DOI: 10.1002/ejoc.

201900680 Full Paper

Fluroalkylation
Cu-Mediated Synthesis of Indolines and Dihydroisoquinolinones
through Arylperfluoroalkylation of Unactivated Alkenes
Dandan Li,*[a] Yan Wang,[b] Zhenzhen Jia,[a] Zhaocheng Ou,[a] Yongrui Dong,[b] Cunjie Lv,[a]
Guangbin Fu,[a] and Deqiang Liang*[b]

Abstract: The copper-mediated fluroalkylation/cyclization of moderate to good yields with unactivated double bonds as the
N-allyl anilines has been described using fluoroalkyl iodides as radical acceptor. This protocol combines a simple experimental
fluoroalkylation reagents for the first time. The reaction pro- procedure with low-costing fluoroalkylated sources and excel-
vides an efficient and direct access to 3-fluoroalkyl indolines in lent functional group tolerance.

Introduction perfluoroalkylation for the synthesis of heterocycles. In 2018,

our group[9] developed the synthesis of CF3CH2-containing ind-
Fluoroalkyl-containing compounds often play unique roles in
olines by transition-metal-free aryltrifluoromethylation of unac-
pharmaceuticals, agrochemicals, and materials because the in-
tivated alkenes. Inspired by recent advances in difunctionaliza-
troduction of fluorinated groups can dramatically modify the
tion of unactivated alkene,[3a,8–10] and in continuation of our
solubility, metabolic stability, and bioavailability of target mol-
interest in the synthesis of biologically active compounds,[9–11]
ecules.[1] Therefore, continuous endeavors have been focused
we speculate that Rf acts as a free radical initiator mediated by
on developing efficient methods for the synthesis of organo-
copper without ligand and N-allyl acts as a free radical acceptor
fluorine compounds.[2] Over the past years, difunctionalization
to achieve the construction of fluorinated indoline structures
of alkenes to incorporate perfluoroalkyl (Rf ) group has attracted
by free radical cascade reaction. Herein, a new radical cascade
considerable attention and has emerged as a powerful strategy
reaction and towards the formation of fluorinated indoline is
for the construction of functionalized Rf-containing com-
described in this work.
pounds.[3] However, most of the perfluoroalkylative reactions
are limited to the difunctionalization of activated olefins.[4]
Therefore, it remains a challenge for the perfluoroalkylative di- Results and Discussion
functionalization of unactivated alkenes.
Initially, we chose perfluorobutyl iodide (2a) as the source of
Indoles, including indolines and oxindoles, are valuable
the C4F9 group and N-(2-methylallyl)-N-phenylacetamide (1a) to
structural motifs that widely existed in bioactive natural prod-
optimize the reaction conditions (Table 1). Firstly, various cop-
ucts, and clinical drugs.[5] Developing convenient and efficient
per sources were tested to mediate the arylperfluoroalkylation
methods for the construction of indole skeleton has long been
at 120 °C in DMSO. However, either no or only a trace amount
received significant attention in industrial and academic society.
of the desired product was obtained (entries 1–6). Gratifyingly,
Compared with the approaches for indole blocks, the pathway
when 1.5 equiv. of Cu powder was added to the reaction, we
for synthesis of indoline scaffolds is rather limited and mainly
could get the desired product 3aa in 68 % yield (entry 7). More-
restricted to the de-aromatization of indole.[6] Moreover, an-
over, the effect of solvent was also explored. DCE, CH3CN, or
other method for preparing indoline frameworks through the
PhMe were not suitable for this transformation (entries 8–10).
reduction of oxoindoles either require the use of harsh reaction
Other solvents such as 1,4-dioxane and DMF failed to give a
conditions or suffer from poor tolerance of functional groups.[7]
better yield than DMSO (entries 11–12). These results indicated
Therefore, it is essential to develop novel and highly efficient
that DMSO was the most effective solvent for this reaction. As
methods for the synthesis of indoline scaffolds. In 2016,
expected, the reaction failed to provide any desired product
Cheng and Yuan group[8] have reported the Pd-catalyzed aryl-
without Cu (entry 13). Reducing the metal Cu loading to
1.1 equiv., the yield of 3aa dropped slightly to 64 % (entry 14).
[a] School of Chemistry and Chemical Engineering, Xuchang University,
No. 88, Bayi Road, Xuchang, Henan 461000, P. R. China. When the temperature was reduced to 80 °C, only 11 % of the
E-mail: dandanli2015@outlook.com target product was obtained even after a prolonged reaction
https://huaxue.xcu.edu.cn/info/1013/3673.htm time (entry 15). In addition, we also attempted to investigate
[b] Department of Chemistry, Kunming University, the effect of perfluorobutyl iodide loading (2a). By decreasing
Kunming 650214, P. R. China.
E-mail: liangdq695@nenu.edu.cn
the amount of 2a, a diminished yield of the desired product
Supporting information and ORCID(s) from the author(s) for this article are was obtained (entry 16). To our pleasure, the yield of 3aa in-
available on the WWW under https://doi.org/10.1002/ejoc.201900680. creased to 74 % by using 3.0 equiv. of 2a (entry 17). When the

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 Full Paper

amount of 2a was further increased to 3.5 equiv., the yield of to the methyl group, we were unable to obtain any target prod-
3aa was not substantially improved (entry 18). Therefore, uct. Interestingly, the substrate N-benzyl-2-methylprop-2-en-1-
1 equiv. of 1a, 1.5 equiv. of Cu, and 3 equiv. of 2a at 120 °C in amine substituted with o-tolylsulfonyl group could also be tol-
DMSO (3 mL) for 6 h were chosen as the optimized conditions erated to give the six-membered product in a highly selective
for the Cu-mediated arylperfluoroalkylation reaction. manner (3xa). Moreover, if the methyl group R1 was replaced by
a hydrogen atom, we still obtained the corresponding indolines
Table 1. Optimization of the reaction conditions.[a] (3ya–3za). Furthermore, the reaction could be successfully ex-
tended to longer chain perfluoroiodo alkanes (C6F13I and
C8F17I), affording the corresponding products in good to excel-
lent yields (3ab–3ac). In addition, when BrCF2CO2Et was em-
ployed as a fluoroalkylating agent, 55 % yield of indoline deriva-
tive (3ad) obtained. We also attempted CF3I and CH3I as sub-

Entry [Cu] Solvent t [h] Yield[%][b]

1 CuBr DMSO 12 trace Table 2. Cu-mediated arylperfluoroalkylation reaction of alkenes.[a,b]
2 CuCl DMSO 12 trace
3 CuI DMSO 12 NR
4 Cu2O DMSO 12 NR
5 CuO DMSO 12 NR
6 CuCl2 DMSO 12 NR
7 Cu DMSO 6 68
8 Cu DCE 6 NR
9 Cu MeCN 6 NR
10 Cu PhMe 6 NR
11 Cu 1,4-dioxane 6 11
12 Cu DMF 12 31
13 – DMSO 6 NR
14[c] Cu DMSO 6 64
15[d] Cu DMSO 24 11
16[e] Cu DMSO 6 49
17[f ] Cu DMSO 6 74
18[g] Cu DMSO 6 75
[a] Reaction conditions: 0.5 mmol of 1a, 1.0 mmol of 2a, and 1.5 equiv. of
[Cu]-catalyst in 3 mL of solvent at 120 °C. [b] Isolated yield. [c] 1.1 equiv. of
Cu used. [d] At 80 °C. [e] 1.5 equiv. of 2a used. [f] 3.0 equiv. of 2a used.
[g] 3.5 equiv. of 2a used.

