Visible light promoted iodofluoroalkylation of alkenes with iodo-3-oxaperfluoroalkanesulphonates

Article abstract of DOI:10.1016/j.jfluchem.2019.03.008

Iodo-3-oxa-perfluoroalkanesulfonyl fluorides (I(CF₂CF₂)_n+1OCF₂CF₂SO₂F, n = 0, 1, 2, 3) was functionalized by phenol to provide phenyl fluoroalkanesulfonate. The ATRA reaction of I(CF_2<

Full text of DOI:10.1016/j.jfluchem.2019.03.008

Accepted Manuscript
Title: Visible Light Promoted Iodofluoroalkylation of Alkenes
with Iodo-3-oxaperfluoroalkanesulphonates
Authors: Dongmei He, Yong Guo, Qing-Yun Chen, Hu Yang,
Tao Lv
PII:
S0022-1139(18)30522-0
DOI:
Reference:
https://doi.org/10.1016/j.jfluchem.2019.03.008
FLUOR 9302
To appear in:
FLUOR
Received date:
Revised date:
Accepted date:
1 January 2019
23 March 2019
25 March 2019
Please cite this article as: He D, Guo Y, Chen Q-Yun, Yang H, Lv T, Visible Light
PromotedIodofluoroalkylationofAlkeneswithIodo-3-oxaperfluoroalkanesulphonates,
Journal of Fluorine Chemistry (2019), https://doi.org/10.1016/j.jfluchem.2019.03.008
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Visible Light Promoted Iodofluoroalkylation of Alkenes with
Iodo-3-oxaperfluoroalkanesulphonates
a
b,*
b,*
a,*
c
Dongmei He , Yong Guo , Qing-Yun Chen , Hu Yang , Tao Lv
aCollege of Chemical Engineering, Sichuan University of Science & Engineering, 180
Xueyuan Road, Zigong 653000, P. R. of China.
bKey Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic
Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, P. R.
of China.
cSanming Hexafluo Chemicals Co., LTD., Fluorinated New Material Industry Park,
Mingxi, Fujian 365200, P. R. China
E-mail: yguo@sioc.ac.cn, chenqy@sioc.ac.cn, yanghu67@163.com
Graphical abstract
Highlight

Visible light promoted radical fluoroalkylation was researched.



The amount of ruthenim catalyst is 1 mol%.
The fluoroalkylating reagent was iodo-3-oxa-perfluoroalkanesulfonate.
Abstract
Iodo-3-oxa-perfluoroalkanesulfonyl fluorides (I(CF
, 2, 3) was functionalized by phenol to provide phenyl fluoroalkanesulfonate. The
ATRA reaction of I(CF CF CF SO Ph with alkenes was realized by visible
Cl
2
CF
2
)
n+1OCF
2
CF
2
SO F, n = 0,
2
1
2
2
)
n+1OCF
2
2
3
light phototcatalysis with Ru(ppy)
3
2
.
Keywords
ATRA; iodo-3-oxa-perfluoroalkanesulfonate; fluoroalkylation; visible light; alkene
Introduction
The increasing demand of new fluorinated compounds in agrochemicals,
pharmaceuticals, and materials attracted widespread attention in the methodology for
the introduction of fluorinated groups into organic molecules [1].
Iodo-3-oxa-perfluoroalkanesulfonyl fluorides (namely, I(CF
2
CF
2
)
n+1OCF
2
CF
2
SO F, 1,
2
n = 0, 1, 2, 3) are widely used fluoroalkylation reagents, which can incorporate
fluorous tags into organic compounds [2]. 1 bearing with both sulfonyl fluoride and
halo groups, it behaves as bi-functional fluoroalkylation reagents. Sulfonyl fluoride
2
group (-SO F) can be functionalized by K
2
SO [3a], NaOH [3b, 3c], and phenols [3d]
3
to provide fluoroalkanesulfite, fluoroalkanesulfonic acid salts, and
fluoroalkanesulfonic acid esters respectively. Perfluoroalkyl iodides (R
f
I) are very
different from their corresponding alkyl iodides (RI). 1 is reactive in a radical [4-8]
and single electron transfer [9-13] processes, and a fluoralkyl radical generated from 1
reacted with alkenes, alkynes and arenes to provide fluoroalkylated products. Visible

light promoted fluoroalkylation are widely researched [14-22] (Scheme 1).
Photosensitive transition metal complexes are usual photocatalysts, allowing atom
transfer radical addition (ATRA) of perfluoroalkyl halides to alkenes under the visible
light irradiation [23-26]. The visible light-promoted reaction has the advantages of
greenness, mildness, and high efficiency. Therefore, we researched the visible light
promoted fluoralkylation with iodo-3-oxa-perfluoroalkanesulfonates.
Previous work:
2
. Results and discussion
Inspired by the above literatures, we initially selected I(CF
2
CF
2
)
2
OCF
2
CF
2
SO F
2
(
1b) as the fluorine-containing starting material and reacted with hex-5-en-1-yl
benzoate (3a) under the irradiation of 23 W fluorescent lamp with Ru(bpy) Cl
photocatalyst, conducting a preliminary investigation. As a result, it was found that no
3
2
as a
1
9
signal of the target product was observed at all by F NMR monitoring. In contrast,
1
9
the F NMR signal of the -SO F of the starting material disappeared. Later, in order
2
to carry out the experiment as originally assumed, we transferred sulfonyl fluoride to
sulfonate by reacting with phenol (Scheme 2), and the obtained products (2a-d) was
subjected to ATRA with the alkenes.
The protocol was investigated with alkene 3a as a model substrate; it was reacted
with 1.5 – 6 equivalents of 2b (Table 1, entries 1 – 6) and 1 mol% of Ru(bpy)
3
Cl in
2
dimethyl sulfoxide (DMSO) under visible light irradiation with a 23 W fluorescent
lamp at room temperature under nitrogen atmosphere for 24 hours. When 6
equivalents of 2b were employed, the yield reached 91% (Table 1, entry 6; detected
1
9
by F NMR spectroscopy). Among the common solvents tested including DCM,
acetonitrile, DMF, NMP, DMPU, THF, and DMSO (Table 1, entry 6-12), all of them
promoted the reaction and DCM was the best, giving product 4b in 98% yield (Table
1
, entry 7). However, considering that the solvent contains chlorine, we chose DMSO
with the second highest yield (91%) as solvent (Table 1, entry 6). And we increased
the solvent from 1 mL to 3 mL of solvent and found that the 2 mL is the best. (Table 1,
entries 6, 13 and 14). A blue LED was applied, and gave the product in 74% yield
(Table 1, entry 15). By increasing the reaction time to 48 h and the best yield (99%) of

the product was obtained (Table 1, entries 16, 17). While continue to extend the
reaction time to 60 h, the yield instead declined (Table 1, entry 18). When we reduced
the amount of Ru(bpy)
9). Notably, 4b could not be obtained in the dark or in the absence of photocatalyst
Table 1, entries 20 and 21). To our delight, employing Eosin Y as a photocatalyst
3
Cl
2
to 0.5 mol%, the yield decreased to 76% (Table 1, entry
1
(
provided 4b in 56% yield (Table 1, entry 22).
With the optimized conditions identified (Table 1, entry 17), we began to explore
the substrate scope of alkenes and the results were summarized in Table 2. Inspiringly,
a wide array of alkenes were subjected to the protocol. And numerous functional
groups were tolerated, including esters (4a - o), halogens (4e, 4h - j), ethers (4p, 4r,
4
s), phthalimide (4q), heterocycles (4m, 4n), ketones (4s), nitro (4g), hydroxyl (4t).
In addition, terminal alkenes derived from relatively complex molecules
-methylumbelliferone (4o) and estrone (4s) were compatible with the reaction
4
conditions and yielded the desired products in moderate yields, which demonstrated
the potential of the reaction in late-stage functionalization. The products of 2 (n=1, 2,
3
) could gave the corresponding products (4b - d) in moderate yields. However, the
a (n=0) only give a 13% yield. Notably, styrenes and electron-poor alkenes are not
4
good candidates for this atom-transfer radical addition (ATRA), thus suggesting a
profound effect of electronic properties of the alkenes.
Table 2 Substrate scope
To gain more insights into the reaction mechanism, inhibition experiments were
conducted on 3a (Scheme 3). The yield of the target product (4b) was reduced from
9
1% to 24% when the reaction was conducted under the optimized conditions in the
presence of 1,4-dinitrobenzene. This demonstrated that the reaction may proceed
through a single electron transfer process. However, there is no effect when using
hydroquinone.
3
. Conclusion
In summary, we developed a fluoroalkylation reaction of alkenes with
iodo-3-oxa-perfluoroalkanesulfonates under visible light irradiation. The reaction was

