Highly chemoselective difluoromethylative homologation of iso(thio)cyanates: expeditious access to unprecedented α,α-difluoro(thio)amides.

Highly chemoselective difluoromethylative homologation of iso(thio)cyanates: expeditious access to unprecedented α,α-difluoro(thio)amides.
Chem Commun (Camb). 2019 Oct 11;:
Authors: Miele M, D'Orsi R, Sridharan V, Holzer W, Pace V
Abstract
The new motif - α,α-difluoromethyl thioamide - has been assembled starting from isothiocyanate (as thioamide precursor) and a formal difluoromethyl-carbanion generated from commercially available TMSCHF2. Upon proper activation of this reagent with potassium tert-amylate, the high-yielding transfer of the difluorinated nucleophile takes place under high chemocontrol. Various sensitive functionalities (e.g. ester, nitrile, nitro, azido groups) can be accommodated across the isothiocyanate core, thus allowing a wide scope. The methodology is highly flexible and adaptable to prepare analogous α,α-difluoromethyl oxoamides by conveniently using isocyanates as the electrophilic building-blocks.
PMID: 31602439 [PubMed - as supplied by publisher]

Source: Chemical Communications - October 10, 2019 Category: Chemistry Authors: Miele M, D'Orsi R, Sridharan V, Holzer W, Pace V Tags: Chem Commun (Camb) Source Type: research