With the optimal conditions in hand, we turned to investi-

gate the scope and the limitations of the reactions. As shown
in Table 2, alkenes with various substitution on the phenyl ring
well tolerated in this transformation, leading to the correspond-
ing perfluoroalkylated indolines (3aa–3da) in moderate to
good yields. It should be noted that the substrate containing
pyridin-4-amine could be smoothly converted into the desired
product 3ea in 71 % yield. The effect of protecting groups on
the nitrogen atom was further examined. N-(2-methylallyl)
anilines protected by propionyl group reacted with 2a
smoothly to provide the corresponding indolines (3fa–3ga) in
60–76 % yields. Similarly, long-chain protecting groups such as
butyl, and octanoyl also showed good reactivity in this transfor-
mation (3ha–3ja). Boc-protected indoline 3ka could be ob-
tained in high yields under the standard conditions. By using
3-chlorobenzoyl group as protecting group, 2a can react selec-
tively with the benzene ring of the N-phenyl group instead of
the benzene ring of the 3-chlorobenzoyl group, furnishing the
product 3la in 62 % yield. Meanwhile, various sulfonyl protect-
ing groups including alkylsulfonyl (such as methylsulfonyl, eth-
ylsulfonyl, and N,N-dimethylsulfamoyl) and arylsulfonyl groups
(phenylsulfonyl, tosyl, and o-tolylsulfonyl) could be applied in
this protocol, bringing out the desired products 3ma–3wa in [a] Reaction conditions: 0.5 mmol of 1, 1.5 mmol of 2, and 1.5 equiv. of Cu
32–79 % yields. Disappointingly, changing the protecting group in 3 mL of DMSO at 120 °C for 6 h. [b] Isolated yield.

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 Full Paper

strates, however, either no or a trace amount of products were ylene under the standard conditions, we still could obtain the
detected. nC4F9-adduct product 6 in 45 % yield. These results indicated
Encouraged by the above-mentioned results, we next ex- that nC4F9 radical could be formed under these conditions.
plored the scope of allylamine protected by benzoyl groups Based on the above experimental results and literature re-
(Table 3). The substrate 4a bearing a methyl group on N atom ports,[8,10a,10b,12] a plausible mechanism for Cu-mediated aryl-
was tolerated under the standard conditions, affording the cor- perfluoroalkylation process was outlined in Scheme 2. First, RfX
responding six-ring product in 57 % yield (5aa). Moreover, two reacts with Cu to produce perfluoroalkyl radical Rf·, which un-
kinds of N-allylated benzylamines were also investigated. Unlike dergoes the addition with 1 to give the intermediate A. Then,
the o-tolylsulfonyl protected benzylamine (Table 2, 2w), the intermediate A is converted to intermediate B through the
benzoyl protected benzylamines selectively underwent ring clo- intramolecular radical cyclization. Finally, the generated Rf·
sure reaction with the phenyl ring of the benzoyl group, rather selectively abstracts a hydrogen atom from the intermediate B
than the phenyl ring of benzylamine group (5ba–5ca). to deliver the target product 3aa. It should be noted that a
mechanism involving Cu(I)-catalyzed perfluoroalkylation path-
Table 3. Synthesis of nC4F9-containing dihydroisoquinolinones by Cu-medi-
way[10c,13] could not be completely excluded.
ated aryltrifluoromethylation of unactivated alkenes.[a,b]

Scheme 2. Plausible mechanism.

[a] Reaction conditions: 0.5 mmol of 4, 1.5 mmol of 2, and 1.5 equiv. of Cu
in 3 mL of DMSO at 120 °C for 6 h. [b] Isolated yield.

In order to gain insights into the reaction mechanism, several Conclusions

control experiments were conducted (Scheme 1). When radical A new copper-mediated cascade cyclization of N-allyl anilines
scavenger (2,2,6,6–tetramethylpiperidin–1-yl)oxy (TEMPO) was with fluoroalkyl iodides has been demonstrated for the first
added into the reaction system, no desired target product time. This reaction allows the direct access to 3-fluoroalkyl ind-
could be observed under the standard reaction conditions olines in moderate to good yields with unactivated double
(Scheme 1). When 1,1-diphenylethylene was added as a radical bonds as the radical acceptor. This synthetic method exhibits
scavenger, the reaction was totally inhibited and the nC4F9-ad- simple operation, good functional group tolerance, and low-
duct product 6 was isolated in 16 % yield. Then, replacing the cost fluoroalkylated sources. Moreover, the preliminary mecha-
N-(2-methylallyl)-N-phenylacetamide (1a) with 1,1-diphenyleth- nistic studies disclose that the reaction may proceed via a radi-
cal pathway.

Experimental Section
General Information: Unless otherwise noted, all commercial ma-
terials and solvents were used without further purification. 1H NMR
and 13C NMR spectra were referenced to TMS and residue CHCl3 at
0.00 ppm and 77.16 ppm, respectively. High-resolution mass spec-
tra (HRMS) were measured with ESI in positive mode.
General Procedure for the Synthesis of N-Allyl Anilines or Sulf-
onamides Substrates (2b as an Example):[14] A mixture of p-tolu-
idine (1.607 g, 15.0 mmol), CH2Cl2 (50.0 mL), and Et3N (4.170 mL,
30.0 mmol), was placed in a round-bottom flask equipped with a
magnetic stir bar. To this mixture was added acetyl chloride
(1.273 mL, 18.0 mmol). The reaction mixture was stirred at room
temperature. After p-toluidine was consumed, as indicated by TLC,
the reaction mixture was quenched with aqueous NaHCO3 (100 mL)
and extracted with CH2Cl2 (100 mL) three times. The combined or-
ganic phase was washed with brine (50 mL) two times. After re-
moval of solvents, the solid of the crude product was further puri-
Scheme 1. Control experiments. fied by washing with a petroleum ether/ethyl acetate mixture (5:1,