catalyzed by 1 mol% Ru(ppy)
3
Cl and ATRA products were obtained. Various alkenes
2
undergo the reaction to afford the corresponding products in moderate to good yields.
4
4
. Experimental section
.1. General information
NMR spectra were obtained on a 400 MHz spectrometer using CDCl as
3
deuterated solvents, with proton, carbon and fluorine resonances at 400 MHz, 100
1
13
MHz and 376 MHz, respectively. H NMR and C NMR chemical shifts were
1
9
determined relative to internal standard TMS at δ 0.0 ppm and F NMR chemical
shifts were determined relatived to CFCl as inter standard. Carbons in the
3
perfluorinated carbon chains are not reported due to their multiple couplings with
fluorine atoms. Chemical shifts (δ) are reported in ppm, and coupling constants (J) are
in hertz (Hz). The following abbreviations were used to explain the multiplicities: s =
singlet, d = doublet, t = triplet, q = quartet, m = multiplet, br = broad. The NMR yield
1
9
19
was determined by F NMR using benzotrifluoride ( F NMR: δ -63.0 ppm) as an
internal standard before working up the reaction. GC-MS (EI) data were determined
on an Agilent 5975C. HRMS (ESI) data were tested on a Water Micromass GCT
Premier. Unless otherwise noted, solvents were freshly dried and degassed according
to the purification handbook Purification of Laboratory Chemicals before using. Flash
column chromatography was carried out using 300 - 400 mesh silica gel.
4
.2. Preparation of I(CF
Synthesis of phenyl
,1,2,2-tetrafluoro-2-(1,1,2,2,3,3,4,4-octafluoro-4-iodobutoxy)ethane-1-sulfonate
2a)
To a 100 mL flask containing a magnetic stirring bar were added triethylamine (40
mL), I(CF OCF CF SO F (1a, 20 mmol, 8.52 g) and phenol (30 mmol, 2.82 g). The
2
CF
2
)
n+1OCF
2
CF
2
SO
3
Ph
1
(
2
)
2
2
2
2
mixture was stirred vigorously at room temperature for 4 hours. After removal of the
solvent under reduced pressure with a rotary evaporator, water (20 mL) was added.
The aqueous phase was extracted with DCM (20 × 3 mL). The organic layers were
combined, washed with H
2
O (50 mL × 2) and brine (50 mL), dried over Na
2
SO
4
,
filtered, and concentrated in vacuo. The resulting residue was purified by silica gel

column chromatography (EA/PE = 1:50 v/v) to give a colorless liquid (8.54 g, 85%
yield).
phenyl
1
,1,2,2-tetrafluoro-2-(1,1,2,2,3,3,4,4-octafluoro-4-iodobutoxy)ethane-1-sulfonate
(2a) [3d]: Obtained as colorless liquid in 85% yield by silica gel flash column
1
chromatography eluted with EA/PE = 1:50 v/v. H NMR (400 MHz, CDCl
3
) δ 7.45 (t,
1
9
J = 8.0 Hz, 2H), 7.38 (t, J = 8.0 Hz, 1H), 7.29 (d, J = 8.0 Hz, 2H). F NMR (376
MHz, CDCl
3
) δ -65.1 (t, J = 5.8 Hz, 2F), -81.8 – -82.0 (m, 2F), -85.4 – -85.5 (m, 2F),
+
-
113.0 (s, 2F). HRMS (ESI): calcd. for [C10
22.8717.
H
5
F
8
IO
4
S + Na ] 522.8718, found
5
The following substrates were prepared according to the procedure described for 2a.
phenyl
2
-((1,1,2,2,3,3,4,4,5,5,6,6-dodecafluoro-6-iodohexyl)oxy)-1,1,2,2-tetrafluoroethane
-
1-sulfonate (2b) [3d]: Obtained as colorless liquid in 85% yield by silica gel flash
1
column chromatography eluted with EA/PE = 1:50 v/v. H NMR (400 MHz, CDCl
3
)
1
9
δ 7.45 (t, J = 7.7 Hz, 2H), 7.38 (t, J = 7.3 Hz, 1H), 7.28 (d, J = 8.0 Hz, 2H). F NMR
376 MHz, CDCl ) δ -59.5 (t, J = 14.0 Hz, 2F), -81.5 – -81.6 (m, 2F), -83.1 – -83.2 (m,
F), -113.1 (s, 2F), -113.4 – -113.5 (m, 2F), -124.4 – -124.5 (m, 2F). HRMS (ESI):
(
3
2
calcd. for [C12
H
5
F12IO
4
S + NH
+] 617.9100, found 617.9091.
4
phenyl
2
-((1,1,2,2,3,3,4,4,5,5,6,6-dodecafluoro-6-iodohexyl)oxy)-1,1,2,2-tetrafluoroethane
-
1-sulfonate (2c) [3d]: Obtained as colorless liquid in 85% yield by silica gel flash
1
column chromatography eluted with EA/PE = 1:50 v/v. H NMR (400 MHz, CDCl
3
)
1
9
δ 7.45 (t, J = 7.7 Hz, 2H), 7.38 (t, J = 7.3 Hz, 1H), 7.27 (d, J = 8.0 Hz, 2H). F NMR
376 MHz, CDCl ) δ -59.2 – -59.4 (m, 2F), -81.5 – -81.6 (m, 2F), -82.8 – -83.0 (m,
F), -113.1 – -113.3 (m, 4F), -121.0 – -121.3 (m, J = 11.3 Hz, 2F), -122.1 (s, 2F),
(
3
2
+
-
125.3 (m, 2F). HRMS (ESI): calcd. for [C14
22.8589.
phenyl
,1,2,2-tetrafluoro-2-((1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-hexadecafluoro-8-iodooctyl)ox
H
5
F
16IO
4
S + Na ] 722.8590, found
7
1

y)ethane-1-sulfonate (2d) [3d]: Obtained as colorless liquid in 85% yield by silica
1
gel flash column chromatography eluted with EA/PE = 1:50 v/v. H NMR (400 MHz,
CDCl
3
) δ 7.45 (t, J = 7.7 Hz, 2H), 7.38 (t, J = 7.3 Hz, 1H), 7.27 (d, J = 8.0 Hz, 2H).
19F NMR (376 MHz, CDCl
) δ -59.2 – -59.4 (m, 2F), -81.6 – -81.7 (m, 2F), -82.8 –
3
-
83.0 (m, 2F), -113.1 – -113.4 (m, 4F), -121.1 (s, 2F), -121.7 – -122.4 (m, 6F), -125.4
+
(
s, 2F). HRMS (ESI): calcd. for [C16
H
5
F
20IO S + Na ] 822.8526, found 822.8523.
4
4
.3. Preparation of various alkenes starting material
Synthesis of hex-5-en-1-yl benzoate (3a)
To a flame-dried 250 mL two-neck flask containing a magnetic stirring bar were
added 4-dimethylaminopyridine (DMAP, 488 mg, 4 mmol),
N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride (EDCI, 7.67 g, 40
mmol), benzoic acid (2.74 g, 24 mmol) and 5-hexen-1-ol (2.00 g, 20 mmol) in 100
mL CH
2
Cl
2
under N atmosphere at 0 ℃. The reaction mixture was stirred at room
2
temperature for 24 h. After that, the organic phase was filtered through a pad of celite
and concentrated. The resulting residue was purified by silica gel column
chromatography (EA/PE = 1:20 v/v) to give a colorless liquid. (4.08 g, yield 87%)
hex-5-en-1-yl benzoate (3a) [27]: Obtained as colorless liquid in 87% yield by silica
1
gel flash column chromatography eluted with EA/PE = 1:20 v/v. H NMR (400 MHz,
CDCl
3
) δ 8.07 – 8.02 (m, 2H), 7.59 – 7.52 (m, 1H), 7.44 (dd, J = 10.6, 4.7 Hz, 2H),
5
2
.82 (ddt, J = 16.9, 10.2, 6.7 Hz, 1H), 5.08 – 4.95 (m, 2H), 4.33 (t, J = 6.6 Hz, 2H),
1
3
.18 – 2.10 (m, 2H), 1.83 – 1.75 (m, 2H), 1.61 – 1.51 (m, 2H). C NMR (100 MHz,
CDCl
3
) δ 166.5, 138.3, 132.8, 130.4, 129.5, 128.3, 114.8, 64.8, 33.3, 28.1, 25.3.
GC-MS (EI): m/z = 204.0 (M+).
The following substrates were prepared according to the procedure described for 3a.
1
hex-5-en-1-yl 2-fluorobenzoate (3e) [27]: H NMR (400 MHz, CDCl
3
) δ 7.93 (td, J
=
7.6, 1.8 Hz, 1H), 7.55 – 7.47 (m, 1H), 7.23 – 7.09 (m, 2H), 5.82 (ddt, J = 16.9, 10.2,
6
1
.7 Hz, 1H), 5.07 – 4.95 (m, 2H), 4.34 (t, J = 6.6 Hz, 2H), 2.17 – 2.09 (m, 2H), 1.83 –
1
9
.73 (m, 2H), 1.60 – 1.51 (m, 2H). F NMR (376 MHz, CDCl
3
) δ -109.50 – -109.61
) δ 164.5 (d, J = 3.6 Hz), 161.9 (d, J = 259.0 Hz),
38.3, 134.3 (d, J = 8.9 Hz), 132.0, 123.8 (d, J = 3.9 Hz), 119.0 (d, J = 9.9 Hz), 116.9
1
3
(
m, 1F). C NMR (100 MHz, CDCl
3
1

