Chemical_Reviews.pdfVIP

+ + Chem. Rev. 1996, 96, 1737?1755 1737 Electrophilic NF Fluorinating Agents G. Sankar Lal, Guido P. Pez,* and Robert G. Syvret Air Products and Chemicals, Inc., 7201 Hamilton Boulevard, Allentown, Pennsylvania 18195-1501 Received November 20, 1995 Revised Manuscript Received May 23, 1996 Contents such nucleophilic fluorinating agents that are useful for laboratory use or fine chemical synthesis pro- I. Introduction 1737 cesses are pyridine.HF, Bu N HF , activated alkali 4 2 II. General Preparative Methods 1738 metal fluorides, etc., and also SF4 and diethylamino - III. Survey of NF Reagents 1741 sulfur trifluoride DAST , which can convert carbon- A. Neutral Compounds R2 NF 1741 oxygen to carbonfluorine bonds.9,10 1. Sulfonyl Derivatives RSO N F R′ 1743 The fluorination of electron-rich centers, in par- 2 2. N-Fluoroamines and N-Fluoroamides 1743 ticular, a direct conversion of CH to CF linkages, + is usually not feasible with HF-based chemistry; for B. Quaternary R3N F A Compounds 1743 1. N-Fluoropyridinium Salts 1743 this radical or electrophilic sources of fluorine are 2. Saturated Derivatives 1744 needed. Elemental fluorine can be used for this C. Nitrogen Fluorides 1744 purpose, but there are significant remaining chal- lenges. At near-ambient temperatures, when acting D. Potential Electrophilic NF Compounds 1744 as a source of F radicals, it is quite indiscriminate IV. Applications in Organic Synthesis 1744 in its chemistry toward organic substrates. However, A. Synthesis of Fluoroaromatics 1744 under carefully regulated conditions fluorine can be B. Fluorination of Carbanions 1745 a useful synthetic reagent.11,12 An efficient perflu- 1. Synthesis of -Fluoro Carbonyl 1745 orination of hydrocarbons and some ethers can, for Compounds instance, be accomplished by the LaMar and aerosol- 2. Synthesis of -Fluoro Carbonyl 1747 controlled fl