Copper-mediated aerobic iodination and perfluoroalkylation of boronic acids with (CF3)2CFI at room temperature

Article abstract of DOI:10.1016/j.jfluchem.2016.07.021

The copper-mediated aerobic reactions between the branched (CF₃)₂CFI and boronic acids (R-B(OH)₂) are described. Different from the linear perfluoroalkyl analogs CF₃(CF₂)_nI (n?=?2, 3, 5, 7), (CF₃)₂CFI reacting with R-B(OH)₂at room temperature under air in the presence of catalytic Cu powder provided exclusively the corresponding iodides (R-I), while the aerobic reactions of arylboronic acids with (CF₃)₂CFI at room temperature in the presence of Cu(OAc)₂gave the perfluoroalkylation products (R-CF(CF₃)₂) in acceptable to moderate yields. The iodination reaction could be further promoted by hydroquinone, the addition of which improved the oxidation ability of (CF₃)₂CFI and provided the ipso-iodination products in high yields. The perfluoroalkylation was facilitated by the copper carboxylates since the addition of these salts into the reaction mixtures could successfully give rise to Ar-CF(CF₃)₂.

Full text of DOI:10.1016/j.jfluchem.2016.07.021

Accepted Manuscript
Title: Copper-Mediated Aerobic Iodination and
Perfluoroalkylation of Boronic Acids with (CF3)2CFI at Room
Temperature
Author: Xi-Hai Liu Jing Leng Su-Jiao Jia Jian-Hong Hao
Fanglin Zhang Hua-Li Qin Cheng-Pan Zhang
PII:
S0022-1139(16)30224-X
DOI:
Reference:
http://dx.doi.org/doi:10.1016/j.jfluchem.2016.07.021
FLUOR 8827
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Received date:
Revised date:
Accepted date:
20-6-2016
29-7-2016
30-7-2016
Please cite this article as: Xi-Hai Liu, Jing Leng, Su-Jiao Jia, Jian-Hong Hao, Fanglin
Zhang, Hua-Li Qin, Cheng-Pan Zhang, Copper-Mediated Aerobic Iodination and
Perfluoroalkylation of Boronic Acids with (CF3)2CFI at Room Temperature, Journal
of Fluorine Chemistry http://dx.doi.org/10.1016/j.jfluchem.2016.07.021
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Copper-Mediated Aerobic Iodination and Perfluoroalkylation of Boronic Acids
with (CF3)2CFI at Room Temperature
Xi-Hai Liu†, Jing Leng†, Su-Jiao Jia, Jian-Hong Hao, Fanglin Zhang, Hua-Li Qin,
Cheng-Pan Zhang*
School of Chemistry, Chemical Engineering and Life Science, Wuhan University of
Technology, 205 Luoshi Road, Wuhan, 430070, China.
E-mail: cpzhang@whut.edu.cn
† These two authors contributed equally

Graphical Abstract – Synopsis
The copper-mediated aerobic reactions between the branched (CF3)2CFI and boronic
acids (R-B(OH)2) are described. Different from the linear perfluoroalkyl analogs
CF3(CF2)nI (n = 2, 3, 5, 7), (CF3)2CFI reacting with R-B(OH)2 at room temperature
under air in the presence of catalytic Cu powder provided exclusively the
corresponding iodides (R-I), while the aerobic reactions of arylboronic acids with
(CF3)2CFI at room temperature in the presence of Cu(OAc)2 gave the
perfluoroalkylation products (R-CF(CF3)2) in acceptable to moderate yields. The
iodination reaction can be further promoted by hydroquinone, the addition of which
improved the oxidation ability of (CF3)2CFI and provided the ipso-iodination products
in high yields. The perfluoroalkylation is facilitated by the copper carboxylates since
the addition of these salts into the reaction mixtures could successfully give rise to
Ar-CF(CF3)2.
Highlights
 (CF3)2CFI showed different reactivity from the linear RfnI.
 The aerobic reaction of (CF3)2CFI with R-B(OH)2 provided exclusively the
iodides.
 Hydroquinone improved the oxidation ability and facilitated the iodination.

This work demonstrates a poor perfluoroalkylation but efficient iodination.

Abstract: The copper-mediated aerobic reactions between the branched (CF3)2CFI
and boronic acids (R-B(OH)2) are described. Different from the linear perfluoroalkyl
analogs CF3(CF2)nI (n = 2, 3, 5, 7), (CF3)2CFI reacting with R-B(OH)2 at room
temperature under air in the presence of catalytic Cu powder provided exclusively the
corresponding iodides (R-I), while the aerobic reactions of arylboronic acids with
(CF3)2CFI at room temperature in the presence of Cu(OAc)2 gave the
perfluoroalkylation products (R-CF(CF3)2) in acceptable to moderate yields. The
iodination reaction could be further promoted by hydroquinone, the addition of which
improved the oxidation ability of (CF3)2CFI and provided the ipso-iodination products
in high yields. The perfluoroalkylation was facilitated by the copper carboxylates
since the addition of these salts into the reaction mixtures could successfully give rise
to Ar-CF(CF3)2.
Keywords: fluorine, copper, steric hindrance, reduction, halogenation

Introduction
Heptafluoroisopropyl iodide ((CF3)2CFI) has been widely used to incorporate
(CF3)2CF group into various organic frameworks, which have found important
applications in areas of chemistry,1 biology,2 and materials science.3 These
transformations can be accomplished by methods including transition-metal-mediated
reactions,4
sulfinatodehalogenation
reactions,5
radical
initiation,6
photoredox-catalyzed functionalization,7 and other approaches.8 Because of the huge
steric hindrance and the strong electron withdrawing ability of the (CF3)2CF moiety,
(CF3)2CFI is easier to initiate than the linear isomers by a large number of reducing
agents,4-8 generating (CF3)2CF• radical for further conversions. This leads to that the
radical perfluoroalkylation is so far the predominant reaction for (CF3)2CFI in organic
synthesis.5-7
On the other hand, (CF3)2CFI has been exploited as a powerful halogen-bond
donor and an oxidant.9-13 Some valuable physicochemical data have been disclosed to
interpret the unique reactivity of (CF3)2CFI. It was reported that the C-I···π halogen
bond interaction between (CF3)2CFI and toluene-d8 is stronger than that between
CF3(CF2)2I and toluene-d8.9 The equilibrium constants of (CF3)2CFI•pyridine formed
via halogen bonding (C-I···N) appear greater than that of CF3(CF2)2I•pyridine.10 All
these indicate the stronger electron affinity of (CF3)2CFI than CF3(CF2)2I. Meanwhile,
the electrochemical studies have uncovered that perfluoroalkyl iodides (RfnI) possess
evident oxidative properties in comparison with the non-fluorinated analogs and that
the branched ones exhibit higher oxidation potentials.11 Practically, (CF3)2CFI was
used as an oxidant and iodination agent in Ni(II)-catalyzed oxidative cross-coupling
of C(sp2)-H bonds and C(sp3)-H bonds.12 The reaction of (CF3)2CFI with toluene in
the presence or absence of Ni(OTf)2 at 140 °C for 24 h afforded benzyl iodide in 40%
or 21% NMR yield, respectively, demonstrating the noticeable iodination ability of
(CF3)2CFI.12 The linear RfnI were also utilized as the iodination reagents.13 The
simultaneous generation of aryl iodides in Cu-mediated aerobic fluoroalkylation of
arylboronic acids with linear RfnI was observed.14a Although the possible oxidative
addition/reductive elimination or nucleophilic substitution mechanism was suggested,
the details of the entire reaction are still elusive. Compared to the linear RfnI, the
branched (CF3)2CFI is more sterically hindered and the C-I bond is more
electron-deficient, which may hint different reactivities.11

