterised a salt with [F(HF) 4 ] − anions within the structure of [ Me CAACH][F(HF) 3.5 ] ( 5 ). Compounds with a lower content of HF were not accessible under vacuum conditions. Me CAAC(H)F ( 1 ) was selectively prepared by abstraction of HF from 3 with CsF or KF, while [ Me CAACH][F(HF)] ( 2 ) was prepared by mixing 3 and 1 in a 1 : 1 ratio. Compound 2 proved to be quite unstable as it tends to disproportionate into 1 and 3 . This observation triggered our computational study, in which the structural relationships between CAAC-based fluoropyrrolidines and dihydropyrrolium fluorides were investigated using different DFT methods. The study showed that the results were very sensitive to the computational method used. For a correct description, the quality of the triple-ζ basis set was crucial. Surprisingly, the isodesmic reaction of [ Me CAACH][F] + [ Me CAACH][F(HF) 2 ] → [ Me CAACH][F(HF)] + [ Me CAACH][F(HF)] did not confirm the low thermodynamic stability of 2 . Furthermore, the use of 3 as a nucleophilic fluorinating reagent was tested on a range of organic substrates, as it is the most stable compound in this series. It was found to have the potential to fluorinate benzyl bromides, 1- and 2-alkyl bromides, silanes and sulfonyls with good to excellent yields of the target fluorides. A series of CAAC-based fluoride compounds has been prepared. Structural relationship between the compounds was investigated by DFT calculations, while their fluoride donating ability was tested on various organic substrates.