(d, J = 22.0 Hz), 114.8, 65.2, 33.2, 28.0, 25.2.
1
hex-5-en-1-yl 3-methylbenzoate (3f) [27]: H NMR (400 MHz, CDCl
3
) δ 7.84 (s,
1
1
1
1
H), 7.83 (d, J = 8.0 Hz, 1H), 7.36 – 7.27 (m, 2H), 5.81 (ddt, J = 16.9, 10.2, 6.7 Hz,
H), 5.07 – 4.93 (m, 2H), 4.30 (t, J = 6.6 Hz, 2H), 2.38 (s, 3H), 2.15 – 2.08 (m, 2H),
1
3
.81 – 1.72 (m, 2H), 1.58 – 1.49 (m, 2H). C NMR (100 MHz, CDCl ) δ 166.8,
3
38.3, 138.0, 133.5, 130.3, 130.0, 128.2, 126.6, 114.8, 64.7, 33.3, 28.1, 25.3, 21.2.
1
hex-5-en-1-yl 3-nitrobenzoate (3g) [27]: H NMR (400 MHz, CDCl
3
) δ 8.88 – 8.81
(m, 1H), 8.45 – 8.35 (m, 2H), 7.68 (t, J = 8.0 Hz, 1H), 5.83 (ddt, J = 16.9, 10.2, 6.7
Hz, 1H), 5.09 – 4.96 (m, 2H), 4.40 (t, J = 6.7 Hz, 2H), 2.19 – 2.11 (m, 2H), 1.88 –
1
3
1
1
.79 (m, 2H), 1.62 – 1.53 (m, 2H). C NMR (100 MHz, CDCl ) δ 164.4, 148.2,
3
38.0, 135.1, 132.1, 129.5, 127.2, 124.4, 114.9, 65.7, 33.1, 27.9, 25.1.
1
hex-5-en-1-yl 4-fluorobenzoate (3h) [27]: H NMR (400 MHz, CDCl
3
) δ 8.09 – 8.02
(m, 2H), 7.15 – 7.07 (m, 2H), 5.82 (ddt, J = 16.9, 10.2, 6.7 Hz, 1H), 5.07 – 4.96 (m,
2
2
H), 4.32 (t, J = 6.6 Hz, 2H), 2.17 – 2.10 (m, 2H), 1.83 – 1.71 (m, 2H), 1.60 – 1.50 (m,
1
9
13
H). F NMR (376 MHz, CDCl
) δ 165.7 (d, J = 252.0 Hz), 165.6, 138.2, 132.0 (d, J = 10.0 Hz), 126.7 (d, J =
.0 Hz), 115.4 (d, J = 22.0 Hz), 114.9, 65.0, 33.3, 28.1, 25.2.
3
) δ -105.70 – -106.25 (m, 1F). C NMR (100 MHz,
CDCl
3
3
1
hex-5-en-1-yl 4-iodobenzoate (3i) [27]: H NMR (400 MHz, CDCl
3
) δ 7.82 – 7.70
(
m, 4H), 5.81 (ddt, J = 16.9, 10.2, 6.7 Hz, 1H), 5.06 – 4.95 (m, 2H), 4.31 (t, J = 6.6
1
3
Hz, 2H), 2.16 – 2.10 (m, 2H), 1.82 – 1.72 (m, 2H), 1.58 – 1.49 (m, 2H). C NMR
(100 MHz, CDCl
3
) δ 166.0, 138.1, 137.6, 130.9, 129.8, 114.9, 100.5, 65.1, 33.2, 28.0,
2
5.2.
1
but-3-en-1-yl 4-chlorobenzoate (3j) [27]: H NMR (400 MHz, CDCl
3
) δ 7.99 – 7.93
(m, 2H), 7.42 – 7.37 (m, 2H), 5.86 (ddt, J = 17.0, 10.2, 6.7 Hz, 1H), 5.21 – 5.08 (m,
1
3
2
1
H), 4.37 (t, J = 6.7 Hz, 2H), 2.55 – 2.48 (m, 2H). C NMR (100 MHz, CDCl ) δ
3
65.5, 139.2, 133.8, 130.9, 128.7, 128.6, 117.3, 64.1, 33.0.
1
but-3-en-1-yl 4-(tert-butyl)benzoate (3k) [27]: H NMR (400 MHz, CDCl
3
) δ 7.97
(d, J = 8.3 Hz, 2H), 7.47 – 7.42 (m, 2H), 5.87 (ddt, J = 17.0, 10.2, 6.7 Hz, 1H), 5.20 –
1
3
5
.07 (m, 2H), 4.36 (t, J = 6.7 Hz, 2H), 2.55 – 2.47 (m, 2H), 1.33 (s, 9H). C NMR
(100 MHz, CDCl
3
) δ 166.4, 156.3, 134.0, 129.3, 127.5, 125.2, 117.1, 63.6, 34.9, 33.1,

3
1.0.
pent-4-en-1-yl 4-methoxybenzoate (3l) [27]: H NMR (400 MHz, CDCl
.95 (m, 2H), 6.91 – 6.86 (m, 2H), 5.82 (ddt, J = 16.9, 10.2, 6.6 Hz, 1H), 5.08 – 4.95
m, 2H), 4.27 (t, J = 6.6 Hz, 2H), 3.81 (s, 3H), 2.22 – 2.15 (m, 2H), 1.87 – 1.79 (m,
1
3
) δ 7.99 –
7
(
1
3
2
6
H). C NMR (100 MHz, CDCl
3
) δ 166.2, 163.2, 137.4, 131.4, 122.7, 115.2, 113.5,
3.9, 55.3, 30.1, 27.9.
1
hex-5-en-1-yl thiophene-2-carboxylate (3m) [27]: H NMR (400 MHz, CDCl
3
) δ
7
5
1
1
.80 – 7.76 (m, 1H), 7.55 – 7.50 (m, 1H), 7.10 – 7.05 (m, 1H), 5.86 – 5.74 (m, 1H),
.06 – 4.94 (m, 2H), 4.31 – 4.25 (m, 2H), 2.15 – 2.06 (m, 2H), 1.79 – 1.70 (m, 2H),
1
3
.57 – 1.47 (m, 2H). C NMR (100 MHz, CDCl ) δ 162.1, 138.2, 133.9, 133.1, 132.1,
3
27.6, 114.8, 64.9, 33.1, 28.0, 25.1.
hex-5-en-1-yl 1-methyl-1H-pyrrole-2-carboxylate (3n) [27]: Obtained as colorless
liquid in 85% yield by silica gel flash column chromatography eluted with EA/PE =
1
1
6
6
2
6
4
:20 v/v. H NMR (400 MHz, CDCl
3
) δ 6.94 (dd, J = 3.7, 1.6 Hz, 1H), 6.77 (s, 1H),
.10 (m, 1H), 5.81 (ddt, J = 16.9, 10.2, 6.7 Hz, 1H), 5.07 – 4.93 (m, 2H), 4.22 (t, J =
.6 Hz, 2H), 3.92 (s, 3H), 2.15 – 2.07 (m, 2H), 1.78 – 1.66 (m, 2H), 1.57 – 1.47 (m,
1
3
H). C NMR (100 MHz, CDCl ) δ 161.3, 138.3, 129.3, 122.6, 117.6, 114.7, 107.7,
3
3.6, 36.7, 33.3, 28.2, 25.3. GC-MS (EI): m/z = 207.1 (M+).
-methyl-2-oxo-2H-chromen-7-yl pent-4-enoate (3o) [27]: Obtained as colorless
liquid in 89% yield by silica gel flash column chromatography eluted with EA/PE =
1
1
1
:3 v/v. H NMR (400 MHz, CDCl
3
) δ 7.60 (d, J = 8.6 Hz, 1H), 7.10 (d, J = 2.0 Hz,
H), 7.08 – 7.03 (dd, J = 8.8, 2.0 Hz, 1H), 6.26 (s, 1H), 5.90 (ddt, J = 16.8, 10.3, 6.5
Hz, 1H), 5.20 – 5.07 (m, 2H), 2.71 (t, J = 7.3 Hz, 2H), 2.56 – 2.48 (m, 2H), 2.43 (s,
1
3
3
H). C NMR (100 MHz, CDCl
3
) δ 170.9, 160.5, 154.2, 153.1, 151.9, 136.0, 125.3,
1
18.1, 117.8, 116.2, 114.5, 110.4, 33.6, 28.7, 18.7. GC-MS (EI): m/z = 258.1 (M+).
1
2
-(pent-4-en-1-yl)-1H-indene-1,3(2H)-dione (3q) [27]: H NMR (400 MHz, CDCl
δ 7.87 – 7.81 (m, 2H), 7.74 – 7.68 (m, 2H), 5.82 (ddt, J = 16.9, 10.2, 6.6 Hz, 1H),
.09 – 4.96 (m, 2H), 3.70 (t, J = 8.0 Hz, 2H), 2.16 – 2.09 (m, 2H), 1.84 – 1.74 (m, 2H).
13C NMR (100 MHz, CDCl
) δ 168.3, 137.2, 133.8, 132.1, 123.1, 115.2, 37.5, 30.9,
7.6.
3
)
5
3
2