Arylboronic acids have been confirmed to be the versatile cross-coupling partners
in transition-metal mediated/catalyzed aerobic reactions with numerous
fluoroalkylation reagents.14,15a Recently, the Cu-mediated reaction of ArB(OH)2 with
(CF3)2CFAg was developed to build the Caryl-CF(CF3)2 bond, which directly used
hexafluoropropene (HFP) as the starting material.15a In this work, we report that the
branched (CF3)2CFI reacted with arylboronic acids exhibiting much different reaction
profiles from the linear analogs in the presence of copper catalysts.
2. Results and discussion
Initially, the reaction of (4-chlorophenyl)boronic acid (1a) or
(1,1'-biphenyl)-4-ylboronic acid (1b) with (CF3)2CFI under the standard reaction
conditions that were favorable for fluoroalkylation of arylboronic acids by linear
RfnI14a afforded exclusively the iodination and homo-coupling products in good yields
(see supporting information (SI)). Further studies showed that (CF3)2CFI was a better
iodination reagent than the linear RfnI (RfnI = CF3CF2I, CF3(CF2)2I, CF3(CF2)3I,
CF3(CF2)5I, CF3(CF2)7I) in Cu(0)-mediated functionalization of 1a (Table 1). The
reaction of 1a (1 equiv) with (CF3)2CFI (1.5 equiv) at room temperature in the
presence of catalytic or equal equivalent of copper powder gave the iodination
product (2a) in good yields (entries 3-4, Table 1). However, the reactions using linear
RfnI afforded 2a in much lower yields (4-14%), and instead the homo-coupling
product 3a was predominated (entries 1, 2, 6, 7, and 8, Table 1 and see SI for more
details). Furthermore, hydroquinone facilitated the Cu(0)-catalyzed iodination with
(CF3)2CFI. The reaction of 1a with (CF3)2CFI in the presence of 2 equivalent of
hydroquinone provided 2a in a quantitative yield, and the formation of 3a was almost
completely inhibited (entry 5, table 1). Nevertheless, treatment of 1a with linear RfnI
in the presence of 2 equivalent of hydroquinone gave no significant changes in the
yields of 2a and 3a (see SI). Other additives such as TEMPO
(2,2,6,6-Tetramethyl-1-piperidinyloxy) and 1,4-dinitrobenzene had little influence on
the reaction of 1a with (CF3)2CFI (see SI). When the reaction was conducted in
darkness without additives, 2a was obtained in 89% yield. These results indicated that
the iodination of 1a by (CF3)2CFI might undergo a non-radical pathway.
Moreover, the choice of solvents and catalysts has significant influence on the
reaction (see SI). The reaction using 50 mol%, 20 mol%, 10 mol%, or 5 mol% Cu

powder gave 2a in good yields (85-88%). Cupric salts such as Cu(NO3)2·3H2O,
Cu(OTf)2, CuOTf, CuCN, CuSCN, Cu2O, CuI, CuBr, and CuCl are suitable catalysts
for the iodination, wherein 2a was formed in 52-88% yields (see SI). When the
reaction of 1a and (CF3)2CFI (1.5 equiv) was conducted in the presence of 20 mol%
Cu(OAc)2, the perfluoroalkylation product (4-ClC6H4CF(CF3)2, 4a) was obtained in
6% yield (see SI). Similar result was also obtained in the aerobic reaction of 1b with
(CF3)2CFI (1.5 equiv) and Cu(OAc)2 (20 mol%) (entry 2, Table 2). If AgNO3, NaOAc,
2,2'-bipyridine, or 1,10-phenathroline was added into the reaction mixture of 1b,
(CF3)2CFI, and Cu(OAc)2, almost no perfluoroalkylation product was obtained (see
SI). Interestingly, using excess 1b to react with (CF3)2CFI, the yield of 4b was
promoted (entries 4-5, Table 2). The reaction of (CF3)2CFI with 3 equiv of 1b and
equal equiv of Cu(OAc)2 at room temperature under air supplied 4b in 64% yield
(entry 6, Table 2). Futher increment of 1b to 4 or 5 equivalents didn’t continueously
improve the yield of 4b (entries 7-8, Table 2). Elevating the reaction temperature
from room temperature to 60 and 80 oC, running the reaction under an O2 atmosphere,
or exposing the reaction mixture to ultrasonic irradation (100 Hz) didn’t increase the
yield of 4b either (see SI). Copper(II) carboxylates seem to be the appropriate
catalysts among the tested catalysts for perfluoroalkylation (see SI). The use of
Cu(OCOCF3)2•H2O, Cu(OCOH)2•H2O, or Cu(OCOPh)2•H2O in the reaction of 1b
and (CF3)2CFI could also give rise to Ar-CF(CF3)2 in acceptable yields (entries 9-11,
Table 2). The combination of Cu(OAc)2 with Cu, CuI, or 4 Å molecular sieves (MS)
hardly promoted the reaction (entries 12-15, Table 2). When the reaction was
performed in DMF in the presence of CuOAc or CuOAc / 4 Å MS, 4b was obtained
in 13% or 15% yield (entries 16-17, Table 2), the employment of which had
successfully improved the Cu-mediated perfluoroalkylation of arylboronic acids by
AgCF(CF3)2.15
With the optimized reaction conditions in hand, the scope of the iodination was
investigated (Table 3). Arylboronic acids 1b-o reacting with excess (CF3)2CFI in the
presence of 2 equivalents of hydroquinone and 20 mol% of Cu(0) at ambient
temperature under air for 24 h gave the corresponding iodination products (2b-o) in
good yields. The reaction showed good functional group tolerance since the substrates
with either electron-donating groups (OCH3, t-Bu) or electron-withdrawing groups
(CF3, F, NO2, CN, CHO, CO2Et) were all readily converted. Arylboronic acids

