Direct Electrophilic (Benzenesulfonyl)Difluoromethylthiolation with a Shelf-Stable Reagent

• Published in: Angewandte Chemie International Edition Vol. 55; no. 15; pp. 4790 - 4793
• Main Authors: Ismalaj, Ermal, Le Bars, Didier, Billard, Thierry
• Format: Journal Article
• Language: English
• Published: Germany Blackwell Publishing Ltd 04-04-2016; Wiley Subscription Services, Inc
• Edition: International ed. in English
• Subjects: (benzenesulfonyl)difluoromethanesulfenamide; Analogs; aromatic substitution; Chemical synthesis; Deuteration; difluoromethylthiolation; electrophilic addition; fluorine; Magnesium; Reduction; electrophilic addition; (benzenesulfonyl)difluoromethanesulfenamide; difluoromethylthiolation; aromatic substitution; fluorine
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201601280

The (benzenesulfonyl)difluoromethylsulfanyl (PhSO2CF2S) group is a valuable substituent with specific properties which can provide access to new applications of fluoroalkylthiolated compounds. Direct introduction of this moiety can be performed by in an electrophilic manner by using a new shelf‐stable reagent, namely a (benzenesulfonyl)difluoromethanesulfenamide. Furthermore, mild magnesium‐mediated reduction of the PhSO2CF2S group leads to a facile synthesis of difluoromethylthiolated molecules and their deuterated analogs.
Chameleon‐like reactivity: (Benzenesulfonyl)difluoromethanesulfenamide was developed as a new, shelf‐stable reagent for the introduction of the PhSO2CF2S group into organic molecules (see scheme). The versatility of the PhSO2 moiety also provides an entry into reductive deuterations.