(8S,9R,13R,14R)-3-(hex-5-en-1-yloxy)-13-methyl-6,7,8,9,11,12,13,14,15,16-decahy
1
dro-17H-cyclopenta[a]phenanthren-17-one (3s) [27]: H NMR (400 MHz, CDCl
3
)
δ 7.19 (d, J = 8.6 Hz, 1H), 6.71 (dd, J = 8.6, 2.7 Hz, 1H), 6.64 (d, J = 2.6 Hz, 1H),
5
2
2
.83 (ddt, J = 16.9, 10.2, 6.7 Hz, 1H), 5.08 – 4.93 (m, 2H), 3.94 (t, J = 6.5 Hz, 2H),
.92 – 2.86 (m, 2H), 2.55 – 2.46 (m, 1H), 2.43 – 2.36 (m, 1H), 2.29 – 2.21 (m, 1H),
1
3
.18 – 1.93 (m, 6H), 1.83 – 1.74 (m, 2H), 1.65 – 1.40 (m, 8H), 0.91 (s, 3H). C NMR
(100 MHz, CDCl
3
) δ 220.9, 157.1, 138.6, 137.7, 131.8, 126.3, 114.7, 114.5, 112.1,
6
4
7.6, 50.4, 48.0, 44.0, 38.4, 35.8, 33.4, 31.6, 29.6, 28.7, 26.5 25.9, 25.3, 21.6, 13.8.
.4. General procedures for the reactions of fluorinated alkyl iodides with
various alkenes
To an oven-dried Schlenk tube equipped with a magnetic stir bar were added in turn
Ru(bpy)
I(CF CF
atmosphere. The mixture was stirred at room temperature and irradiated by a 23W
3
Cl
2
·6H
2
O (1 mol%, 1.5 mg), alkene substrate (0.2 mmol),
2
2
)
n+1OCF
2
CF
2
SO Ar (1.2 mmol) and freshly-distilled DMSO (2.0 mL) under
3
N
2
compact fluorescent lamp for 48 h. Benzotrifluoride (0.2 mmol, 24 uL) was then
added into the reaction mixture as an internal standard, and the yield of the desired
1
9
product was measured by F NMR before working up. Water (15 mL) was added and
the resulting mixture was extracted with DCM (20 mL × 3). The organic layers were
combined, washed with H
2
O (50 mL × 2) and brine (50 mL), dried over Na
2
SO ,
4
filtered, and concentrated in vacuo. The crude product was purified by silica gel
column chromatography to give the desired product.
7
,7,8,8-tetrafluoro-5-iodo-8-(1,1,2,2-tetrafluoro-2-(phenoxysulfonyl)ethoxy)octyl
benzoate (4a): Obtained as yellow liquid in yield 13% by silica gel flash column
1
chromatography eluted with EA/PE = 1:15 v/v. H NMR (400 MHz, CDCl
3
) δ 8.05 (d,
J = 7.9 Hz, 2H), 7.56 (t, J = 7.4 Hz, 1H), 7.49 – 7.40 (m, 4H), 7.41 – 7.35 (m, 1H),
7
1
.30 – 7.24 (m, 2H), 4.37 – 4.30 (m, 3H), 2.96 – 2.69 (m, 2H), 1.92 – 1.67 (m, 5H),
1
9
.64 – 1.56 (m, 1H). F NMR (376 MHz, CDCl ) δ -81.9 – -82.1 (m, 2F), -87.7 –
3
-
89.1 (ABm, J = 142 Hz, 2F), -113.2 (s, 2F), -118.4 – -118.9 (AB, J = 260 Hz, 2F).

13C NMR (100 MHz, CDCl
) δ 166.6, 149.8, 132.9, 130.3, 130.2, 129.5, 128.4, 128.3,
3
1
1
21.4, 64.5, 41.2 (tm, J = 21.0 Hz), 39.8, 27.7, 26.2, 20.0. IR (film) vmax: 2954, 1720,
-1
602, 1585, 1488, 1422, 1276, 881, 773, 713 cm . HRMS (ESI): calcd. for
+
[C
23
H
21
F
8
IO
6
S + Na ] 726.9868, found 726.9865.
7
,7,8,8,9,9,10,10-octafluoro-5-iodo-10-(1,1,2,2-tetrafluoro-2-(phenoxysulfonyl)eth
oxy)decyl benzoate (4b): Obtained as yellow liquid in yield 71% by silica gel flash
1
column chromatography eluted with EA/PE = 1:15 v/v. H NMR (400 MHz, CDCl
3
):
δ 8.05 (dd, J = 8.2, 1.0 Hz, 2H), 7.56 (tt, J = 16.0, 7.4 Hz, 1H), 7.51 – 7.35 (m, 5H),
7
1
.31 – 7.25 (m, 2H), 4.38 – 4.29 (m, 3H), 3.01 – 2.69 (m, 2H), 1.97 – 1.68 (m, 5H),
1
9
.65 – 1.57 (m, 1H). F NMR (376 MHz, CDCl ) δ -81.5 – -81.6 (m, 2F), -83.0 –
3
-
83.2 (m, 2F), -111.4 – -115.2 (AB, J = 263 Hz, 2F), -113.0 (s, 2F), -123.9 (s, 2F),
1
3
-
124.9 – -125.1 (m, 2F). C NMR (100 MHz, CDCl
3
) δ 166.6, 149.8, 132.9, 130.3,
1
30.2, 129.6, 128.4, 128.3, 121.4, 64.4, 41.5 (tm, J = 21.0 Hz), 39.7, 27.7, 26.3, 20.2.
-1
IR (film) vmax: 3382, 2974, 1718, 1603, 1488, 1425, 1208, 1050, 881, 713 cm .
+
HRMS (ESI): calcd. for [C25
H
21
F12IO
6
S + H ] 804.9985, found 804.9993.
7
,7,8,8,9,9,10,10,11,11,12,12-dodecafluoro-5-iodo-12-(1,1,2,2-tetrafluoro-2-(pheno
xysulfonyl)ethoxy)dodecyl benzoate (4c): Obtained as yellow liquid in yield 69% by
1
silica gel flash column chromatography eluted with EA/PE = 1:15 v/v. H NMR (400
MHz, CDCl
3
) δ 8.05 (d, J = 7.3 Hz, 2H), 7.55 (t, J = 7.4 Hz, 1H), 7.44 (dt, J = 7.8, 1.9
Hz, 4H), 7.37 (t, J = 7.3 Hz, 1H), 7.30 – 7.24 (m, 2H), 4.39 – 4.29 (m, 3H), 3.01 –
1
9
2
.69 (m, 2H), 3.02 – 1.69 (m, 5H), 1.66 – 1.53 (m, 1H). F NMR (376 MHz, CDCl
3
)
δ -81.5 – -81.6 (m, 2F), -83.0 – -83.2 (m, 2F), -111.4 – -115.2 (AB, J = 263 Hz, 2F),
-
113.0 (s, 2F), -121.8 (s, 2F), -122.2 (s, 2F), -123.7 (s, 2F), -125.2 – -125.4 (m, 2F).
13C NMR (100 MHz, CDCl
) δ 166.6, 149.8, 132.9, 130.3, 130.2, 129.5, 128.4, 128.3,
3
1
1
21.3, 64.4, 41.6 (tm, J = 21.0 Hz), 39.8, 27.7, 26.3, 20.2. IR (film) vmax: 2956, 1712,
-1
488, 1421, 1358, 1262, 1208, 1145, 882, 734 cm . HRMS (ESI): calcd. for
+
[C
27
H
21
F16IO
6
S + Na ] 926.9740, found 926.9743.
7
,7,8,8,9,9,10,10,11,11,12,12,13,13,14,14-hexadecafluoro-5-iodo-14-(1,1,2,2-tetrafl
uoro-2-(phenoxysulfonyl)ethoxy)tetradecyl benzoate (4d): Obtained as yellow
liquid in yield 66% by silica gel flash column chromatography eluted with EA/PE =