bearing ortho-, meta-, or para-substituent afforded the desired products (2c-e, 2i-j) in
comparable yields, suggesting that the steric hindrance of the substituents on the
phenyl rings hardly affects the iodination. The reaction was also amenable to vinyl
and heteroaryl boronic acids. Treatment of 1p with (CF3)2CFI under the standard
reaction conditions provided 2p in 85% yield (Z-isomer only), and the reaction of
1q-s with (CF3)2CFI afforded 2q-s in 72-90% yields. Notably, if CF3(CF2)2I was used
instead of (CF3)2CFI in the same reaction, much low yields of the iodination products
(e.g. 2b, 2g, 2h, 2o, 2t) were observed.
In addition, the Cu(OAc)2-mediated aerobic perfluoroalkylation with (CF3)2CFI
was tested by various arylboronic acids (Table 4). It was found that
(4-chlorophenyl)boronic acid (1a, 3 equiv), (4-cyanophenyl)boronic acid (1k, 3
equiv), naphthalen-2-ylboronic acid (1o, 3 equiv), and phenylboronic acid (1t, 3 equiv)
reacted with (CF3)2CFI in the presence of equal equivalent of Cu(OAc)2 at ambient
temperature under air for 24 h to afford 4a in 28% yield, 4k in 17% yield, 4o in 26%
yield, and 4t in 50% yield, respectively. These results showed that the
perfluoroalkylation with (CF3)2CFI is less effective than the corresponding iodination
since the poor yields of the perfluoroalkylation products were obtained. The
transformation was also suitable to other arylboronic acids. Treatment of 1v-c’ with
(CF3)2CFI under the standard reaction conditions, 4v-c’ were furnished in 21-54%
yields. It was surprising that using the liner CF3(CF2)2I instead of (CF3)2CFI to react
with 1a (3 equiv) or 1b (3 equiv) under the standard reaction conditions, the
perfluoroalkylation product was obtained in only 4% or 2% 19F NMR yield,
respectively (Scheme 1).
It was known that the branched perfluoroalkyl iodides is easier to reduce than the
linear ones.11 To precisely compare the cyclic voltammograms of (CF3)2CFI and the
commonly used linear RfnI (n = 3, 4, 6, 8),16 we studied their electrochemical
behaviors in an identical system (see SI). The experiments were performed at ambient
temperature under air on a glass carbon (gc) working electrode, a Pt wire counter
electrode, and a SCE reference electrode in DMF using n-Bu4NPF6 (0.1 M)
supporting electrolyte with a scan rate of 0.2 V/s. The reduction waves were
scrupulously referenced to an external ferrocene/ferrocenium redox couple in DMF
(E° = 0.45 V vs SCE). It was shown that (CF3)2CFI was irreversibly reduced at a

potential of -0.75 V (-0.66 V 11), whereas CF3(CF2)2I was reduced at -1.40V (-1.00 V
11) (see SI). This trend was in agreement with that measured on a platinum working
electrode in CH3CN containing 0.1 M n-Bu4NBF4 supporting electrolyte in the
literature.11 More importantly, it matched the iodination trend (Table 1), suggesting
that the oxidation ability (or electron affinity) of RfnI might reflect their capacity of
Cu-catalyzed aerobic iodination of arylboronic acids. Besides, the cyclic
voltammograms of CF3(CF2)2I (-1.40 V), CF3(CF2)3I (-1.32 V), CF3(CF2)5I (-1.34 V,
-1.32 16a), and CF3(CF2)7I (-1.22 V) showed comparable peak potentials (see SI).
Their electron affinity slightly changed with increasing the length of the
perfluoroalkyl chains, wherein no significant differences were found in the iodination
reactions (Table 1). The addition of hydroquinone to a mixture of (CF3)2CFI,
n-Bu4NPF6, and DMF could further decrease the one-electron reduction potential of
(CF3)2CFI (Figure 1). When 1, 2, and 4 equivalents of hydroquinone were added into
the electrochemical system, the positive shifts of the reduction potential from -0.75 V
to -0.61 V, -0.58 V, and -0.55 V were observed, respectively. These trends again
agreed with the promoted iodination of arylboronic acids by (CF3)2CFI in the
presence of hydroquinone (entry 5, Table 1). We speculated that hydroquinone might
rapidly trap the (CF3)2CF• radical once it formed in the concerted
reduction/bond-cleavage process,16a which led to the positive shift of the reduction
19
potential of (CF3)2CFI. The F NMR and GC-MS analyses of the reaction mixture
suggested the formation of (CF3)2CF-hydroquinone adduct (m/z = 278.0, see SI).
Although the assumption fits the linear perfluoroalkyl iodides as well, the addition of
hydroquinone into the reaction mixtures of 1a and the linear RfnI didn’t cause
remarkable changes in the formation of 2a (see SI).
Furthermore, the Cu-mediated cross-coupling of aryl iodide with (CF3)2CFI has
been disclosed.4a Since C6H5I was successfully perfluoroalkylated by (CF3)2CFI at
120 oC in the presence of excess copper powder, we wonder whether the aryl iodides
formed in the reactions of arylboronic acids and (CF3)2CFI could be further
transformed in one pot. Thus, the reaction of 1b with (CF3)2CFI (3, 4, or 5 equiv) and
Cu (3 or 4 equiv) was performed in DMF at 100 oC or 120 oC under a N2 atmosphere
for 3 days, wherein 4b was formed in 4-9% yields (Scheme 2). If the reaction of 1b,
(CF3)2CFI (3, 4, or 5 equiv), and Cu (3 or 4 equiv) was conducted at room
o
temperature in air for 24 h and heated at 120 C in a sealed tube for another 24 h, 4b