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 Full Paper
v/v), affording N-(p-tolyl)acetamide as a white crystal. To a stirred 1.51 (d, J = 2.4 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ = 168.45,
solution of N-(ptolyl)acetamide (1.492 g, 10.0 mmol) and NaOH 138.98, 138.15, 133.97, 129.44, 122.62, 117.23, 61.64 (d, J = 6.3 Hz),
(600 mg, 15.0 mmol) in DMF (30.0 mL) was added 3-bromo-2-meth- 41.81, 39.41 (t, J = 20.4 Hz), 26.67 (d, J = 3.7 Hz), 24.25, 21.24; 19F
ylprop-1-ene (1.311 mL, 13.0 mmol), and the mixture was stirred at NMR (376 MHz, CDCl3) δ = –81.01 (t, J = 11.4 Hz, 3F), –107.82 to
ambient temperature. After N-(p-tolyl)acetamide was consumed, as –114.39 (m, 2F), –124.47 to –124.56 (m, 2F), –125.59 to –125.85 (m,
indicated by TLC, the reaction mixture was quenched with brine 2F); HRMS (ESI): m/z [M + H]+ calcd. for C17H17F9NO: 433.1161, found
(60 mL) and extracted with CH2Cl2 three times. The residue ob- 433.1163.
tained after evaporation of the solvent was purified by column
1-(5-Chloro-3-methyl-3-(2,2,3,3,4,4,5,5,5-nonafluoropentyl)-
chromatography on silica gel (petroleum ether/ethyl acetate = 20:1,
indolin-1-yl)ethanone (3ca): Yield 82 % (180.8 mg), white solid,
v/v) to afford N-(2-methylallyl)-N-(p-tolyl)acetamide 2a as a colorless
m.p. 89–90 °C. 1H NMR (400 MHz, CDCl3) δ = 8.16 (d, J = 8.6 Hz,
oil.
1H), 7.22 (dd, J = 8.6, 2.2 Hz, 1H), 7.10 (d, J = 2.2 Hz, 1H), 4.11 (d,
General Procedure for the Cu-Mediated Synthesis of Indolines J = 10.9 Hz, 1H), 3.91 (dd, J = 10.9, 1.6 Hz, 1H), 2.55–2.39 (m, 2H),
and Dihydroisoquinolinones: A mixture of N-allyl anilines 1a (1b– 2.24 (s, 3H), 1.53 (d, J = 2.3 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ =
z and 4a–c, 0.5 mmol), Cu (1.0 mmol, 63.5 mg) and RfX (1.5 mmol) 168.74, 139.97, 139.73, 129.09, 128.94, 122.52, 118.50, 61.57 (d, J =
in DMSO (3 mL) was stirred at 120 °C. The reaction was monitored 6.2 Hz), 41.86, 39.28 (t, J = 20.5 Hz), 26.77 (d, J = 3.7 Hz), 24.18; 19F
by TLC and stopped at the desired time. After the reaction was NMR (376 MHz, CDCl3) δ = –81.05 (t, J = 11.4 Hz, 3F), –108.02 to
finished, the mixture was filtered by a silica gel plug with ethyl –114.08 (m, 2F), –124.41 to –124.55 (m, 2F), –125.70 to –125.80 (m,
acetate (30 mL) as the eluent. The filtrate was washed with satu- 2F); HRMS (ESI): m/z [M + H]+ calcd. for C16H14ClF9NO: 442.0615,
rated brine (3 × 10 mL) and the organic phase was dried with found 442.0619.
Na2SO4, filtered, and concentrated under reduced pressure. The resi-
1-(3-Methyl-3-(2,2,3,3,4,4,5,5,5-nonafluoropentyl)-5-phenyl-
due was separated on a silica gel column with petroleum ether/
indolin-1-yl)ethanone(3da): Yield 58 % (140.0 mg), white solid,
ethyl acetate as the eluent to get product 3aa (3ba–3za, 3ab–ac,
m.p. 151–152 °C. 1H NMR (400 MHz, CDCl3) δ = 8.28 (d, J = 8.4 Hz,
and 5aa–ca).
1H), 7.56 (dd, J = 8.3, 1.3 Hz, 2H), 7.51 (dd, J = 8.4, 1.9 Hz, 1H), 7.44
Experimental Details: N-(2-methylallyl)-N-phenylacetamide 1a (t, J = 7.6 Hz, 2H), 7.37–7.31 (m, 2H), 4.14 (d, J = 10.8 Hz, 1H), 3.94
(0.5 mmol), Cu (1.0 mmol, 63.5 mg), nC4H9I 2a (1.5 mmol, 258.2 μL), (dd, J = 10.8, 1.6 Hz, 1H), 2.63–2.46 (m, 2H), 2.27 (s, 3H), 1.58 (d, J =
and 1,1-diphenylethenein (1.0 mmol, 176.5 μL) in DMSO (3 mL) was 2.4 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ = 168.74, 140.73, 140.64,
stirred at 120 °C. The reaction was monitored by TLC and stopped 138.68, 137.57, 128.96, 127.92, 127.33, 127.02, 120.78, 117.63, 61.75
at the desired time. After the reaction was finished, the mixture was (d, J = 6.5 Hz), 41.90, 39.44, 26.82 (d, J = 3.7 Hz), 24.31; 19F NMR
filtered by a silica gel plug with ethyl acetate (30 mL) as the eluent. (376 MHz, CDCl3) δ = –81.02 (t, J = 11.4 Hz, 3F), –107.80 to –114.22
The filtrate was washed with saturated brine (3 × 10 mL) and the (m, 2F), –124.40 to –124.50 (m, 2F), –125.59 to –125.82 (m, 2F);
organic phase was dried with Na2SO4, filtered, and concentrated HRMS (ESI): m/z [M + H]+ calcd. for C22H19F9NO: 484.1317, found
under reduced pressure. The residue was separated on a silica gel 484.1319.
column with petroleum ether/ethyl acetate as the eluent to get
1-(3-Methyl-3-(2,2,3,3,4,4,5,5,5-nonafluoropentyl)-2,3-dihydro-
product 6 (16 %, 31.9 mg).
1H-pyrrolo[3,2-c]pyridin-1-yl)ethanone (3ea): Yield 71 %
nC4H9I 2a (1.5 mmol, 258.2 μL), Cu (1.0 mmol, 63.5 mg), and 1,1- (144.8 mg), white solid, m.p. 103–104 °C. 1H NMR (400 MHz, CDCl3)
diphenylethenein (1.0 mmol, 176.5 μL) in DMSO (3 mL) was stirred δ = 8.51–8.36 (m, 2H), 8.04 (d, J = 5.6 Hz, 1H), 4.14 (d, J = 10.9 Hz,
at 120 °C. The reaction was monitored by TLC and stopped at the 1H), 3.93 (d, J = 10.9 Hz, 1H), 2.67–2.46 (m, 2H), 2.27 (s, 3H), 1.59 (s,
desired time. After the reaction was finished, the mixture was fil- 3H); 13C NMR (101 MHz, CDCl3) δ = 169.70, 150.86, 147.94, 144.22,
tered by a silica gel plug with ethyl acetate (30 mL) as the eluent. 133.26, 111.69, 65.38–60.33 (m), 41.11, 39.46 (t, J = 20.4 Hz) 27.37
The filtrate was washed with saturated brine (3 × 10 mL) and the (d, J = 3.1 Hz), 24.33; 19F NMR (376 MHz, CDCl3) δ = –81.05 (t, J =
organic phase was dried with Na2SO4, filtered, and concentrated 11.7 Hz, 3F), –108.16 to –113.86 (m, 2F), –124.41 to –124.51 (m, 2F),
under reduced pressure. The residue was separated on a silica gel –125.62 to –125.82 (m, 2F); HRMS (ESI): m/z [M + H]+ calcd. for
column with petroleum ether/ethyl acetate as the eluent to get C15H14F9N2O: 409.0957, found 409.0958.
product 6 (45 %, 89.7 mg).
1-(3,5-Dimethyl-3-(2,2,3,3,4,4,5,5,5-nonafluoropentyl)indolin-1-
1-(3-Methyl-3-(2,2,3,3,4,4,5,5,5-nonafluoropentyl)indolin-1-yl)- yl)propan-1-one (3fa): Yield 76 % (165.0 mg), white solid, m.p.
ethanone (3aa): Yield 74 % (150.5 mg), white solid, m.p. 103– 106–107 °C. 1H NMR (400 MHz, CDCl3) δ = 8.24 (d, J = 8.2 Hz, 1H),
104 °C. 1H NMR (400 MHz, CDCl3) δ = 8.22 (d, J = 8.1 Hz, 1H), 7.29– 7.19 (dd, J = 8.3, 1.8 Hz, 1H), 7.05 (s, 1H), 4.19 (d, J = 10.8 Hz, 1H),
7.25 (m, 1H), 7.14 (d, J = 6.1 Hz, 1H), 7.09 (td, J = 7.4, 1.1 Hz, 1H), 3.99 (d, J = 10.8 Hz, 1H), 2.63–2.53 (m, 4H), 2.46 (s, 3H), 1.36 (t, J =
4.10 (d, J = 10.9 Hz, 1H), 3.89 (dd, J = 10.9, 1.5 Hz, 1H), 2.58–2.40 7.4 Hz, 3H);13C NMR (101 MHz, CDCl3) δ = 171.88, 139.21, 138.05,
(m, 2H), 2.25 (s, 3H), 1.53 (d, J = 2.4 Hz, 3H); 13C NMR (101 MHz, 133.81, 129.45, 122.60, 117.17, 60.69 (d, J = 6.4 Hz), 41.81, 39.37 (t,
CDCl3) δ = 168.81, 141.28, 137.98, 128.98, 124.27, 122.10, 117.49, J = 20.3 Hz), 29.26, 26.59 (d, J = 3.6 Hz), 21.22, 8.84; 19 F NMR
61.50 (d, J = 6.2 Hz), 41.83, 39.41 (t, J = 20.6 Hz), 26.78 (d, J = 3.8 Hz), (376 MHz, CDCl 3 ) δ = –80.90 (t, J = 11.5 Hz, 3F), –107.95 to
24.38. 19F NMR (376 MHz, CDCl3) δ = –81.01 (t, J = 12.3 Hz, 3F), –114.06(m, 2F), –124.39 to –124.49 (m, 2F), –125.56 to –125.77 (m,
–107.46 to –114.59 (m, 2F), –124.46 to –124.58 (m, 2F), –125.60 to 2F); HRMS (ESI): m/z [M + H]+ calcd. for C18H19F9NO: 436.1317, found
–125.83 (m, 2F); HRMS (ESI): m/z [M + H]+ calcd. for C16H15F9NO: 436.1319.
408.1004, found 408.1007.
1-(5-Chloro-3-methyl-3-(2,2,3,3,4,4,5,5,5-nonafluoropentyl)-
1-(3,5-Dimethyl-3-(2,2,3,3,4,4,5,5,5-nonafluoropentyl)indolin-1- indolin-1-yl)propan-1-one (3ga): Yield 60 % (136.8 mg), white
yl)ethanone (3ba): Yield 80 % (172.8 mg), white solid, m.p. 119– solid, m.p. 104–105 °C. 1H NMR (400 MHz, CDCl3) δ = 8.19 (d, J =
120 °C. 11H NMR (400 MHz, CDCl3) δ = 8.09 (d, J = 8.2 Hz, 1H), 7.07 8.7 Hz, 1H), 7.23 (dd, J = 8.7, 2.2 Hz, 1H), 7.09 (d, J = 2.3 Hz, 1H),
(dd, J = 8.4, 1.6 Hz, 1H), 6.93 (s, 1H), 4.07 (d, J = 10.8 Hz, 1H), 3.88 4.10 (d, J = 10.8 Hz, 1H), 3.89 (d, J = 10.9 Hz, 1H), 2.50–2.40 (m, 4H),
(dd, J = 10.9, 1.6 Hz, 1H), 2.52–2.40 (m, 2H), 2.34 (s, 3H), 2.23 (s, 3H), 1.51 (s, 3H), 1.24 (t, J = 7.3 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ =

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 Full Paper
172.18, 140.19, 139.62, 128.96, 128.92, 122.50, 118.43, 60.65 (d, J = 2.66–2.29 (m, 2H), 1.55(d, J = 2.0 Hz, 3H); 13C NMR (101 MHz, CDCl3)
6.5 Hz), 41.87, 39.25 (t, J = 20.4 Hz), 29.28, 26.73 (d, J = 3.6 Hz), 8.73. δ = 167.30, 140.77, 138.95, 138.02, 134.91, 130.83, 130.14, 128.56,
19
F NMR (376 MHz, CDCl3) δ = –81.01 (t, J = 12.0 Hz, 3F), –107.95 127.46, 125.21, 124.81, 122.47, 117.66, 62.58, 41.54, 38.84 (t, J =
to –114.06 (m, 2F), –124.39 to –124.53 (m, 2F), –125.57 to –125.77 20.6 Hz), 26.08; 19F NMR (376 MHz, CDCl3) δ = –80.04 (t, J = 10.5 Hz,
(m, 2F); HRMS (ESI): m/z [M + H]+ calcd. for C17H16ClF9NO: 456.0771, 3F), –108.63 to –114.06 (m, 2F), –124.42 to –124.52 (m, 2F), –125.60
found 456.0776. to –125.80 (m, 2F). HRMS (ESI): m/z [M + H]+ calcd. for
C21H16ClF9NO: 504.0771, found 504.0776.
1-(5-Chloro-3-methyl-3-(2,2,3,3,4,4,5,5,5-nonafluoropentyl)-
indolin-1-yl)-2,2-dimethylpropan-1-one (3ha): Yield 86 % 5-Chloro-3-methyl-1-(methylsulfonyl)-3-(2,2,3,3,4,4,5,5,5-nona-
(207.7 mg), white solid, m.p. 100–101 °C. 1H NMR (400 MHz, CDCl3) fluoropentyl)indoline (3ma): Yield 65 % (150.2 mg), yellow oil. 1H
δ = 8.17 (d, J = 8.7 Hz, 1H), 7.22 (dd, J = 8.8, 2.2 Hz, 1H), 7.09 (d, NMR (400 MHz, CDCl3) δ = 7.36 (d, J = 8.6 Hz, 1H), 7.23 (dd, J = 8.6,
J = 2.2 Hz, 1H), 4.30 (d, J = 10.8 Hz, 1H), 4.07 (dd, J = 10.8, 1.6 Hz, 2.1 Hz, 1H), 7.14 (d, J = 2.1 Hz, 1H), 3.99 (dd, J = 10.7, 0.9 Hz, 1H),
1H), 2.50–2.31 (m, 2H), 1.52 (d, J = 2.6 Hz, 3H), 1.37 (s, 9H); 13C NMR 3.85 (dd, J = 10.6, 1.7 Hz, 1H), 2.93 (s, 3H), 2.58–2.39 (m, 2H), 1.54
(101 MHz, CDCl3) δ = 176.71, 141.74, 139.62, 129.22, 128.73, 122.12, (d, J = 2.1 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ = 139.49, 139.19,
120.02, 61.65 (d, J = 6.6 Hz) 42.53, 40.28, 38.14 (t, J = 20.6 Hz), 27.67, 129.33, 129.31, 123.63, 114.72, 62.43 (d, J = 5.9 Hz), 41.81, 38.75 (t,
24.80, 24.76. 19F NMR (376 MHz, CDCl3) δ = –81.02 (t, J = 11.2 Hz, J = 20.6 Hz), 35.19, 26.44 (d, J = 3.1 Hz); 19F NMR (376 MHz, CDCl3)
3F), –107.73 to –114.73 (m, 2F), –124.44 to –124.53 (m, 2F), –125.38 δ = –81.06 (t, J = 10.9 Hz, 3F), –108.08 to –113.61 (m, 2F), –124.38
to –126.08 (m, 2F); HRMS (ESI): m/z [M + H]+ calcd. for to –124.44 (m, 2F), –125.62 to –125.79 (m, 2F). HRMS (ESI): m/z [M
C19H20ClF9NO: 484.1084, found 484.1087. + H]+ calcd. for C15H14ClF9NO2S: 478.0285, found 478.0288.
1-(5-Chloro-3-methyl-3-(2,2,3,3,4,4,5,5,5-nonafluoropentyl)- 3-Methyl-1-(methylsulfonyl)-3-(2,2,3,3,4,4,5,5,5-nonafluoro-
indolin-1-yl)octan-1-one (3ia): Yield 66 % (173.4 mg), white solid, pentyl)-5-phenylindoline (3na): Yield 75 % (194.5 mg), white solid,
m.p. 92–93 °C. 1H NMR (400 MHz, CDCl3) δ = 8.19 (d, J = 8.7 Hz, m.p. 115–116 °C. 1H NMR (400 MHz, CDCl3) δ = 7.57–7.51 (m, 2H),
1H), 7.22 (dd, J = 8.6, 2.2 Hz, 1H), 7.09 (d, J = 2.2 Hz, 1H), 4.11 (d, 7.49 (d, J = 1.2 Hz, 2H), 7.44 (t, J = 7.6 Hz, 2H), 7.38–7.32 (m, 2H),
J = 10.8 Hz, 1H), 3.90 (d, J = 10.8 Hz, 1H), 2.57–2.27 (m, 4H), 1.76– 4.02 (dd, J = 10.6, 0.9 Hz, 1H), 3.89 (dd, J = 10.6, 1.7 Hz, 1H), 2.96
1.69 (m, 2H), 1.52 (d, J = 2.3 Hz, 3H), 1.42–1.25 (m, 8H), 0.92–0.85 (s, 3H), 2.66–2.44 (m, 2H), 1.59 (d, J = 2.2 Hz, 3H); 13C NMR (101 MHz,
(m, 3H); 13 C NMR (101 MHz, CDCl 3 ) δ = 171.66, 140.19, 139.68, CDCl3) δ = 140.43, 139.83, 138.41, 137.70, 129.05, 128.31, 127.54,
128.93, 122.47, 118.52, 60.80 (d, J = 6.4 Hz), 41.85, 39.22 (t, J = 127.04, 121.94, 113.87, 62.58 (d, J = 5.9 Hz), 41.85, 38.96, 35.08,
20.5 Hz), 36.03, 31.82, 29.41, 29.26, 26.65 (d, J = 3.7 Hz), 24.65, 22.76, 26.48 (d, J = 3.5 Hz); 19F NMR (376 MHz, CDCl3) δ = –81.02 (t, J =
14.19. 19F NMR (376 MHz, CDCl3) δ = –81.02 (t, J = 11.4 Hz, 3F), 11.7 Hz, 3F), –107.91 to –113.66 (m, 2F), –124.32 to –124.40 (m, 2F),
–107.96 to –114.07 (m, 2F), –124.33 to –124.56 (m, 2F), –125.57 to –125.57 to –125.74 (m, 2F); HRMS (ESI): m/z [M + H]+ calcd. for
–125.79 (m, 2F); HRMS (ESI): m/z [M + H]+ calcd. for C22H26ClF9NO: C21H19F9NO2S: 520.0987, found 520.0989.
526.1554, found 526.1557.