1
1
7
3
:20 v/v. H NMR (400 MHz, CDCl
3
) δ 8.09 – 8.01 (m, 2H), 7.56 (t, J = 7.4 Hz, 1H),
.49 – 7.41 (m, 4H), 7.38 (t, J = 7.3 Hz, 1H), 7.31 – 7.24 (m, 2H), 4.35 (t, J = 5.8 Hz,
1
9
H), 3.02 – 2.70 (m, 2H), 1.97 – 1.70 (m, 5H), 1.66 – 1.54 (m, 1H). F NMR (376
MHz, CDCl
63 Hz, 2F), -113.0 (s, 2F), -121.9 (m, 8F), -123.7 (s, 2F), -125.3 (s, 2F). C NMR
100 MHz, CDCl ) δ 166.6, 149.8, 132.9, 130.3, 130.2, 129.5, 128.4, 128.3, 121.3,
4.4, 41.7 (tm, J = 21.0 Hz), 39.8, 27.7, 26.3, 20.1. IR (film) vmax: 1953, 1720, 1488,
3
) δ -81.5 – -81.6 (m, 2F), -83.0 – -83.2 (m, 2F), -111.4 – -115.2 (AB, J =
1
3
2
(
3
6
1
-1
427, 1276, 1220, 1150, 882, 713 cm . HRMS (ESI): calcd. for [C29
H
21
F
20IO S +
6
+
Na ] 1026.9676, found 1026.9681.
7
,7,8,8,9,9,10,10-octafluoro-5-iodo-10-(1,1,2,2-tetrafluoro-2-(phenoxysulfonyl)eth
oxy)decyl 2-fluorobenzoate (4e): Obtained as yellow liquid in yield 64% by silica
1
gel flash column chromatography eluted with EA/PE = 1:15 v/v. H NMR (400 MHz,
CDCl
3
) δ 7.94 (td, J = 7.6, 1.7 Hz, 1H), 7.54 – 7.48 (m, 1H), 7.47 – 7.41 (m, 2H),
.41 – 7.35 (m, 1H), 7.31 – 7.25 (m, 2H), 7.23 – 7.17 (m, 1H), 7.16 – 7.09 (m, 1H),
.38 – 4.29 (m, 3H), 3.00 – 2.69 (m, 2H), 1.95 – 1.68 (m, 5H), 1.65 – 1.53 (m, 1H).
) δ -81.5 – -81.6 (m, 2F), -83.0 – -83.2 (m, 2F), -109.4 –
109.5 (m, 1F), -111.4 – -115.2 (AB, J = 263 Hz, 2F), -113.0 (s, 2F), -123.9 (s, 2F),
7
4
19F NMR (376 MHz, CDCl
3
-
-
(
1
3
124.9 – -125.1 (m, 2F). C NMR (100 MHz, CDCl
3
) δ 164.5 (d, J = 3.6 Hz), 161.9
d, J = 260 Hz), 149.8, 134.4 (d, J = 9.0 Hz), 132.1, 130.2, 128.3, 123.9 (d, J = 3.9
Hz), 121.4, 118.8 (d, J = 9.8 Hz)116.9 (d, J = 22.0 Hz), 64.8, 41.5 (tm, J = 21.0 Hz),
3
8
8
7
9.7, 27.6, 26.2, 20.1. IR (film) vmax: 2955, 1728, 1614, 1488, 1425, 1300, 1208, 1143,
-1
+
82, 759 cm . HRMS (ESI): calcd. for [C25
H
20
F
13IO S + Na ] 844.9710, found
6
44.9714.
,7,8,8,9,9,10,10-octafluoro-5-iodo-10-(1,1,2,2-tetrafluoro-2-(phenoxysulfonyl)eth
oxy)decyl 3-methylbenzoate (4f): Obtained as yellow liquid in yield 59% by silica
1
gel flash column chromatography eluted with EA/PE = 1:15 v/v. H NMR (400 MHz,
CDCl
3
) δ 7.85 (d, J = 11.1 Hz, 2H), 7.49 – 7.41 (m, 2H), 7.41 – 7.25 (m, 5H), 4.38 –
4
1
.29 (m, 3H), 3.02 – 2.69 (m, 2H), 2.40 (s, 3H), 1.94 – 1.70 (m, 5H), 1.65 – 1.52 (m,
1
9
H). F NMR (376 MHz, CDCl ) δ -81.5 – -81.6 (m, 2F), -83.0 – -83.2 (m, 2F),
3
-
111.4 – -115.2 (AB, J = 263 Hz, 2F), -113.0 (s, 2F), -123.9 (s, 2F), -124.9 – -125.1

1
3
(
m, 2F). C NMR (100 MHz, CDCl
3
) δ 166.8, 149.8, 138.2, 133.7, 130.3, 130.2,
1
2
30.1, 128.3, 128.2, 126.7, 121.4, 64.4, 41.5 (tm, J = 21.0 Hz), 39.8, 27.7, 26.3, 21.2,
-1
0.3. IR (film) vmax: 2953, 1720, 1587, 1488, 1424, 1208, 1143, 1009, 881, 754 cm .
+
HRMS (ESI): calcd. for [C26
H
23
F12IO
6
S + H ] 819.0141, found 819.0152.
7
,7,8,8,9,9,10,10-octafluoro-5-iodo-10-(1,1,2,2-tetrafluoro-2-(phenoxysulfonyl)eth
oxy)decyl 3-nitrobenzoate (4g): Obtained as yellow liquid in yield 47% by silica gel
1
flash column chromatography eluted with EA/PE = 1:30 v/v. H NMR (400 MHz,
CDCl
3
) δ 8.87 (s, 1H), 8.36 – 8.44 (m, 2H), 7.66 (t, J = 8.0 Hz, 1H), 7.46 (t, J = 7.6
Hz, 2H), 7.39 (t, J = 7.2 Hz, 1H), 7.28 (d, J = 8.2 Hz, 2H), 4.44 – 4.30 (m, 3H), 3.02 –
1
9
2
.70 (m, 2H), 1.97 – 1.70 (m, 5H), 1.69 – 1.54 (m, 1H). F NMR (376 MHz, CDCl
3
)
δ -81.5 – -81.6 (m, 2F), -83.0 – -83.2 (m, 2F), -111.4 – -115.2 (AB, J = 263 Hz, 2F),
1
3
-
113.0 (s, 2F), -123.8 (s, 2F), -124.9 – -125.1 (m, 2F). C NMR (100 MHz, CDCl
3
) δ
1
64.6, 149.9, 148.4, 135.4, 132.2, 130.4, 129.8, 128.5, 127.5, 124.7, 121.5, 65.5, 41.5
(
tm, J = 21.0 Hz), 39.7, 27.7, 26.4, 20.3. IR (film) vmax: 2953, 1728, 1618, 1585, 1537,
-1
1
488, 1425, 1352, 1143, 882, 720 cm . HRMS (ESI): calcd. for [C25
H
20
F
12INO S +
8
+
Na ] 871.9655, found 871.9654.
7
,7,8,8,9,9,10,10-octafluoro-5-iodo-10-(1,1,2,2-tetrafluoro-2-(phenoxysulfonyl)eth
oxy)decyl 4-fluorobenzoate (4h): Obtained as yellow liquid in yield 70% by silica
1
gel flash column chromatography eluted with EA/PE = 1:20 v/v. H NMR (400 MHz,
CDCl
3
) δ 8.11 – 8.02 (m, 2H), 7.45 (t, J = 7.7 Hz, 2H), 7.39 (t, J = 7.3 Hz, 1H), 7.28
(
d, J = 8.0 Hz, 2H), 7.11 (t, J = 8.6 Hz, 2H), 4.39 – 4.28 (m, 3H), 3.01 – 2.68 (m, 2H),
1
9
1
.96 – 1.67 (m, 5H), 1.64 – 1.52 (m, 1H). F NMR (376 MHz, CDCl
3
) δ -81.5 –
-
81.6 (m, 2F), -83.0 – -83.2 (m, 2F), -105.8 (m, 1F), -111.4 – -115.2 (AB, J = 263 Hz,
1
3
2
F), -113.0 (s, 2F), -123.9 (s, 2F), -124.9 – -125.1 (m, 2F). C NMR (100 MHz,
) δ 165.8 (d, J = 252 Hz), 165.6, 149.8, 132.1 (d, J = 9.2 Hz), 130.2, 128.3,
26.5 (d, J = 3.0 Hz), 121.4, 115.5 (d, J = 21.9 Hz), 64.6, 41.6 (tm, J = 21.0 Hz), 39.7,
7.7, 26.3, 20.2. IR (film) vmax: 3393, 2973, 1718, 1605, 1508, 1425, 1208, 1146, 881,
CDCl
3
1
2
7
7
-1
+
70 cm . HRMS (ESI): calcd. for [C25
H
20
F13IO
6
S + H ] 822.9890, found 822.9896.
,7,8,8,9,9,10,10-octafluoro-5-iodo-10-(1,1,2,2-tetrafluoro-2-(phenoxysulfonyl)eth
oxy)decyl 4-iodobenzoate (4i): Obtained as yellow liquid in yield 72% by silica gel