was obtained in < 1% yield, implying that the conversion of aryl iodide formed in situ
in the reaction to perfluoroalkylation product is much cumbersome.
Based on the results above, a plausible halogenophilic mechanism was suggested
for the reaction (Scheme 3).14a First, [ArCu] is derived from arylboronic acid in the
presence of air and Cu powder or cupric salts.14a Then (CF3)2CFI is halogenophilically
attacked by [ArCu] to produce Cu[ArICF(CF3)2] or ArCuI[CF(CF3)2]. The
coordination intermediate Cu[ArICF(CF3)2] is unstable and rapidly decomposes,
generating ArI and “CuCF(CF3)2”. The “CuCF(CF3)2” species might be quenched by
the environment releasing HCF(CF3)2 or perfluoroalkylate ArB(OH)2, which was
19
determined by F NMR analysis of the reaction mixture. On the other hand, the
oxidative-addition intermediate ArCuI[CF(CF3)2] cannot be excluded, which might
undergo reductive elimination to form ArI and/or ArCF(CF3)2. Owing to the strong
electron affinity (E1/2 = -0.75 V) and the huge steric hindrance of (CF3)2CFI, the
formation of Cu[ArICF(CF3)2] may be predominant in the reaction. The observation
that iodination proceeded much more easily than perfluoroalkylation using (CF3)2CFI
in the presence of Cu-catalysts is tentatively ascribed to the huge steric hindrance and
−
the low nucleophilicity of the CF(CF3)2 moiety. Nevertheless, the exact mechanism
is still unclear.
Conclusions
In conclusion, we have disclosed the different reactivity of the branched
(CF3)2CFI from the linear perfluoroalkyl iodides (CF3(CF2)nI) in the aerobic
transformation of arylboronic acids at room temperature in the presence of diverse
Cu-catalysts. The reaction of (CF3)2CFI with R-B(OH)2 at room temperature under air
in the presence of catalytic Cu powder provided exclusively the iodides (R-I),17
showing better iodination ability than the linear analogs, while the aerobic reactions
of arylboronic acids with (CF3)2CFI at room temperature in the presence of Cu(OAc)2
gave the perfluoroalkylated products (R-CF(CF3)2) in acceptable to moderate yields.
(CF3)2CFI is thermodynamically easier to reduce than the linear analogs. The addition
of hydroquinone further increased the oxidation ability (or electron affinity) of
(CF3)2CFI, which facilitated the iodination of boronic acids and provided the
ipso-iodination products in high yields. The copper carboxylates might favor the
perfluoroalkylation, the addition of which could successfully give rise to Ar-CF(CF3)2.

These transformations have tuned the iodination and perfluoroalkylation of
arylboronic acids with (CF3)2CFI by the choice of appropriate copper-catalysts. The
mechanistic study and the application of (CF3)2CFI as a versatile oxidant, iodination
reagent, and (CF3)2CF source will be continued in the near future.
Experimental Section
All reactions were performed in air (air balloon) in a closed tube with a rubber stopper.
All reagents and solvents were purchased from commercial sources and used without
further purification. Unless otherwise stated, NMR spectra were recorded in CDCl3 at
1
19
500 or 400 MHz for H NMR, 471 or 376 MHz for F NMR, and 126 or 100 MHz
13
for C NMR on Bruker Avance spectrometers. The chemical shifts were reported in
ppm relative to TMS (0 ppm) or CFCl3 (0 ppm) as an internal or external standard.
19
The F NMR yields of the products were determined by using PhCF3 as an internal
standards. The HPLC experiments were carried out on a Waters e2695 instrument
(column: J&K, RP-C18, 5 μm, 4.6 × 150 mm), and the yields of the products were
determined by using the corresponding pure compounds as the external standards. The
cyclic voltammograms of (CF3)2CFI and the linear RfnI were measured on a CS310
CorrTest instrument. The melting points of the products were measured and
uncorrected.
Typical procedure for the iodination of 1a-t by (CF3)2CFI
(4-Nitrophenyl)boronic acid (0.067 g, 0.4 mmol), copper powder (0.0052 g, 0.08
mmol,), (CF3)2CFI (0.178 g, 0.6 mmol), and DMF (2 mL) were placed in a closed
tube with a rubber stopper. The mixture was reacted at room temperature equipped
with an air balloon for 24 h. The resulting suspension was poured into water and
extracted with ethyl acetate. The organic layer was dried over anhydrous Na2SO4 and
concentrated to dryness. The crude product was purified by flash column
chromatography on silica gel using petroleum ether / ethyl acetate = 20 : 1 (v / v) as
eluent to give 0.086 g of 2j as a light yellow solid (0.35 mmol, 87%).
4-Iodo-1,1'-biphenyl (2b)18a
Yield: 49.3 mg (88%); white solid; mp 108.3−109.2 °C.
1H NMR (400 MHz, CDCl3): δ 7.69 (dm, J = 8.3 Hz, 2H, ArH), 7.47 (dm, J = 7.3 Hz,
2H, ArH), 7.36 (tm, J = 7.4 Hz, 2H, ArH), 7.28 (tt, J = 7.3 Hz, J = 1.2 Hz, 1H, ArH),