5-Chloro-1-(ethylsulfonyl)-3-methyl-3-(2,2,3,3,4,4,5,5,5-nona-
1-(5-Bromo-3-methyl-3-(2,2,3,3,4,4,5,5,5-nonafluoropentyl)- fluoropentyl)indoline (3oa): Yield 76 % (186.6 mg), yellow oil. 1H
indolin-1-yl)octan-1-one (3ja): Yield 59 % (167.9 mg), white solid, NMR (400 MHz, CDCl3) δ = 7.33 (d, J = 8.6 Hz, 1H), 7.20 (dd, J = 8.5,
m.p. 96–97 °C. 1H NMR (400 MHz, CDCl3) δ = 8.14 (d, J = 8.7 Hz, 2.1 Hz, 1H), 7.12 (d, J = 2.1 Hz, 1H), 4.09–4.01 (m, 1H), 3.90 (dd, J =
1H), 7.37 (dd, J = 8.6, 2.0 Hz, 1H), 7.24 (d, J = 2.0 Hz, 1H), 4.10 (d, 10.6, 1.7 Hz, 1H), 3.14 (q, J = 7.4 Hz, 2H), 2.57–2.39 (m, 2H), 1.53 (d,
J = 10.8 Hz, 1H), 3.89 (d, J = 10.8 Hz, 1H), 2.57–2.30 (m, 4H), 1.73 (p, J = 2.2 Hz, 3H), 1.42 (t, J = 7.4 Hz, 3H); 13C NMR (101 MHz, CDCl3)
J = 7.4 Hz, 2H), 1.51 (s, 3H), 1.42–1.25 (m, 8H), 0.93–0.84 (m, 3H); δ = 139.49, 139.29, 129.14, 128.83, 123.51, 114.69, 62.41 (d, J =
13
C NMR (101 MHz, CDCl 3 ) δ = 171.71, 140.68, 140.06, 131.88, 6.1 Hz), 44.88, 41.90, 38.79 (t, J = 20.5 Hz), 26.40 (d, J = 3.5 Hz), 7.84;
19
125.37, 118.99, 116.33, 60.76 (d, J = 6.2 Hz), 41.84, 39.26 (t, J = F NMR (376 MHz, CDCl3) δ = –81.06 (t, J = 11.3 Hz, 3F), –107.97
20.5 Hz), 36.07, 31.83, 29.41, 29.26, 26.69 (d, J = 3.4 Hz), 24.64, 22.76, to –113.79 (m, 2F), –124.40 to –124.49 (m, 2F), –125.61 to –125.79
14.19; 19 F NMR (376 MHz, CDCl 3 ) δ = –80.86 to –81.17 (m, 3F), (m, 2F); HRMS (ESI): m/z [M + H] + calcd. for C 16 H 16 ClF 9 NO 2 S:
–107.93 to –114.06 (m, 2F), –124.37 to –124.47 (m, 2F), –125.56 to 492.0441, found 492.0446.
–125.77 (m, 2F);HRMS (ESI): m/z [M + H]+ calcd. for C22H26BrF9NO:
1-(Ethylsulfonyl)-3-methyl-3-(2,2,3,3,4,4,5,5,5-nonafluoro-
570.1049, found 570.1050.
pentyl)-5-phenylindoline (3pa): Yield 74 % (197.2 mg), white solid,
tert-Butyl-5-chloro-3-methyl-3-(2,2,3,3,4,4,5,5,5-nonafluoro- m.p. 109–110 °C. 1H NMR (400 MHz, CDCl3) δ = 7.57–7.50 (m, 2H),
pentyl)indoline-1-carboxylate (3ka): Yield 84 % (209.6 mg), white 7.50–7.40 (m, 4H), 7.35 (d, J = 7.2 Hz, 2H), 4.09 (d, J = 10.6 Hz, 1H),
solid, m.p. 77–78 °C. 1H NMR (400 MHz, CDCl3) δ = 7.80 (s, 1H), 7.18 3.95 (dd, J = 10.6, 1.7 Hz, 1H), 3.18 (q, J = 7.4 Hz, 2H), 2.65–2.44 (m,
(dd, J = 8.6, 2.2 Hz, 1H), 7.06 (d, J = 2.2 Hz, 1H), 4.01 (d, J = 11.7 Hz, 2H), 1.58 (d, J = 2.2 Hz, 3H), 1.45 (t, J = 7.4 Hz, 3H); 13 C NMR
1H), 3.84 (d, J = 11.9 Hz, 1H), 2.56–2.29 (m, 2H), 1.57 (s, 9H), 1.48 (d, (101 MHz, CDCl3) δ = 140.51, 140.10, 138.23, 137.24, 129.02, 128.15,
J = 2.3 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ = 152.30, 140.08, 127.45, 127.00, 121.85, 113.80, 62.56 (d, J = 6.1 Hz), 44.71, 41.92,
139.52, 128.71, 127.66, 122.79, 116.23, 81.61, 60.60 (d, J = 5.9 Hz), 39.00 (t, J = 20.5 Hz), 26.44 (d, J = 3.4 Hz), 7.89; 19F NMR (376 MHz,
41.08, 39.39 (t, J = 20.5 Hz), 28.50, 26.84 (d, J = 2.9 Hz); 19F NMR CDCl3) δ = –80.03 (t, J = 11.3 Hz, 3F), –107.80 to –113.84 (m, 2F),
(376 MHz, CDCl3) δ = –81.09 (t, J = 10.2 Hz, 3F), –107.99 to –114.18 –124.36 to –124.42 (m, 2F), –125.57 to –125.75 (m, 2F); HRMS (ESI):
(m, 2F), –124.46 to –124.55 (m, 2F), –125.70 to –125.83 (m, 2F); m/z [M + H]+ calcd. for C22H21F9NO2S: 534.1144, found 534.1147.
HRMS (ESI): m/z [M + H]+ calcd. for C19H20F9NO2: 500.1033, found
4,6-Dichloro-1-(ethylsulfonyl)-3-methyl-3-(2,2,3,3,4,4,5,5,5-
500.1037.
nonafluoropentyl)indoline (3qa): Yield 72 % (188.9 mg), colorless
(3-Chlorophenyl)(3-methyl-3-(2,2,3,3,4,4,5,5,5-nonafluoropent- oil. 1H NMR (400 MHz, CDCl3) δ = 7.35 (d, J = 1.8 Hz, 1H), 7.00 (d,
yl)indolin-1-yl)methanone (3la): Yield 62 % (160.1 mg), colorless J = 1.8 Hz, 1H), 4.17 (d, J = 10.8 Hz, 1H), 3.90 (d, J = 10.7 Hz, 1H),
oil. 1H NMR (400 MHz, CDCl3) δ = 8.14 (s, 1H), 7.54 (t, J = 1.4 Hz, 3.22–3.13 (m, 2H), 2.89–2.65 (m, 2H), 1.65 (d, J = 1.6 Hz, 3H), 1.43
1H), 7.50–7.47 (m, 1H), 7.41 (d, J = 5.0 Hz, 2H), 7.29–7.16 (m, 2H), (t, J = 7.4 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ = 143.84, 135.81,
7.12 (d, J = 7.4 Hz, 1H), 4.12 (d, J = 11.4 Hz, 1H), 4.02–3.70 (m, 1H), 131.52, 130.82, 124.64, 112.48, 62.20 (dd, J = 4.9, 2.7 Hz), 45.37,