1
flash column chromatography eluted with EA/PE = 1:15 v/v. H NMR (400 MHz,
CDCl ) δ 7.83 – 7.77 (m, 2H), 7.77 – 7.72 (m, 2H), 7.49 – 7.41 (m, 2H), 7.41 – 7.36
m, 1H), 7.30 – 7.26 (m, 2H), 4.37 – 4.30 (m, 3H), 3.01 – 2.68 (m, 2H), 1.94 – 1.67
3
(
1
9
(
m, 5H), 1.63 – 1.51 (m, 1H). F NMR (376 MHz, CDCl
3
) δ -81.5 – -81.6 (m, 2F),
-
83.0 – -83.2 (m, 2F), -111.4 – -115.2 (AB, J = 263 Hz, 2F), -113.0 (s, 2F), -123.8 (s,
1
3
2
1
F), -125.0 (m, 2F). C NMR (100 MHz, CDCl
3
) δ 166.1, 149.8, 137.7, 131.0, 130.2,
29.7, 128.3, 121.4, 100.7, 64.7, 41.6 (tm, J = 21.0 Hz), 39.7, 27.6, 26.2, 20.2. IR
-1
(
film) vmax: 2954, 1718, 1488, 1425, 1280, 1201, 1146, 881, 747 cm . HRMS (ESI):
+
calcd. for [C25
H
20
12
F I
2
O
6
S + Na ] 952.8771, found 952.8763.
5
,5,6,6,7,7,8,8-octafluoro-3-iodo-8-(1,1,2,2-tetrafluoro-2-(phenoxysulfonyl)ethoxy
)octyl 4-chlorobenzoate (4j): Obtained as yellow liquid in yield 66% by silica gel
1
flash column chromatography eluted with EA/PE = 1:25 v/v. H NMR (400 MHz,
CDCl
4.52 (m, 1H), 4.51 – 4.38 (m, 2H), 3.09 – 2.79 (m, 2H), 2.40 – 2.18 (m, 2H). F
NMR (376 MHz, CDCl ) δ -81.5 – -81.6 (m, 2F), -83.0 – -83.2 (m, 2F), -111.4 –
115.2 (AB, J = 263 Hz, 2F), -113.0 (s, 2F), -123.8 (s, 2F), -125.1 – -124.9 (m, 2F).
13C NMR (100 MHz, CDCl
) δ 165.4, 150.0, 139.7, 131.0, 130.2, 128.8, 128.3, 128.2,
21.3, 64.8, 41.8 (tm, J = 21.0 Hz), 38.8, 15.0. IR (film) vmax: 1725, 1596, 1488, 1425,
3
) δ 7.95 (d, J = 8.1 Hz, 2H), 7.49 – 7.35 (m, 5H), 7.28 (d, J = 8.0 Hz, 2H), 4.61
1
9
–
3
-
3
1
1
-1
273, 1205, 1144, 1016, 882, 760 cm . HRMS (ESI): calcd. for [C23
H
16ClF12IO S +
6
+
Na ] 832.9101, found 832.9100.
5
,5,6,6,7,7,8,8-octafluoro-3-iodo-8-(1,1,2,2-tetrafluoro-2-(phenoxysulfonyl)ethoxy
)octyl 4-(tert-butyl)benzoate (4k): Obtained as yellow liquid in yield 59% by silica
1
gel flash column chromatography eluted with EA/PE = 1:35 v/v. H NMR (400 MHz,
CDCl
3
) δ 7.95 (d, J = 8.2 Hz, 2H), 7.50 – 7.41 (m, 4H), 7.41 – 7.35 (m, 1H), 7.27 (d,
J = 7.9 Hz, 2H), 4.58 – 4.37 (m, 3H), 3.07 – 2.80 (m, 2H), 2.39 – 2.16 (m, 2H), 1.34
1
9
(
-
(
s, 9H). F NMR (376 MHz, CDCl
3
) δ -81.5 – -81.6 (m, 2F), -83.0 – -83.2 (m, 2F),
111.4 – -115.2 (AB, J = 263 Hz, 2F), -113.0 (s, 2F), -123.8 (s, 2F), -125.1 – -124.9
1
3
m, 2F). C NMR (100 MHz, CDCl
3
) δ 166.3, 156.9, 149.8, 130.2, 129.4, 128.3,
1
2
27.0, 125.4, 121.3, 64.3, 41.8 (tm, J = 21.0 Hz), 39.0, 35.1, 31.1, 15.3. IR (film) vmax
:
-1
966, 1721, 1610, 1488, 1425, 1275, 1190, 1144, 1018, 881, 774 cm . HRMS (ESI):