7.25 (dm, J = 8.6 Hz, 2H, ArH).
13C NMR (100 MHz, CDCl3): δ 140.8 (s), 140.1 (s), 137.9 (s), 129.1 (s), 128.9 (s),
127.7 (s), 126.9 (s), 93.1 (s).
1-Iodo-2-methoxybenzene (2c)18b
Yield: 40.3 mg (86%); light yellow liquid.
1H NMR (400 MHz, CDCl3): δ 7.70 (dd, J = 7.6 Hz, J = 1.5 Hz, 1H, ArH), 7.24 (tm, J
= 8.3 Hz, 1H, ArH), 6.76 (dd, J = 8.2 Hz, J = 1.2 Hz, 1H, ArH), 6.64 (td, J = 7.6 Hz, J
= 1.2 Hz, 1H, ArH), 3.81 (s, 3H, CH3).
13C NMR (100 MHz, CDCl3): δ 158.1 (s), 139.5 (s), 129.5 (s), 122.5 (s), 111.0 (s), 86.0
(s), 56.3 (s).
1-Iodo-3-methoxybenzene (2d)18c
Yield: 39.3 mg (84%); light yellow liquid.
1H NMR (400 MHz, CDCl3): δ 7.21 (dm, J = 7.6 Hz, 1H, ArH), 7.18 (m, 1H, ArH),
6.93 (t, J = 8.5 Hz, 1H, ArH), 6.80 (dm, J = 8.5 Hz, 1H, ArH), 3.71 (s, 3H, CH3).
13C NMR (100 MHz, CDCl3): δ 160.2 (s), 130.8 (s), 129.9 (s), 123.0 (s), 113.8 (s), 94.4
(s), 55.4 (s).
1-Iodo-4-methoxybenzene (2e)18d
Yield: 39.8 mg (85%); off-white solid; mp 46.7−47.5 °C
1H NMR (400 MHz, CDCl3): δ 7.48 (dm, J = 9.1 Hz, 2H, ArH), 6.60 (d, J = 9.1 Hz,
2H, ArH), 3.70 (s, 3H, CH3).
13C NMR (100 MHz, CDCl3): δ 159.5 (s), 138.2 (s), 116.4 (s), 82.7 (s), 55.4 (s).
1-Tert-butyl-4-iodobenzene (2f)18e
Yield: 44.7 mg (86%); colorless liquid.
1H NMR (400 MHz, CDCl3): δ 7.54 (d, J = 8.5 Hz, 2H, ArH), 7.06 (d, J = 8.6 Hz, 2H,
ArH), 1.22 (s, 9H, CH3).
13C NMR (100 MHz, CDCl3): δ 150.9 (s), 137.1 (s), 127.6 (s) , 90.6 (s), 34.6 (s), 31.2
(s).
1-Iodo-4-(trifluoromethyl)benzene (2g)
Yield: 87%, determined by HPLC using 1-iodo-4-(trifluoromethyl)benzene as the

external standard (retention time = 5.342 min, λmax = 238 nm, methanol / water = 80 :
20 (v / v)).
1-Fluoro-4-iodobenzene (2h)
Yield: 92%, determined by HPLC using 1-fluoro-4-iodobenzene as the external
standard (retention time = 4.378 min, λmax = 224 nm, methanol / water = 80 : 20 (v /
v)).
1-Iodo-3-nitrobenzene (2i)18c
Yield: 43.8 mg (88%); light yellow liquid.
1H NMR (400 MHz, CDCl3): δ 8.48 (t, J = 1.8 Hz, 1H, ArH), 8.13 (dm, J = 8.5 Hz,
1H, ArH), 7.95 (dm, J = 7.9 Hz, 1H, ArH), 7.22 (t, J = 7.9 Hz, 1H, ArH).
13C NMR (100 MHz, CDCl3): δ 148.5 (s), 143.5 (s), 132.4 (s), 130.7 (s), 122.8 (s), 93.5
(s).
1-Iodo-4-nitrobenzene (2j)18f
Mp 168.4−169.5 °C.
1H NMR (400 MHz, CDCl3): δ 7.86 (AB peak, J = 14.7 Hz, J = 9.4 Hz, 4H, ArH).
13C NMR (100 MHz, CDCl3): δ 147.8 (s), 138.7 (s), 124.9 (s), 102.7 (s).
4-Iodobenzonitrile (2k)18f
Yield: 38.9 mg (85%); off white solid; mp 121.2−122.1 °C.
1H NMR (400 MHz, CDCl3): δ 7.78 (dm, J = 8.8 Hz, 2H, ArH), 7.30 (dm, J = 8.5 Hz,
2H, ArH).
13C NMR (100 MHz, CDCl3): δ 138.6 (s), 133.2 (s), 118.3 (s), 111.8 (s), 100.3 (s).
2-Iodobenzaldehyde (2l)18g
Yield: 38.5 mg (83%); light yellow liquid.
1H NMR (400 MHz, CDCl3): δ 10.0 (s, 1H, CHO), 7.88 (dd, J = 7.9 Hz, J = 1.1 Hz,
1H, ArH), 7.81 (dd, J = 7.6 Hz, J = 1.8 Hz, 1H, ArH), 7.39 (tm, J = 7.6 Hz, 1H, ArH),
7.21 (td, J = 7.9 Hz, J = 1.8 Hz, 1H, ArH).
13C NMR (100 MHz, CDCl3): δ 195.8 (s), 140.7 (s), 135.5 (s), 135.2 (s), 130.3 (s),
128.8 (s), 100.7 (s).

Ethyl 4-iodobenzoate (2m)18f
Yield: 45.1 mg (82%); colorless liquid.
1H NMR (400 MHz, CDCl3): δ 7.70 (AB peak, J = 20.5 Hz, J = 8.5 Hz, 4H, ArH),
3.30 (q, J = 7.0 Hz, 2H, CH2), 1.32 (t, J = 7.1 Hz, 3H, CH3).
13C NMR (100 MHz, CDCl3): δ 166.2 (s), 137.7 (s), 131.0 (s), 130.0 (s), 100.6 (s), 61.3
(s), 14.3 (s).
1-Iodonaphthalene (2n)18d
Yield: 43.5 mg (86%); brown liquid.
1H NMR (400 MHz, CDCl3): δ 8.02 (m, 1H, ArH), 8.00 (m, 1H, ArH), 7.76 (dm, J =
8.4 Hz, 1H, ArH), 7.69 (dm, J = 8.2 Hz, 1H, ArH), 7.50 (tm, J = 7.0 Hz, 1H, ArH),
7.44 (tm, J = 7.1 Hz, 1H, ArH), 7.10 (dd, J = 8.2 Hz, J = 7.3 Hz, 1H, ArH).
13C NMR (100 MHz, CDCl3): δ 137.5 (s), 134.4 (s), 134.2 (s), 132.2 (s), 129.0 (s),
128.6 (s), 127.7 (s), 126.9 (s), 126.8 (s), 99.6 (s).
2-Iodonaphthalene (2o)18f
Yield: 40.3 mg (79%); brown solid; mp 46.4−47.1 °C.
1H NMR (400 MHz, CDCl3): δ 8.17 (d, J = 1.1 Hz, 1H, ArH), 7.72 (m, 1H, ArH),
7.66−7.63 (m, 2H, ArH), 7.50 (d, J = 8.8 Hz, 1H, ArH), 7.42 (m, 2H, ArH).
13C NMR (100 MHz, CDCl3): δ 136.7 (s), 135.0 (s), 134.4 (s), 132.1 (s), 129.5 (s),
127.9 (s), 126.8 (s), 126.7 (s), 126.5 (s), 91.5 (s).
(E)-(2-Iodovinyl)benzene (2p)18h
Yield: 78.2 mg (85%); yellow liquid.
1H NMR (400 MHz, CDCl3): δ 7.36 (d, J = 15.0 Hz, 1H, Hvinyl), 7.28−7.21 (m, 5H,
ArH), 6.76 (d, J = 15.0 Hz, 1H, Hvinyl).
13C NMR (100 MHz, CDCl3): δ 145.0 (s), 137.7 (s), 128.7 (s), 128.4 (s), 126.0 (s).
2-Bromo-5-iodopyridine (2q)18i
Yield: 44.7 mg (79%); white solid; mp 113.9−115.9 °C.
1H NMR (400 MHz, CDCl3): δ 8.52 (d, J = 2.1 Hz, 1H, ArH), 7.75 (dd, J = 8.2 Hz, J
= 2.3 Hz, 1H, ArH), 7.22 (d, J = 8.2 Hz, 1H, ArH).
13C NMR (100 MHz, CDCl3): δ 156.2 (s), 146.6 (s), 141.5 (s), 130.0 (s), 91.7 (s).

