Journal of Organic Chemistry 2010-05-21

Aminodifluorosulfinium salts: selective fluorination reagents with enhanced thermal stability and ease of handling.

Alexandre L'heureux, Francis Beaulieu, Christopher Bennett, David R Bill, Simon Clayton, François Laflamme, Mahmoud Mirmehrabi, Sam Tadayon, David Tovell, Michel Couturier

Index: J. Org. Chem. 75 , 3401, (2010)

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Abstract

Diethylaminodifluorosulfinium tetrafluoroborate (XtalFluor-E) and morpholinodifluorosulfinium tetrafluoroborate (XtalFluor-M) are crystalline fluorinating agents that are more easily handled and significantly more stable than Deoxo-Fluor, DAST, and their analogues. These reagents can be prepared in a safer and more cost-efficient manner by avoiding the laborious and hazardous distillation of dialkylaminosulfur trifluorides. Unlike DAST, Deoxo-Fluor, and Fluolead, XtalFluor reagents do not generate highly corrosive free-HF and therefore can be used in standard borosilicate vessels. When used in conjunction with promoters such as Et(3)N.3HF, Et(3)N.2HF, or DBU, XtalFluor reagents effectively convert alcohols to alkyl fluorides and carbonyls to gem-difluorides. These reagents are typically more selective than DAST and Deoxo-Fluor and exhibit superior performance by providing significantly less elimination side products.