Table 1.

Catalyst Discovery for the Intermolecular Olefin Aminofluorination

entrya	Fe(X)2	ligand	2	Et3N·3HF (equiv)	XtalFluor-E (equiv)	yield (3)b	yield (4)b
1	Fe(NTf2)2	L1	2a	1.5	1.5	16%	30%
2c	none	none	2a	1.5	1.5	NA	NA
3	Fe(NTf2)2	L1	2a	1.5	2.5	42%	17%
4	Fe(NTf2)2	L1	2b	1.5	2.5	45%	23%
5d	Fe(NTf2)2	L1	2b	1.5	3.0	23%	52%
6e	Fe(NTf2)2	L1	2b	none	1.5	NA	NA
7d	Fe(NTf2)2	L1	2c	1.5	2.5	46%	44%
8d	Fe(NTf2)2	L1	2d	1.5	2.5	73%	<5%
9d	Fe(NTf2)2	L1	2d	2.4	4.0	81%	<5%
10d	Fe(NTf2)2	L2	2d	2.4	4.0	78%	<5%
11f	6: Fe(L1)(BF4)2(MeCN)(H2O)2	none	2d	1.5	2.5	88%	<5%

^aReactions were carried out under N₂ at −15 °C in 2 h, and 4 Å activated molecular sieves (powder) were used to remove deleterious moisture, unless stated otherwise. The reaction was quenched with saturated NaHCO₃ solution.

^bIsolated yield.

^cNo reaction; 1 and 2a were recovered.

^dThe yield of 5 is 8–12%.

^eNo desired product observed, and 5 (42%) was isolated.

^fPreformed complex 6 was used as the catalyst in CH₂Cl₂ in the absence of MeCN; −15 °C, 2 h; the yield of 5 is less than 5%.