2-Iodobenzo[b]thiophene (2r)18j
Yield: 46.8 mg (90%); white solid; mp 58.1−59.1 °C.
1H NMR (400 MHz, CDCl3): δ 7.69−7.67 (m, 1H, ArH), 7.64−7.62 (m, 1H, ArH),
7.45 (d, J = 0.9 Hz, 1H, ArH), 7.24−7.18 (m, 2H, ArH).
13C NMR (100 MHz, CDCl3): δ 144.4 (s), 140.8 (s), 133.8 (s), 124.5 (s), 124.4 (s),
122.3 (s), 121.3 (s), 78.4 (s).
2-Iodobenzofuran (2s)18j
Yield: 35.1 mg (72%); light yellow liquid.
1H NMR (400 MHz, CDCl3): δ 7.52−7.46 (m, 2H, ArH), 7.23−7.18 (m, 2H, ArH),
6.95 (d, J = 0.9 Hz, 1H, ArH).
13C NMR (100 MHz, CDCl3): δ 158.2 (s), 129.2 (s), 124.3 (s), 123.2 (s), 119.7 (s),
117.3 (s), 110.9 (s), 95.9 (s).
Iodobenzene (2t)
Yield: 98%, determined by HPLC using iodobenzene as the external standard
(retention time = 4.751 min, λmax = 226 nm, methanol / water = 80 : 20 (v / v)).
Typical procedure for the perfluoroalkylation of 1a, 1b, 1k, 1o, 1t, 1v-z, and
1a’-c’ by (CF3)2CFI
(1,1'-Biphenyl)-4-ylboronic acid (0.119 g, 0.6 mmol), heptafluoroisopropyl iodide
(0.059 g, 0.2 mmol), Cu(OAc)2 (0.036 g, 0.2 mmol), and DMF (2 mL) were placed in
a closed tube with a rubber stopper. The mixture was reacted at room temperature
under air for 24 h. The resulting suspension was poured into water and extracted with
ethyl acetate (for three times). The combined organic layers were washed with water,
dried over anhydrous Na2SO4, and concentrated to dryness. The residue was purified
by flash column chromatography on silica gel using petroleum ether or hexane as
eluent to give 4b as a white solid (40 mg, 0.12 mmol, 62%).
1-Chloro-4-(perfluoropropan-2-yl)benzene (4a)18k
Yield: 28%, determined by 19F NMR using PhCF3 as an internal standard.

4-(Perfluoropropan-2-yl)-1,1'-biphenyl (4b)15a
Mp 88.9−90.1 °C.
1H (400 MHz, CDCl3): δ 7.71 (AB peak, J = 13.6 Hz, J = 8.9 Hz, 4H, ArH), δ 7.62 (d,
J = 7.5 Hz, 2H, ArH), δ 7.49 (t, J = 7.6 Hz, 2H, ArH), δ 7.41 (t, J = 7.4 Hz, 1H, ArH).
13C (100 MHz, CDCl3): δ 144.0 (s), 139.6 (s), 129.0 (s), 128.2 (s), 127.5 (d, J = 1.9
Hz), 127.2 (s), 126.2 (d, J = 10.4 Hz), 125.5 (d, J = 21.1 Hz), 120.7 (qd, J = 286.2,
27.4 Hz, CF3), 92.9−90.2 (m, CF).
19F (376 MHz, CDCl3): δ -75.6 (d, J = 7.9 Hz, 6F), δ -182.5 (hept, J = 7.9 Hz, 1F).
4-(Perfluoropropan-2-yl)benzonitrile (4k)15a
Yield: 17%, determined by 19F NMR using PhCF3 as an internal standard.
2-(Perfluoropropan-2-yl)naphthalene (4o)15a
Yield: 15.4 mg (26%); white solid; mp 62.0−63.0 °C.
1H NMR (400 MHz, CDCl3): δ 8.16 (s, 1H, ArH), 7.98−7.90 (m, 3H, ArH), 7.66−7.57
(m, 3H, ArH).
13C NMR (100 MHz, CDCl3): δ 134.1 (s), 132.5 (d, J = 2.1 Hz), 128.9 (d, J = 2.1 Hz),
128.8 (s), 128.0 (s), 127.7 (s), 127.2 (s), 126.5 (d, J = 12.0 Hz), 124.0 (d, J = 20.8 Hz),
121.6 (d, J = 9.6 Hz), 120.8 (qd, J = 287.6 Hz, J = 27.1 Hz, CF3), 90.8−86.5 (m, CF).
19F NMR (376 MHz, CDCl3): δ -75.4 (d, J = 7.2 Hz, 6F), -181.9 (hept, J = 7.2 Hz,
1F).
(Perfluoropropan-2-yl)benzene (4t)15a
Yield: 50%, determined by 19F NMR using PhCF3 as an internal standard.
1-(Benzyloxy)-4-(perfluoropropan-2-yl)benzene (4v)15b
Yield: 14.8 mg (21%); white solid; mp 75.1−76.8 °C.
1H NMR (400 MHz, CDCl3): δ 7.53 (d, J = 8.8 Hz, 2H, ArH), 7.46−7.34 (m, 5H,
ArH), 7.08 (d, J = 8.9 Hz, 2H, ArH), 5.11 (s, 2H, CH2).
13C NMR (100 MHz, CDCl3): δ 160.7 (s), 136.3 (s), 128.7 (s), 128.3 (s), 127.5 (s)

