Aminodifluorosulfinium salts: selective fluorination reagents with enhanced thermal stability and ease of handling.
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.
L'heureux
Alexandre
A
OmegaChem Inc., 480 Rue Perreault, St-Romuald (Qc) G6W 7V6, Canada.
Beaulieu
Francis
F
Bennett
Christopher
C
Bill
David R
DR
Clayton
Simon
S
Laflamme
François
F
Mirmehrabi
Mahmoud
M
Tadayon
Sam
S
Tovell
David
D
Couturier
Michel
M
D001881:Borates / Q000138:chemical synthesis / Q000737:chemistry*; D054879:Halogenation; D006845:Hydrocarbons, Fluorinated / Q000138:chemical synthesis / Q000737:chemistry*; D015394:Molecular Structure; D009025:Morpholines / Q000138:chemical synthesis / Q000737:chemistry*; D012492:Salts / Q000138:chemical synthesis / Q000737:chemistry; D013237:Stereoisomerism; D013457:Sulfur Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D013696:Temperature
D001881:Borates; D006845:Hydrocarbons, Fluorinated; D009025:Morpholines; D012492:Salts; D013457:Sulfur Compounds; C551695:diethylaminodifluorosulfinium tetrafluoroborate; C551696:morpholinodifluorosulfinium tetrafluoroborate
Org Lett. 2009 Nov 5;11(21):5050-3
19799406
Chem Commun (Camb). 2002 Aug 7;(15):1618-9
12170810
J Med Chem. 2008 Aug 14;51(15):4359-69
18570365
J Org Chem. 2001 Oct 5;66(20):6775-86
11578234
Bioorg Khim. 1996 Oct-Nov;22(10-11):814-22
9036841
Org Lett. 2004 Apr 29;6(9):1465-8
15101768
J Org Chem. 2000 Aug 11;65(16):4830-2
10956459
Chem Soc Rev. 2008 Feb;37(2):320-30
18197348
Science. 2007 Sep 28;317(5846):1881-6
17901324