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42.77, 36.56, 25.64 (d, J = 2.8 Hz), 7.79; 19F NMR (376 MHz, CDCl3) (376 MHz, CDCl3) δ = –80.97 to –81.06 (t, J = 11.3 Hz, 3F), –107.70
δ = –81.05 (t, J = 12.0 Hz, 3F), –109.29 to –113.66 (m, 2F), –124.51 to –114.42 (m, 2F), –124.47 to –124.56 (m, 2F), –125.64 to –125.84
to –124.62 (m, 2F), –125.67 to –125.80 (m, 2F); HRMS (ESI): m/z [M (m, 2F); HRMS (ESI): m/z [M + H + calcd. for C22H21F9NO2S: 534.1144,
+ H]+ calcd. for C16H15Cl2F9NO2S: 526.0051, found 526.0051. found 534.1147.
N,N,3-trimethyl-3-(2,2,3,3,4,4,5,5,5-nonafluoropentyl)-5-phen- 5-Chloro-3-methyl-3-(2,2,3,3,4,4,5,5,5-nonafluoropentyl)-1-
ylindoline-1-sulfonamide (3ra): Yield 71 % (194.6 mg), yellow (o-tolylsulfonyl)indoline (3wa): Yield 51 % (283.3 mg), colorless
solid, m.p. 123–124 °C. 1H NMR (400 MHz, CDCl3) δ = 7.58–7.51 (m, oil. 1H NMR (400 MHz, CDCl3) δ = 7.96 (dd, J = 7.9, 1.5 Hz, 1H), 7.48
2H), 7.50–7.39 (m, 4H), 7.37–7.30 (m, 2H), 4.05 (d, J = 10.5 Hz, 1H), (td, J = 7.5, 1.4 Hz, 1H), 7.40 (d, J = 8.6 Hz, 1H), 7.33 (t, J = 7.8 Hz,
3.88 (dd, J = 10.5, 1.8 Hz, 1H), 2.94 (s, 6H), 2.63–2.43 (m, 2H), 1.58 2H), 7.18 (dd, J = 8.6, 2.1 Hz, 1H), 7.07 (d, J = 2.1 Hz, 1H), 3.97 (dd,
(d, J = 2.3 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ = 140.98, 140.68, J = 10.9, 0.9 Hz, 1H), 3.80 (dd, J = 11.0, 1.7 Hz, 1H), 2.60 (s, 3H),
138.07, 136.86, 129.00, 128.00, 127.34, 127.01, 121.47, 114.35, 62.81 2.42–2.24 (m, 2H), 1.37 (d, J = 2.4 Hz, 3H); 13C NMR (101 MHz, CDCl3)
(d, J = 6.4 Hz), 41.92, 39.20, 39.00, 38.80, 38.39, 26.15 (d, J = 3.4 Hz); δ = 139.81, 139.71, 138.25, 136.90, 133.62, 133.20, 129.65, 129.07,
19
F NMR (376 MHz, CDCl3) δ = –80.90 to –81.00 (m, J = 10.9 Hz, 3F), 129.01, 126.60, 123.33, 115.98, 61.71 (d, J = 6.4 Hz), 41.98, 38.78 (t,
–107.78 to –114.40 (m, 2F), –124.40 to –124.50 (m, 2F), –125.57 to J = 20.5 Hz), 25.92 (d, J = 3.7 Hz), 20.89; 19F NMR (376 MHz, CDCl3)
–125.78 (m, 2F); HRMS (ESI): m/z [M + H]+ calcd. for C22H22F9N2O2S: δ = –81.04 (t, J = 11.6 Hz, 3F), –107.82 to –114.23 (m, 2F), –124.42
549.1253, found 549.1253. to –124.48 (m, 2F), –125.63 to –125.82 (m, 2F); HRMS (ESI): m/z [M
+ H]+ calcd. for C21H18ClF9NO2S: 554.0598, found 554.0599.
3-Methyl-3-(2,2,3,3,4,4,5,5,5-nonafluoropentyl)-1-(phenylsulf-
onyl)indoline (3sa): Yield 74 % (186.8 mg), yellow oil. 1 H NMR 4-Methyl-4-(2,2,3,3,4,4,5,5,5-nonafluoropentyl)-2-(o-tolylsulf-
(400 MHz, CDCl3) δ = 7.90–7.79 (m, 2H), 7.71 (d, J = 8.1 Hz, 1H), onyl)-1,2,3,4-tetrahydroisoquinoline (3xa): Yield 25 % (66.7 mg),
7.56 (t, J = 7.4 Hz, 1H), 7.46 (dd, J = 8.5, 7.0 Hz, 2H), 7.29–7.24 (m, colorless oil. 1H NMR (400 MHz, CDCl3) δ = 7.99 (dd, J = 7.9, 1.4 Hz,
1H), 7.10–6.99 (m, 2H), 3.99–3.90 (m, 1H), 3.80 (dd, J = 11.1, 1.6 Hz, 1H), 7.48 (td, J = 7.5, 1.4 Hz, 1H), 7.37 (d, J = 7.8 Hz, 1H), 7.32 (dd,
1H), 2.41–2.07 (m, 2H), 1.26 (d, J = 2.5 Hz, 3H); 13C NMR (101 MHz, J = 8.0, 3.8 Hz, 2H), 7.27–7.18 (m, 2H), 7.07– 7.05 (m, 1H), 4.52 (d,
CDCl3) δ = 140.31, 138.19, 136.99, 133.55, 129.29, 129.09, 127.30, J = 15.1 Hz, 1H), 4.31 (d, J = 15.1 Hz, 1H), 3.67 (d, J = 12.5 Hz, 1H),
124.25, 122.96, 114.97, 61.84 (d, J = 6.2 Hz), 41.75, 39.07, 26.21 (d, 3.10 (d, J = 12.5 Hz, 1H), 2.67 (s, 3H), 2.67–2.45 (m, 1H), 2.39–2.25
J = 3.6 Hz); 19F NMR (376 MHz, CDCl3) δ = –81.12 (t, J = 10.9 Hz, (m, 1H), 1.48 (d, J = 2.4 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ =
3F), –107.75 to –114.16 (m, 2F), –124.46 to –124.56 (m, 2F), –125.69 140.39, 138.32, 135.35, 133.36, 133.11, 130.84, 130.56, 127.62,
to –125.90 (m, 2F); HRMS (ESI): m/z [M + H]+ calcd. for 127.23, 126.85, 126.49, 126.38, 53.72 (d, J = 4.3 Hz), 47.59, 38.08 (t,
C20H17F9NO2S: 506.0831, found 506.0836. J = 20.0 Hz), 37.59, 25.33 (d, J = 4.4 Hz), 20.93; 19F NMR (376 MHz,
CDCl3) δ = –81.12 (t, J = 10.7 Hz, 3F), –107.72 to –114.42 (m, 2F),
3-Methyl-3-(2,2,3,3,4,4,5,5,5-nonafluoropentyl)-1-tosylindoline
–124.04 to –124.24 (m, 2F), –125.65 to –125.83 (m, 2F); HRMS (ESI):
(3ta): Yield 79 % (205.1 mg), pale yellow oil. 1H NMR (400 MHz,
