Table 11.

Reactions of thiols RC₆H₄SH and HetArSH with R_FI in organic solvents and in biphasic conditions without initiators.

R	SH, (SCat+)	RF	Base	Reaction conditions	Yields of ArSRF, %	Ref.
Thiophenols
H	SNa	C8F17	—	DMF, 25 °C, 17 h	90	[188]
H	SNa	C8F17	—	DMF, 25 °C, 17 h + norbornene	77	[188]
H	SNa	C8F17	—	DMF, 25 °C, 17 h + styrene	0	[188]
H	SNa	CF(CF3)2	—	DMF, 25 °C, 17 h	76	[188]
H	SNBu4	C6F13	—	CH2Cl2/H2O, 40 °C, 4 h	48	[188]
H	SNBu4	C6F13	—	C6H6/H2O, 25 °C, 2.5 h	76a	[188]
H		R(CF2)n		DMF, conditions are not presented	56–87	[205]
4-NH2	SH	C2F5	K2CO3	DMF, 10 °C	84	[206]
4-F	SNa	C10F21	—	DMF, 70 °C, 1 h	97	[204]
4-F	SNa	CF2)4I	—	DMF, 25 °C,12 h, 60 °C, 1 h	86b
4-Cl	SNa	(CF2)8I	—	DMF, 50 °C, 6 h
H	SH	C4F9	NaH	DMF, 20–25 °C, 17–18 h	66	[201]
4-CH3	SH	C4F9	NaH	DMF, 20–25 °C, 17–18 h	77	[201]
4-OH	SH	C4F9	NaH	DMF, 20–25 °C, 17–18 h	30	[201]
4-Cl	SH	C4F9	NaH	DMF, 20–25 °C, 17–18 h	83	[201]
4-NO2	SH	C4–C8	NaH	DMF, 20–25 °C, 17–18 h	93–99	[201]
F5	SCu	CF2=CF	—	DMAC, 70 °C, 20 h	65	[207]
F5	SCu	C8F17		DMAC, 70 °C, 20 h	0	[207]
H	SeNa	CF3Br		EtOH, 20 °C, 2 h, olefins	2–60	[160]
H	SeNa	C4F9I–C8F17I		EtOH, 20 °C, 2 h, olefins		[160]
Heterocyclic thiols
Heterocycle		RF	Base	Reaction conditions	Yields	Ref.
2-SH-benzothiazole		C3F7	NEt3	DMF, 55–60 °C, 3–48 h	Traces	[189]
		C3F7	NEt3	DMF, 20–22 °C, 120 h	59	[189]
		Cl(CF2)4–6	NaH	DMF, 70 °C, 10 h	0–4.5c	[169]
2-SH-benzimidazole		Cl(CF2)4–6	NaH	DMF, 70 °C, 10 h	0–3d	[169]
8-SNa-quinoline		C3F7	NEt3	DMF, 20–22 °C, 24 h	72	[189]

^aIn the presence of norbornene and styrene the yields are 30% and 0%, respectively.

^bα, ω-Bis(SAr)perfluoroalkanes.

^c8.5% conver. R_FI.

^d~3% conver. R_FI.