+
calcd. for [C27
H
25
F12IO
6
S + Na ] 855.0117, found 855.0115.
6
,6,7,7,8,8,9,9-octafluoro-4-iodo-9-(1,1,2,2-tetrafluoro-2-(phenoxysulfonyl)ethoxy
)nonyl 4-methoxybenzoate (4l): Obtained as yellow liquid in yield 57% by silica gel
1
flash column chromatography eluted with EA/PE = 1:10 v/v. H NMR (400 MHz,
CDCl
3
) δ 7.99 (d, J = 8.8 Hz, 2H), 7.45 (t, J = 7.7 Hz, 2H), 7.38 (t, J = 7.2 Hz, 1H),
7
3
.27 (d, J = 9.2 Hz, 2H), 6.92 (d, J = 8.8 Hz, 2H), 4.43 – 4.31 (m, 3H), 3.86 (s, 3H),
1
9
.03 – 2.70 (m, 2H), 2.07 – 1.86 (m, 4H). F NMR (376 MHz, CDCl ) δ -81.5 –
3
-
81.6 (m, 2F), -83.0 – -83.2 (m, 2F), -111.4 – -115.2 (AB, J = 263 Hz, 2F), -113.0 (s,
1
3
2
1
F), -123.8 (s, 2F), -124.9 – -125.1 (m, 2F). C NMR (100 MHz, CDCl
3
) δ 166.2,
63.4, 149.8, 131.6, 130.2, 128.3, 122.5, 121.4, 113.6, 63.2, 55.4, 41.6 (tm, J = 21.0
Hz), 36.9, 29.0, 19.6. IR (film) vmax: 3355, 2974, 2896, 1716, 1608, 1425, 1260, 1090,
-
1
+
1
8
7
050, 881 cm . HRMS (ESI): calcd. for [C25
H
21
F
12IO S + H ] 820.9934, found
7
20.9936.
,7,8,8,9,9,10,10-octafluoro-5-iodo-10-(1,1,2,2-tetrafluoro-2-(phenoxysulfonyl)eth
oxy)decyl thiophene-2-carboxylate (4m): Obtained as yellow liquid in yield 70% by
1
silica gel flash column chromatography eluted with EA/PE = 1:15 v/v. H NMR (400
MHz, CDCl
3
) δ 7.83 – 7.78 (m, 1H), 7.56 (dd, J = 6.0, 5.0 Hz, 1H), 7.46 (t, J = 7.6 Hz,
2
4
H), 7.39 (t, J = 7.3 Hz, 1H), 7.31 – 7.25 (m, 2H), 7.12 (t, J = 4.0 Hz, 1H), 4.36 –
1
9
.28 (m, 3H), 2.99 – 2.69 (m, 2H), 1.78 – 1.69 (m, 5H), 1.63 – 1.53 (m, 1H). F
) δ -81.5 – -81.6 (m, 2F), -83.0 – -83.2 (m, 2F), -111.4 –
115.2 (AB, J = 263 Hz, 2F), -113.0 (s, 2F), -123.9 (s, 2F), -124.9 – -125.1 (m, 2F).
13C NMR (100 MHz, CDCl
) δ 162.2, 149.8, 133.8, 133.4, 132.3, 130.2, 128.3, 127.7,
21.4, 64.6, 41.5 (tm, J = 21.0 Hz), 39.7, 27.6, 26.2, 20.2. IR (film) vmax: 2954, 1720,
NMR (376 MHz, CDCl
3
-
3
1
1
-1
586, 1488, 1426, 1276, 1220, 1147, 1071, 882, 713 cm . HRMS (ESI): calcd. for
+
[C
23
H
19
F12IO
6
S
2
+ Na ] 832.9368, found 832.9373.
7
,7,8,8,9,9,10,10-octafluoro-5-iodo-10-(1,1,2,2-tetrafluoro-2-(phenoxysulfonyl)eth
oxy)decyl 1-methyl-1H-pyrrole-2-carboxylate (4n): Obtained as yellow liquid in
yield 43% by silica gel flash column chromatography eluted with EA/PE = 1:15 v/v.
1H NMR (400 MHz, CDCl
) δ 7.45 (t, J = 7.7 Hz, 2H), 7.39 (t, J = 7.4 Hz, 1H), 7.30
3
–
7.25 (m, 2H), 6.97 – 6.93 (m, 1H), 6.78 (s, 1H), 6.13 – 6.09 (m, 1H), 4.38 – 4.28 (m,

1
1
H), 4.24 (t, J = 6.1 Hz, 2H), 3.92 (s, 3H), 2.99 – 2.70 (m, 2H), 1.92 – 1.64 (m, 5H),
1
9
.60 – 1.52 (m, 1H). F NMR (376 MHz, CDCl ) δ -81.5 – -81.6 (m, 2F), -83.0 –
3
-
-
83.2 (m, 2F), -111.4 – -115.2 (AB, J = 263 Hz, 2F), -113.0 (s, 2F), -123.8 (s, 2F),
1
3
125.1 – -124.9 (m, 2F). C NMR (100 MHz, CDCl
3
) δ 161.3, 149.8, 130.2, 129.5,
1
2
28.3, 122.5, 121.4, 117.8, 107.8, 63.2, 41.5 (tm, J = 21.0 Hz), 39.8, 36.8, 27.8, 26.3,
-1
0.3. IR (film) vmax: 2923, 1702, 1488, 1417, 1321, 1208, 1146, 881, 738 cm .
+
HRMS (ESI): calcd. for [C24
H
22
F
12INO
6
S + Na ] 829.9913, found 829.9910.
4
6
-methyl-2-oxo-2H-chromen-7-yl
,6,7,7,8,8,9,9-octafluoro-4-iodo-9-(1,1,2,2-tetrafluoro-2-(phenoxysulfonyl)ethoxy
)nonanoate (4o): Obtained as yellow liquid in yield 43% by silica gel flash column
1
chromatography eluted with EA/PE = 1:2 v/v. H NMR (400 MHz, CDCl
3
) δ 7.61 (d,
J = 8.6 Hz, 1H), 7.45 (t, J = 7.5 Hz, 2H), 7.38 (t, J = 7.5 Hz, 1H), 7.28 (d, J = 7.9 Hz,
2
4
H), 7.10 (td, J = 11, 4 Hz, 2H), 6.27 (s, 1H), 4.48 – 4.40 (m, 1H), 3.07 – 2.74 (m,
1
9
H), 2.43 (s, 3H), 2.35 – 2.14 (m, 2H). F NMR (376 MHz, CDCl ) δ -81.5 – -81.6
3
(
-
m, 2F), -83.0 – -83.2 (m, 2F), -111.4 – -115.2 (AB, J = 263 Hz, 2F), -113.0 (s, 2F),
1
3
123.8 (s, 2F), -125.1 – -124.9 (m, 2F). C NMR (100 MHz, CDCl
54.1, 152.8, 151.9, 149.8, 130.2, 128.3, 125.4, 121.3, 118.0, 117.9, 114.5, 110.3, 41.7
tm, J = 21.0 Hz), 34.9, 34.7, 18.6, 18.5. IR (film) vmax: 1732, 1615, 1488, 1421, 1388,
3
) δ 170.0, 160.4,
1
(
-1
+
1
208, 1135, 881, 774 cm . HRMS (ESI): calcd. for [C27
H
19
F
12IO S + Na ] 880.9546,
8
found 880.9543.
phenyl
2
-((7-(3,4-dimethoxyphenyl)-1,1,2,2,3,3,4,4-octafluoro-6-iodoheptyl)oxy)-1,1,2,2-t
etrafluoroethane-1-sulfonate (4p): Obtained as yellow liquid in yield 51% by silica
1
gel flash column chromatography eluted with EA/PE = 1:8 v/v. H NMR (400 MHz,
CDCl
3
) δ 7.49 – 7.42 (m, 2H), 7.41 – 7.35 (m, 1H), 7.31 – 7.25 (m, 2H), 6.83 (d, J =
8
3
.1 Hz, 1H), 6.77 – 6.69 (m, 2H), 4.49 – 4.39 (m, 1H), 3.89 (s, 3H), 3.88 (s, 3H), ,
1
9
.26 – 3.09 (m, 2H), 2.95 – 2.75 (m, 2H). F NMR (376 MHz, CDCl ) δ -81.5 –
3
-
81.6 (m, 2F), -83.0 – -83.2 (m, 2F), -111.4 – -115.2 (AB, J = 263 Hz, 2F), -113.0 (s,
1
3
2
1
F), -123.9 (s, 2F), -125.0 (m, 2F). C NMR (100 MHz, CDCl
3
) δ 149.8, 148.9,
48.2, 131.0, 130.2, 128.3, 121.3, 121.2, 112.1, 111.1, 55.84, 55.81, 46.6, 40.5 (tm, J