127.3 (d, J = 10.5 Hz), 120.7 (qd, J = 287.0 Hz, J = 27.6 Hz, CF3), 118.8 (d, J = 20.9
Hz), 115.1 (d, J = 1.9 Hz), 93.0−90.2 (m, CF), 70.2 (s).
19F NMR (376 MHz, CDCl3): δ -75.9 (d, J = 7.3 Hz, 6F), -181.7 (hept, J = 7.7 Hz,
1F).
1-(Benzyloxy)-2-chloro-4-(perfluoropropan-2-yl)benzene (4w)
Yield: 18.6 mg (24%); white solid; mp 48.0−49.0 °C.
IR (KBr): 2918, 2871, 1605, 1508, 1453, 1413, 1380, 1314, 1270, 1230, 1209, 1165,
1105, 1068, 1036, 979, 884, 805, 727, 693 cm−1.
1H NMR (500 MHz, CDCl3): δ 7.64 (s, 1H, ArH), 7.47−7.40 (m, 5H, ArH), 7.36 (t, J
= 7.1 Hz, 1H, ArH), 7.06 (d, J = 8.8 Hz, 1H, ArH), 5.21 (s, 2H, CH2).
13C NMR (126 MHz, CDCl3): δ 156.3 (s), 135.7 (s), 128.8 (s), 128.3 (s), 127.9 (d, J =
11.6 Hz), 127.1 (s), 125.4 (d, J = 10.9 Hz), 124.1 (d, J = 2.2 Hz), 120.5 (qd, J = 288.7
Hz, J = 27.6 Hz, CF3), 119.6 (d, J = 21.7 Hz), 113.6 (d, J = 1.8 Hz), 90.1−87.3 (m,
CF), 70.9 (s).
19F NMR (471 MHz, CDCl3): δ -75.8 (d, J = 7.3 Hz, 6F), -181.5 (hept, J = 7.1 Hz,
1F).
MS (EI): m/z = 386.0.
HRMS-EI: m/z [M]+ calcd for C16H10ClF7O: 386.0308; found: 386.0310.
1-(Perfluoropropan-2-yl)-4-phenoxybenzene (4x)
Yield: 14.2 mg (42%, 0.1 mmol scale of (CF3)2CFI); light yellow liquid.
IR (KBr): 3079, 3043, 2927, 2047, 1901, 1614, 1588, 1512, 1490, 1424, 1199, 1133,
1097, 1070, 1022, 982, 954, 915, 871, 830, 800, 764, 748, 736, 703, 695 cm−1.
1H NMR (400 MHz, CDCl3): δ 7.54 (d, J = 8.8 Hz, 2H, ArH), 7.40 (t, J = 8.0 Hz, 2H,
ArH), 7.20 (t, J = 7.4 Hz, 1H, ArH), 7.09−7.05 (m, 4H, ArH).
13C NMR (126 MHz, CDCl3): δ 159.9 (s), 155.6 (s), 130.1 (s), 127.5 (d, J = 11.0 Hz),
124.6 (s), 120.6 (qd, J = 287.2 Hz, J = 27.9 Hz, CF3), 120.5 (d, J = 20.4 Hz), 120.1 (s),
117.9 (d, J = 2.1 Hz), 91.5 (dm, J = 201.5 Hz, J = 32.8 Hz, CF).
19F NMR (376 MHz, CDCl3): δ -75.8 (d, J = 7.3 Hz, 6F), -181.6 (m, 1F).
MS (EI): m/z = 338.1.

HRMS-EI: m/z [M]+ calcd for C15H9F7O: 338.0542 ; found: 338.0550.
3-(Perfluoropropan-2-yl)-1,1'-biphenyl (4y)
Yield: 13.6 mg (21%); colorless liquid.
IR (KBr): 3018, 2924, 1734, 1654, 1481, 1282, 1226, 1202, 1167, 1125, 982, 757,
745, 725, 697 cm−1.
1H NMR (500 MHz, CDCl3): δ 7.82 (s, 1H, ArH), 7.76 (d, J = 7.0 Hz, 1H, ArH),
7.60−7.56 (m, 4H, ArH), 7.48 (t, J = 7.1 Hz, 2H, ArH), 7.41 (t, J = 7.1 Hz, 1H, ArH).
13C NMR (126 MHz, CDCl3): δ 142.2 (d, J = 2.1 Hz), 139.9 (s), 129.8 (s), 129.3 (d, J
= 2.1 Hz), 129.0 (s), 128.0 (s), 127.5 (s), 127.3 (s), 124.4 (t, J = 8.9 Hz), 120.7 (qd, J
= 287.3 Hz, J = 28.1 Hz, CF3), 91.5 (dq, J = 202.0 Hz, J = 33.2 Hz, CF).
19F NMR (471 MHz, CDCl3): δ -75.5 (d, J = 7.1 Hz, 6F), -182.3 (hept, J = 7.4 Hz,
1F).
MS (EI): m/z = 322.1.
HRMS-EI: m/z [M]+ calcd for C17H9F7: 322.0592; found: 322.0584.
2-Methoxy-6-(perfluoropropan-2-yl)naphthalene (4z)15a
Yield: 16.6 mg (25%); white solid; mp 49.0−51.0 °C.
1H NMR (500 MHz, CDCl3): δ 8.05 (s, 1H, ArH), 7.83 (t, J = 9.4 Hz, 2H, ArH), 7.59
(d, J = 8.7 Hz, 1H, ArH), 7.24 (d, J = 9.0 Hz, 1H, ArH), 7.17 (s, 1H, ArH), 3.95 (s,
3H, CH3).
13C NMR (100 MHz, CDCl3): δ 159.3 (s), 135.5 (s), 130.2 (s), 128.0 (d, J = 2.2 Hz),
127.6 (d, J = 2.1 Hz), 126.1 (d, J = 11.6 Hz), 122.2 (d, J = 9.3 Hz), 121.6 (d, J = 20.6
Hz), 120.8 (qd, J = 287.2 Hz, J = 27.6 Hz, CF3), 120.2 (s), 105.5 (s), 55.4 (s).
19F NMR (471 MHz, CDCl3): δ -75.5 (d, J = 7.2 Hz, 6F), -181.7 (hept, J = 6.9 Hz,
1F).
9-(Perfluoropropan-2-yl)phenanthrene (4a')
Yield: 15.9 mg (46%, 0.1 mmol scale of (CF3)2CFI); white solid; mp 87.0−88.0 °C.

