Table 1.

Chronological list of the development of N-F fluorinating agents.

year	structure	“F” source	yield	references
1964		HF	7.5–13%	[16–22]
1981		XeF2	50–65%	[23]
1983		5% F2/N2	63%	[24–25]
1984	R1 = p-tolyl, n-butyl; R2 = methyl, tert-butyl, exo/endo-2-norbornyl, cyclohexyl, neopentyl	1–5% F2/N2	11–71%	[26–27]
1986– 1991	X = OTf, BF4, PF6, AsF6, SbF6, ONf, OMs, etc. R1, R2, R3, R4, R5 = H, Me, Cl, F, COOMe, OMe, CH2OMe, CH2OAc, CF3, CN, NO2, OMenth, etc.; (total 62 examples)	10% F2/N2	15–96%	[28–34,36–41]
1986		100% F2	86%	[43–44]
1987	Rf1,2 = CF3, C4F9, C6F13	100% F2	61–96%	[45–49]
1988		100% F2	80–88%	[50–51]
1988	R = H, CH3	10% F2/N2	75–80%	[52]
1989		10% F2/N2	74%	[53]
1990		100% F2	89%	[54]
1990		0.05% 18F2/Ne	33–79%	[55–56]
1991		10% F2/N2	>90%	[57–58]
1991		10% F2/N2	70%	[59]
1991	X = SO2, CO	Cs+-OSO2OF	48–69%	[60]
1992	X = OTf, BF4 R = CH3, CH2Cl, CH2CF3 SelectfluorTM (R = CH2Cl, X = BF4)	10% F2/N2	87–95%	[42,61–74]
1993		10% F2/N2	68%	[75]
1995	R3, R4, R5, R6 = H, CH3, CF3, Cl, C2H5, tert-butyl	10% F2/N2	65–95%	[76]
1995	NFTh/AccufluorTM	10% F2/N2	75%	[78–80]
1995		5% F2/N2	83%	[81]
1996		100% F2	75%	[82]
1996	X1, X2 = OTf, BF4, HSO4, SbF6, PF6, etc.	10% F2/N2	56–87%	[83]
1997	R = BF3, F, CH3	10% F2/N2	62–82%	[85]
1997	R1 = CH3, CH2OCOCH3 R2 = CH3, p-tolyl	FClO3	13–52%	[92]
1998	X = OTf, BF4, PF6, SbF6 bipyridyl = 2,2', 2,4', 3,3', 4,4'; R = H, CH3, Cl, CF3, Ph, COOCH3	10-20% F2/N2	64–97%	[86]
1998		5% F2/N2	–	[87–88]
1999	R = CH3, CF3	10% F2/N2	65–82%	[89]
1999		FClO3	71%	[90]
1999	(R)-(+) (S)-(–)	15% F2/He	51–65%	[91]
2000	(R), (S)	FClO3	66–83%	[93]
2000	(S,R,R), (S,S,R)	FClO3	44–81%	[94]
2000		SelectfluorTM	prepared in situ	[95–96]
2000	R = H, OCH3	SelectfluorTM	84%	[97–98]
2003	X = BF4, OTf, N(SO2Ph)2	Selectfluor (F-TEDA-BF4) F-TEDA-OTf NFTh NFSI N-F-diCl-pyridinium BF4	100%	[99]
2003		100% F2	95%	[100]
2011	NFBSI	10% F2/N2	57%	[102]
2012	R = F, Cl, Br, CF3, OCF3, t-Bu, Me, OCH3	10% F2/N2	20.9–89.4%	[103–105]
2013	R = 3,5-(CF3)2C6H3, C6F5	XeF2	29–51%	[106]
2013	R1 = H, CF3; R2 = H, CH3	10% F2/N2 or	>95%	[107]
2013	(R), R = H; (S), R = 3,5-(CF3)2C6H3	0.2% F2/N2	27–67%	[108]
2016	Me-NFSI	10% F2/N2	76%	[111]
2016			>95% conversion	[113]
2018		20% F2/N2	50%	[114]
2018	Ar1 = C6H5, 4-Cl-C6H4, 2,4,6-triMe-C6H2, etc.; Ar2 = 4-CF3-C6H4, 3-CF3-C6H4, 3,5-diCF3C6H3	NFSI	20–93%	[115]