m/z [M + H]+ calcd. for C22H21F9NO2S: 534.1144, found 534.1144.
CDCl3) δ = 7.70 (t, J = 8.4 Hz, 3H), 7.26 (t, J = 8.9 Hz, 3H), 7.04 (q,
J = 3.8 Hz, 2H), 3.92 (d, J = 11.1 Hz, 1H), 3.78 (dd, J = 11.1, 1.5 Hz, 1-(5-Chloro-3-(2,2,3,3,4,4,5,5,5-nonafluoropentyl)indolin-1-yl)-
1H), 2.46–2.02 (m, 5H), 1.28 (d, J = 2.4 Hz, 3H); 13C NMR (101 MHz, ethanone (3ya): Yield 48 % (102.6 mg), white solid, m.p. 83–84 °C.
1
CDCl3) δ = 144.55, 140.46, 138.19, 134.01, 129.89, 129.05, 127.36, H NMR (400 MHz, CDCl3) δ = 8.17 (d, J = 8.7 Hz, 1H), 7.23 (dd, J =
124.13, 122.94, 115.01, 61.85 (d, J = 6.1 Hz), 41.73, 39.09, 26.14 (d, 8.7, 2.1 Hz, 1H), 7.17–7.10 (m, 1H), 4.41–4.28 (m, 1H), 3.97–3.79 (m,
J = 3.3 Hz), 21.55; 19F NMR (376 MHz, CDCl3) δ = –81.12 (t, J = 2H), 2.61 (dt, J = 30.9, 12.7 Hz, 1H), 2.45–2.30 (m, 1H), 2.24 (s, 3H);
13
11.3 Hz, 3F), –107.78 to –114.19 (m, 2F), –124.48 to –124.57 (m, 2F), C NMR (101 MHz, CDCl 3 ) δ = 168.68, 141.33, 133.77, 129.04,
–125.15 to –125.91 (m, 2F); HRMS (ESI): m/z [M + H]+ calcd. for 123.85, 118.33, 55.41 (d, J = 4.4 Hz) 36.05 (t, J = 21.0 Hz), 34.10–
C21H19F9NO2S: 520.0987, found 520.0988. 32.85 (m), 24.22; 19 F NMR (376 MHz, CDCl 3 ) δ = –80.96 (t, J =
11.3 Hz, 3F), –111.86 to –114.15 (m, 2F), –124.22 to –124.33 (m, 2F),
3-Methyl-3-(2,2,3,3,4,4,5,5,5-nonafluoropentyl)-1-(o-tolylsulf-
–125.75 to –125.90 (m, 2F); HRMS (ESI): m/z [M + H]+ calcd. for
onyl)indoline (3ua): Yield 32 % (83.2 mg), yellow oil. 1 H NMR
C15H12ClF9NO: 428.0458, found 428.0460.
(400 MHz, CDCl3) δ = 7.99 (d, J = 8.1 Hz, 1H), 7.52–7.39 (m, 2H),
7.32 (t, J = 8.1 Hz, 2H), 7.21 (t, J = 7.7 Hz, 1H), 7.11 (d, J = 7.5 Hz, 5-Chloro-1-(ethylsulfonyl)-3-(2,2,3,3,4,4,5,5,5-nonafluoropent-
1H), 7.04 (t, J = 7.4 Hz, 1H), 3.99 (d, J = 10.9 Hz, 1H), 3.82 (d, J = yl)indoline (3za): Yield 57 % (136.1 mg), yellow solid, m.p. 87–
11.6 Hz, 1H), 2.73–2.50 (m, 3H), 2.48–2.22 (m, 2H), 1.39 (d, J = 2.4 Hz, 88 °C. 1H NMR (400 MHz, CDCl3) δ = 7.33 (dd, J = 8.6, 1.5 Hz, 1H),
3H); 13C NMR (101 MHz, CDCl3) δ = 141.05, 138.26, 137.93, 137.32, 7.21 (dd, J = 8.6, 2.2 Hz, 1H), 7.17 (d, J = 2.0 Hz, 1H), 4.38–4.23 (m,
133.40, 133.11, 129.62, 128.96, 126.50, 123.88, 122.88, 114.89, 61.58 1H), 3.90–3.75 (m, 2H), 3.16–3.10 (m, 2H), 2.70–2.50 (m, 1H), 2.48–
(d, J = 6.3 Hz), 41.89, 38.94 (t, J = 20.6 Hz), 25.95 (d, J = 3.8 Hz) 2.27 (m, 1H), 1.46–1.34 (m, 3H); 13C NMR (101 MHz, CDCl3) δ =
20.87; 19F NMR (376 MHz, CDCl3) δ = –81.05 (t, J = 11.3 Hz, 3F), 140.74, 133.81, 129.25, 129.00, 124.79, 114.87, (d, J = 4.6 Hz), 45.53–
–107.76 to –114.36 (m, 2F), –124.45 to –124.52 (m, 2F), –125.64– 44.40 (m), 35.42 (t, J = 21.4 Hz), 33.59 (d, J = 3.2 Hz), 7.85; 19F NMR
125.84 (m, 2F); HRMS (ESI): m/z [M + H]+ calcd. for C21H19F9NO2S: (376 MHz, CDCl3) δ = –81.06 (t, J = 11.3 Hz, 3F), –111.93 to –114.14
520.0987, found 520.0988. (m, 2F), –124.24 to –124.36 (m, 2F), –125.81 to –125.96 (m, 2F);
HRMS (ESI): m/z [M + H]+ calcd. for C15H14ClF9NO2S: 478.0285, found
3,5-Dimethyl-3-(2,2,3,3,4,4,5,5,5-nonafluoropentyl)-1-(o-tolyl-
478.0287.
sulfonyl)indoline (3va): Yield 39 % (104.0 mg), yellow oil. 1H NMR
(400 MHz, CDCl3) δ = 7.97 (dd, J = 8.2, 1.2 Hz, 1H), 7.50–7.42 (m, 1-(3-Methyl-3-(2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptyl)-
1H), 7.36–7.27 (m, 3H), 7.02–7.01 (m, 1H), 6.89 (d, J = 1.7 Hz, 1H), indolin-1-yl)ethanone (3ab): Yield 83 % (201.5 mg), white solid,
3.96 (dd, J = 11.0, 1.0 Hz, 1H), 3.80 (dd, J = 11.0, 1.7 Hz, 1H), 2.61 m.p. 126–127 °C. 1H NMR (400 MHz, CDCl3) δ = 8.22 (d, J = 8.1 Hz,
(s, 3H), 2.45–2.21 (m, 5H), 1.36 (d, J = 2.5 Hz, 3H); 13C NMR (101 MHz, 1H), 7.31–7.23 (m, 1H), 7.14 (s, 1H), 7.09 (dd, J = 7.4, 1.1 Hz, 1H),
CDCl3) δ = 138.66, 138.24, 138.19, 137.34, 133.71, 133.29, 133.07, 4.10 (d, J = 10.8 Hz, 1H), 3.94–3.85 (m, 1H), 2.57–2.40 (m, 2H), 2.25
129.62, 129.47, 126.45, 123.40, 114.80, 61.70 (d, J = 6.7 Hz), 41.92, (s, 3H), 1.53 (d, J = 2.4 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ =
38.95 (t, J = 20.4 Hz), 29.85, 25.84, 21.02 (d, J = 15.8 Hz); 19F NMR 168.79, 141.29, 138.00, 128.96, 124.26, 122.09, 117.49, 61.50 (d, J =