IR (KBr): 2960, 2920, 2850, 1960, 1540, 1501, 1450, 1289, 1260, 1244, 1210, 1182,
1161, 1127, 1099, 1071, 973, 804, 763, 749, 729, 718 cm−1.
1H NMR (400 MHz, CDCl3): δ 8.81 (d, J = 7.8 Hz, 1H, ArH), 8.71 (d, J = 8.4 Hz, 1H,
ArH), 8.56 (d, J = 8.5 Hz, 1H, ArH), 8.11 (s, 1H, ArH), 7.94 (d, J = 7.9 Hz, 1H, ArH),
7.78 (tm, J = 7.8 Hz, 1H, ArH), 7.73 (t, J = 7.5 Hz, 1H, ArH), 7.67 (tm, J = 7.4 Hz,
2H, ArH).
13C NMR (126 MHz, CDCl3): δ 132.5 (s), 131.4 (d, J = 9.6 Hz), 130.9 (s), 129.9 (s),
129.3 (s), 129.1 (s), 129.0 (d, J = 2.1 Hz), 127.4 (s), 127.3 (d, J = 3.1 Hz), 127.1 (s),
126.4 (d, J = 22.6 Hz), 123.3 (s), 122.6 (s), 121.3 (qd, J = 288.5 Hz, J = 28.4 Hz, CF3),
120.7 (d, J = 19.2 Hz), 95.6 (dm, J = 207.0 Hz, CF).
19F NMR (376 MHz, CDCl3): δ -73.0 (d, J = 6.9 Hz, 6F), -174.2 (hept, J = 6.7 Hz,
1F).
MS (EI): m/z = 346.1.
HRMS-EI: m/z [M]+ calcd for C17H9F7: 346.0592; found: 346.0588.
4-(Perfluoropropan-2-yl)dibenzo[b,d]furan (4b')
Yield: 18.1 mg (54%, 0.1 mmol scale of (CF3)2CFI); white solid; mp 76.0−77.0 °C.
IR (KBr): 3064, 3046, 1894, 1785, 1596, 1471, 1444, 1343, 1321, 1307, 1241, 1195,
1153, 1099, 1007, 928, 849, 840, 749, 721 cm−1.
1H NMR (400 MHz, CDCl3): δ 8.14 (dd, J = 7.7 Hz, J = 0.9 Hz, 1H, ArH), 7.99 (d, J
= 7.5 Hz, 1H, ArH), 7.69 (d, J = 7.9 Hz, 1H, ArH), 7.64 (d, J = 8.3 Hz, 1H, ArH),
7.53 (td, J = 7.8, 1.1 Hz, 1H, ArH), 7.47 (t, J = 7.8 Hz, 1H, ArH), 7.40 (t, J = 7.5 Hz,
1H, ArH).
13C NMR (100 MHz, CDCl3) δ 156.2 (s), 152.7 (d, J = 3.1 Hz), 128.2 (s), 126.4 (s),
124.8 (d, J = 13.2 Hz), 123.8 (s), 123.4 (s), 122.8 (s), 122.8 (d, J = 2.0 Hz), 120.8 (qd,
J = 287.3 Hz, J = 28.1 Hz, CF3), 120.6 (s), 112.1 (s), 111.3 (d, J = 22.7 Hz),
91.4−88.6 (m, CF).
19F NMR (471 MHz, CDCl3) δ -75.0 (d, J = 7.0 Hz, 6F), -179.4 (m, 1F).
MS (EI): m/z = 336.0.
HRMS-EI: m/z [M]+ calcd for C15H7F7O: 336.0385; found: 336.0372.

Methyl 4-(perfluoropropan-2-yl)benzoate (4c')15a
Yield: 24%, determined by 19F NMR using PhCF3 as an internal standard.
Acknowledgements
We thank Wuhan University of Technology, the Natural Science Foundation of
Hubei Province (China) (2015CFB176), the “Chutian Scholar” Program from
Department of Education of Hubei Province (China), and the “Hundred Talent”
Program of Hubei Province for financial support.

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4E-5
2E-5
0
-2E-5
-4E-5
Ⅲ
-6E-5
Ⅱ
Ⅰ
-8E-5
Ⅳ
-0.0001
-0.00012
-0.00014
-3
-2
-1
E (V)
0
1
Figure 1 Cyclic voltammograms of (CF3)2CFI (I, 0.01 M, black), (CF3)2CFI and
hydroquinone (II, 0.01 M/0.01 M, red), (CF3)2CFI and hydroquinone (III, 0.01
M/0.02 M, green), and (CF3)2CFI and hydroquinone (IV, 0.01 M/0.04 M, blue) in
DMF containing n-Bu4NPF6 supporting electrolyte (0.1 M), and recorded on a gc
working electrode, a Pt wire counter electrode, and a SCE reference electrode. The
experiments were carried out at ambient temperature under air with a scan rate of 0.2
V/s. The peak potentials of I-IV are -0.75 V, -0.61 V, -0.58 V, and -0.55 V,
respectively, referenced to Fc/Fc+ in DMF (0.45 V vs SCE).

Scheme 1 Cu(OAc)2-mediated aerobic perfluoroalkylation of ArB(OH)2 by the linear
CF3CF2CF2I under the standard reaction conditions

Scheme 2 The Cu-mediated one-pot perfluoroalkylation of 1b by (CF3)2CFI at 100 or
120 oC

Scheme 3 A proposed reaction mechanism for Cu-mediated aerobic iodination and
perfluoroalkylation of ArB(OH)2 by (CF3)2CFI

Table 1 Iodination of arylboronic acid (1a) by linear RfnI and the branched (CF3)2CFI
Yield
(2a, %) b
Yield
(3a, %) c
55
Entry RfnI a
X
Additive
1
2
3
4
5
6
7
8
CF3CF2I
1.0
1.0
0.2
1.0
0.2
1.0
1.0
1.0
-
4
CF3(CF2)2I
(CF3)2CFI
(CF3)2CFI
(CF3)2CFI
CF3(CF2)3I
CF3(CF2)5I
CF3(CF2)7I
-
10
88
81
> 99
9
56
-
10
-
4.5
Hydroquinone
0.01
62
-
-
-
9
59
8
51
a Reaction conditions: 1a (0.2 mmol) / RfnI (0.3 mmol) / Cu powder (0.04 or 0.2
mmol) / DMF (2 mL) / r.t. / air / 24 h / hydroquinone (0.4 mmol or none).
b Yields
c
were determined by HPLC using 2a as the external standard.
determined by HPLC using 3a as the external standard.
Yields were