=
21.0 Hz) 20.0. IR (film) vmax: 2938, 1518, 1424, 1488, 1208, 1144, 1029, 882, 772
-1
+
cm . HRMS (ESI): calcd. for [C23
H
19
F
12IO S + Na ] 800.9648, found 800.9651.
6
phenyl
2
-((9-(1,3-dioxoisoindolin-2-yl)-1,1,2,2,3,3,4,4-octafluoro-6-iodononyl)oxy)-1,1,2,2
-
tetrafluoroethane-1-sulfonate (4q): Obtained as yellow liquid in yield 52% by
1
silica gel flash column chromatography eluted with EA/PE = 1:5 v/v. H NMR (400
MHz, CDCl
3
) δ 7.88 – 7.82 (m, 2H), 7.75 – 7.69 (m, 2H), 7.46 (t, J = 7.7 Hz, 2H),
7
2
.39 (t, J = 7.3 Hz, 1H), 7.31 – 7.25 (m, 2H), 4.37 – 4.29 (m, 1H), 3.80 – 3.70 (m, 2H),
1
9
.97 – 2.64 (m, 2H), 2.04 – 1.92 (m, 1H), 1.92 – 1.75 (m, 3H). F NMR (376 MHz,
CDCl
Hz, 2F), -113.0 (s, 2F), -123.9 (s, 2F), -125.0 – -125.1 (m, 2F). C NMR (100 MHz,
CDCl ) δ 168.3, 149.8, 134.0, 132.0, 130.2, 128.3, 123.3, 121.4, 41.4 (tm, J = 21 Hz),
7.3, 36.7, 28.9, 19.1. IR (film) vmax: 2954, 1720, 1488, 1426, 1276, 1220, 1150, 882,
3
) δ -81.5 – -81.6 (m, 2F), -83.0 – -83.2 (m, 2F), -111.4 – -115.2 (AB, J = 263
1
3
3
3
7
8
-
1
+
13 cm . HRMS (ESI): calcd. for [C25
H
18
F
12INO S + Na ] 837.9600, found
6
37.9603.
phenyl
-((1,1,2,2,3,3,4,4,5,5,6,6-dodecafluoro-8-iodo-9-(4-phenoxyphenyl)nonyl)oxy)-1,1
2
,
2,2-tetrafluoroethane-1-sulfonate (4r): Obtained as yellow liquid in yield 48% by
1
silica gel flash column chromatography eluted with EA/PE = 1:30 v/v. H NMR (400
MHz, CDCl
3
) δ 7.45 (t, J = 7.6 Hz, 2H), 7.41 – 7.31 (m, 3H), 7.30 – 7.24 (m, 2H),
7
5
.18 – 7.08 (m, 3H), 6.99 (q, J = 8.2 Hz, 4H), 4.47 – 4.38 (m, 1H), 3.26 (dd, J = 14.6,
1
9
.6 Hz, 1H), 3.12 – 3.20 (m, 1H), 2.97 – 2.78 (m, 2H). F NMR (376 MHz, CDCl ) δ
3
-
81.5 – -81.6 (m, 2F), -83.0 – -83.2 (m, 2F), -111.4 – -115.2 (AB system, J = 263.0 Hz,
1
3
2
F), -113.0 (s, 2F), -121.7 (s, 2F), -122.2 (s, 2F), -123.6 (s, 2F), -125.2 (s, 2F). C
) δ 157.0, 156.5, 149.8, 133.3, 130.3, 130.2, 129.8, 128.3,
23.4, 121.4, 119.0, 118.8, 46.4, 41.8 (tm, J = 21.0 Hz), 20.0. IR (film) vmax: 1590,
NMR (100 MHz, CDCl
3
1
1
-1
507, 1488, 1426, 1224, 1146, 881, 773 cm . HRMS (ESI): calcd. for
+
[C
29
H
19
F16IO
5
S + Na ] 932.9635, found 932.9649.
phenyl
,1,2,2-tetrafluoro-2-((1,1,2,2,3,3,4,4-octafluoro-6-iodo-10-(((8S,9R,13R,14R)-13-
1

methyl-17-oxo-7,8,9,11,12,13,14,15,16,17-decahydro-6H-cyclopenta[a]phenanthre
n-3-yl)oxy)decyl)oxy)ethane-1-sulfonate (4s): Obtained as yellow liquid in yield 58%
1
by silica gel flash column chromatography eluted with EA/PE = 1:5 v/v. H NMR
(
400 MHz, CDCl
Hz, 2H), 7.19 (d, J = 8.6 Hz, 1H), 6.71 (d, J = 8.5 Hz, 1H), 6.64 (s, 1H), 4.37 – 4.29
m, 1H), 3.95 (t, J = 5.9 Hz, 2H), 2.98 – 2.70 (m, 4H), 2.56 – 2.44 (m, 1H), 2.43 –
3
) δ 7.45 (t, J = 7.6 Hz, 2H), 7.39 (t, J = 7.6 Hz, 1H), 7.27 (t, J = 7.6
(
2
1
.37 (m, 1H), 2.31 – 2.18 (m, 1H), 2.17 – 1.93 (m, 4H), 1.89 – 1.72 (m, 4H), 1.66 –
1
9
.41 (m, 8H), 0.90 (s, 3H). F NMR (376 MHz, CDCl ) δ -81.5 – -81.6 (m, 2F),
3
-
83.0 – -83.2 (m, 2F), -111.4 – -115.2 (AB, J = 263 Hz, 2F), -113.0 (s, 2F), -123.8 (s,
1
3
2
1
F), -124.9 – -125.1 (m, 2F). C NMR (100 MHz, CDCl
3
) δ 221.0, 156.9, 149.8,
37.7, 132.1, 130.2, 128.3, 126.3, 121.3, 114.6, 112.1, 67.4, 50.4, 48.0, 44.0, 41.5 (tm,
J = 21.0 Hz), 40.0, 38.4, 35.8, 31.6, 29.6, 28.2, 26.5, 26.4, 25.9, 21.6, 20.3, 13.9. IR
-1
(
film) vmax: 2930, 1739, 1609, 1488, 1424, 1201, 1146, 881, 774, 524 cm . HRMS
+
(ESI): calcd. for [C36
H
37
F12IO
6
S + Na ] 975.1056, found 975.1061.
phenyl
,1,2,2-tetrafluoro-2-((1,1,2,2,3,3,4,4-octafluoro-10-hydroxy-6-iododecyl)oxy)etha
1
ne-1-sulfonate (4t): Obtained as yellow liquid in yield 66% by silica gel flash column
1
chromatography eluted with EA/PE = 1:2 v/v. H NMR (400 MHz, CDCl
3
) δ 7.50 –
7
.42 (m, 2H), 7.42 – 7.36 (m, 1H), 7.31 – 7.25 (m, 2H), 4.37 – 4.29 (m, 1H), 3.67 (t, J
1
9
=
6.5 Hz, 2H), 3.00 – 2.68 (m, 2H), 1.89 – 1.77 (m, 2H), 1.68 – 1.41 (m, 5H). F
) δ -81.5 – -81.6 (m, 2F), -83.0 – -83.2 (m, 2F), -111.4 –
115.2 (AB, J = 263 Hz, 2F), -113.0 (s, 2F), -123.9 (s, 2F), -125.0 – -125.1 (m, 2F).
13C NMR (100 MHz, CDCl
) δ 149.8, 130.2, 128.3, 121.4, 62.4, 41.5 (tm, J = 21.0
Hz), 40.0, 31.5, 26.0, 20.5. IR (film) vmax: 3365, 2939, 1723, 1586, 1488, 1424, 1318,
NMR (376 MHz, CDCl
3
-
3
-1
+
1
143, 882, 773 cm . HRMS (ESI): calcd. for [C18
H
17
F
12IO S + Na ] 722.9542, found
5
7
22.9547.
Supporting Information
The Supporting Information is available free of charge on the website at DOI: Copies

of NMR spectra (PDF)
Acknowledgements
Support of our work by the National Natural Science Foundation of China (Nos.
2
1737004, 21672239, 21421002), the Foundation of Science and technology on
Sanming Institute of Fluorochemical Industry (FCIT201704GR, FCIT201705GR,
FCIT201701BR), and Sichuan University of Science & Engineering (y2017040) is
gratefully acknowledged.
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Scheme 1 Fluoroalkylation of terminal alkenes under visible light promotion

Scheme 2 Synthesis of sulfonates

Scheme 3 Inhibition experiments

Table 1 Screening of reaction conditions
Table 1 Screening of reaction conditions
ratio
Entrya
solvent
Photocatalyst
light
t (h)
yield (%)e
(
3a:2b)
1:1.5
1:2
1:3
1:4
1:5
1:6
1:6
1:6
1:6
1:6
1:6
1:6
1:6
1:6
1:6
1:6
1:6
1:6
1:6
1:6
1:6
1:6
1
2
3
4
5
6
7
8
9
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DCM
Ru(bpy)
Ru(bpy)
Ru(bpy)
Ru(bpy)
Ru(bpy)
Ru(bpy)
Ru(bpy)
Ru(bpy)
Ru(bpy)
Ru(bpy)
Ru(bpy)
Ru(bpy)
Ru(bpy)
Ru(bpy)
Ru(bpy)
Ru(bpy)
Ru(bpy)
Ru(bpy)
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
white light
white light
white light
white light
white light
white light
white light
white light
white light
white light
white light
white light
white light
white light
blue LED
white light
white light
white light
white light
dark
24
24
24
24
24
24
24
24
24
24
24
24
24
24
24
36
48
60
48
48
48
48
31
35
45
56
77
91
98
51
56
53
83
79
86
76
74
94
99
78
76
0
MeCN
DMF
1
0
1
NMP
1
DMPU
1
1
1
1
1
1
1
1
2
2
2
2
3
4
5
6
7
8
9
0
1
2
THF
DMSOb
DMSOc
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
d
Ru(bpy)
Ru(bpy)
-
3
Cl
2
3
Cl
2
white light
0
Eosin Y
white light
56
aReaction conditions: 3a (0.2 mmol), solvent (2.0 mL), Photocatalyst (1 mol%), visible light,
2
under N .
b
c
d
DMSO (1.0 mL), DMSO (3.0 mL), Photocatalyst (0.5 mol%).
e
19
Yields were determined by F NMR spectroscopy using benzotrifluoride as the internal standard.