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6.4 Hz), 41.85, 39.52 (t, J = 20.4 Hz), 26.75 (d, J = 3.7 Hz), 24.32; 19F 7.37–7.32 (m, 2H), 7.30–7.26 (m, 1H), 7.26–7.22 (m, 1H), 4.99 (d, J =
NMR (376 MHz, CDCl3) δ = –80.59 to –80.89 (t, J = 11.3 Hz, 3F), 14.6 Hz, 1H), 4.53 (d, J = 14.6 Hz, 1H), 3.51–3.37 (m, 2H), 2.43–2.07
–107.64 to –113.92 (m, 2F), –121.47 to –12163, (m, 2F), –122.73 to (m, 2H), 1.56 (d, J = 2.3 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ =
–122.86 (m, 2F), –123.53 to –123.64 (m, 2F), –126.01 to –126.18 (m, 164.36, 144.35, 138.80, 134.81, 132.83, 130.19, 129.43, 128.70,
2F); HRMS (ESI): m/z [M + H]+ calcd. for C18H15F13NO: 508.0941, 128.15, 128.06, 127.89, 126.83, 124.22, 55.68 (d, J = 3.9 Hz), 50.38,
found 508.0947. 36.91 (t, J = 20.3 Hz), 36.09, 22.86 (d, J = 2.0 Hz); 19F NMR (376 MHz,
CDCl3) δ = –81.06 (t, J = 11.9 Hz, 3F), –110.00 to –113.50 (m, 2F),
1-(3-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-Heptadecafluorononyl)-3-
–124.00 to –124.33 (m, 2F), –125.54 to –125.95 (m, 2F); HRMS (ESI):
methylindolin-1-yl)ethanone (3ac): Yield 50 % (151.8 mg), white
m/z [M + H]+ calcd. for C22H18ClF9NO: 518.0928; found: 518.0932.
solid. 1H NMR (400 MHz, CDCl3) δ = 8.22 (d, J = 8.1 Hz, 1H), 7.30–
7.24 (m, 1H), 7.13 (s, 1H), 7.09 (dd, J = 7.4, 1.1 Hz, 1H), 4.08 (s, 1H), (3,3,4,4,5,5,6,6,6-Nonafluorohex-1-ene-1,1-diyl)dibenzene (6):
3.94–3.85 (m, 1H), 2.61–2.38 (m, 2H), 2.25 (s, 3H), 1.53 (d, J = 2.4 Hz, Yield 45 % (89.7 mg), white solid, m.p. 71–72 °C. 1H NMR (400 MHz,
3H); 13C NMR (101 MHz, CDCl3) δ = 168.79, 141.29, 138.01, 128.97, CDCl3) δ = 7.43–7.30 (m, 6H), 7.25–7.21 (m, 4H), 6.09 (t, J = 14.7 Hz,
124.26, 122.09, 117.50, 61.51 (d, J = 6.3 Hz), 41.86, 39.53 (t, J = 3H); 13C NMR (101 MHz, CDCl3) δ = 154.59 (t, J = 4.5 Hz), 140.89,
20.4 Hz), 26.75 (d, J = 3.6 Hz), 24.33; 19F NMR (376 MHz, CDCl3) δ = 140.87, 137.62, 129.67, 129.16 (t, J = 2.8 Hz), 128.66, 128.49, 128.09,
–80.73(t, J = 11.3 Hz, 3F). –107.63 to –113.90 (m, 2F), –121.30 to 128.01, 112.79 (t, J = 21.1 Hz); 19F NMR (376 MHz, CDCl3) δ = –81.05
–121.86 (m, 2F), –122.30 to –123.56 (m, 6F), –123.54 (d, J = 15.0 Hz, (t, J = 10.9 Hz, 3F), –103.71 to –103.83 (m, 2F), –123.89 to –123.98
2F), –126.07 (dd, J = 20.1, 11.7 Hz, 2F). to –80.85 (m, 3F); HRMS (ESI): (m, 2F), –125.61 to –125.68 (m, 2F); HRMS (ESI): m/z [M + H]+ calcd.
m/z [M + H] + calcd. for C20H15F17NO: 608.0877, found 608.0879. for C18H12F9: 399.0790; found: 399.0794.
Ethyl 3-(1-acetyl-3-methylindolin-3-yl)-2,2-difluoropropanoate
(3ad): Yield 55 % (85.6 mg), yellow solid, m.p. 208–209 °C. 1H NMR Acknowledgments
(400 MHz, CDCl3) δ = 8.20 (d, J = 8.1 Hz, 1H), 7.26–7.21 (m, 1H),
7.11 (d, J = 1.4 Hz, 1H), 7.05 (td, J = 7.5, 1.1 Hz, 1H), 4.24–4.11 (m, This work was supported by the National Natural Science Foun-
3H), 3.82 (d, J = 10.7 Hz, 1H), 2.63–2.37 (m, 2H), 2.24 (s, 3H), 1.47 (d, dation of China (21702083), the Program for Innovative Re-
J = 1.6 Hz, 3H), 1.30 (t, J = 7.1 Hz, 3H); 13C NMR (101 MHz, CDCl3) search Team (in Science and Technology) in Universities of
δ = 164.36, 144.35, 138.80, 134.81, 132.83, 130.19, 129.43, 128.70, Yunnan Province, and the Yunnan Ten Thousand Talent Program
128.15, 128.06, 127.89, 126.83, 124.22, 55.68 (d, J = 3.9 Hz), 50.38, for Young Top-Notch Talents, and the key project of education
38.35–35.53 (m) 22.86; 13 C NMR (101 MHz, CDCl 3 ) δ = 168.83, department of Henan Province (Nos. 17A150050).
164.31, 163.99, 163.67, 141.65, 137.82, 128.75, 124.01, 122.40,
118.58, 117.37, 116.08, 113.57, 63.38, 61.45 (d, J = 4.5 Hz), 43.59 (t,
J = 22.0 Hz), 41.71, 27.08 (d, J = 2.6 Hz), 24.36, 13.96; 19F NMR Keywords: Copper · Fluoroalkylation · Homogeneous
(376 MHz, CDCl3) δ = –100.40 to –104.22 (m, 2F); HRMS (ESI): m/z catalysis · Nitrogen heterocycles · Radical reactions
[M + H]+ calcd. for C16H20F2NO3: 312.1406, found 312.1409.
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Fluroalkylation
D. Li,* Y. Wang, Z. Jia, Z. Ou,
Y. Dong, C. Lv, G. Fu, D. Liang* ...... 1–9
Cu-Mediated Synthesis of Indolines
and Dihydroisoquinolinones through The copper-mediated fluroalkylation/ moderate to good yields. This protocol
Arylperfluoroalkylation of Unacti- cyclization of N-allyl anilines has been combines a simple experimental pro-
vated Alkenes described with unactivated double cedure with low-costing fluoroalkyl-
bonds as the radical acceptor. The re- ated sources and excellent functional
action provides an efficient and direct group tolerance.
access to 3-fluoroalkyl indolines in

DOI: 10.1002/ejoc.201900680

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