Light-induced BiOBr nanosheets accelerated highly regioselective intermolecular trifluoromethylation/arylation of alkenes to synthesize CF3-containing aza-heterocycles

Article abstract of DOI:10.1016/j.tet.2015.04.056

A light-induced, BiOBr nanosheets accelerated intermolecular one-pot tandem trifluoromethylation/arylation of alkenes was presented. With this method, a series of CF₃-containing aza-heterocycles with high selectivity were fabricated in moderate to good yields. Preliminary mechanistic studies revealed that the exceptional transformation was originated from the synergistic effect of photogenerated electrons and holes. Density function theory (DFT) was adopted to understand the high selectivity of this photocatalytic chemical transformation.

Full text of DOI:10.1016/j.tet.2015.04.056

Accepted Manuscript
Light-Induced BiOBr Nanosheets Accelerated Highly Regioselective Intermolecular
Trifluoromethylation/Arylation of Alkenes to Synthesize CF -Containing Aza-
3
Heterocycles
Cuibo Liu, Weiwei Zhao, Yi Huang, Hongming Wang, Bin Zhang
PII:
S0040-4020(15)00555-4
10.1016/j.tet.2015.04.056
TET 26659
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 9 March 2015
Revised Date: 13 April 2015
Accepted Date: 18 April 2015
Please cite this article as: Liu C, Zhao W, Huang Y, Wang H, Zhang B, Light-Induced BiOBr Nanosheets
Accelerated Highly Regioselective Intermolecular Trifluoromethylation/Arylation of Alkenes to Synthesize
CF -Containing Aza-Heterocycles, Tetrahedron (2015), doi: 10.1016/j.tet.2015.04.056.
3
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Light-Induced BiOBr Nanosheets
Accelerated Highly Regioselective
Intermolecular
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Trifluoromethylation/Arylation of Alkenes to
Synthesize CF -Containing Aza-Heterocycles
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Cuibo Liu, Weiwei Zhao, Yi Huang, Hongming Wang, and Bin Zhang*
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Department of Chemistry, School of Science, Tianjin University, and Collaborative Innovation Center of
Chemical Science and Engineering (Tianjin), Tianjin 300072, China. E-mail: bzhang@tju.edu.cn
b
Institute for Advanced Study, Nanchang University, Nanchang 330031, China.

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Tetrahedron
journal homepage: www.elsevier.com
Light-Induced BiOBr Nanosheets Accelerated Highly Regioselective Intermolecular
Trifluoromethylation/Arylation of Alkenes to Synthesize CF -Containing Aza-
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4 Cuibo Liu , Weiwei Zhao , Yi Huang , Hongming Wang , and Bin Zhang*
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Department of Chemistry, School of Science, Tianjin University, and Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin
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00072, China. E-mail: bzhang@tju.edu.cn
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Institute for Advanced Study, Nanchang University, Nanchang 330031, China.
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
A
light-induced, BiOBr nanosheets accelerated intermolecular one-pot tandem
trifluoromethylation/arylation of alkenes was presented. With this method, a series of CF
containing aza-heterocycles with high selectivity were fabricated in moderate to good yields.
Preliminary mechanistic studies revealed that the exceptional transformation was originated
from the synergistic effect of photogenerated electrons and holes. Density function theory (DFT)
was adopted to understand the high selectivity of this photocatalytic chemical transformation.
3
-
Available online
Keywords:
2
009 Elsevier Ltd. All rights reserved.
BiOBr nanosheets;
Photocatalysis;
Trifluoromethylation;
Arylation;
Aza-heterocycles.
9
5 1. Introduction
6
relatively limited. Literatures revealed that inorganic nanosheets
were found to be superior in dramatically improving their
intrinsic catalytic properties owing to the higher surface-to-
volume ratio and the faster arrival to the reaction sites of the
The use of photocatalysts to initiate organic transformations1
7
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0
1
2
3
4
5
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1
has been one of the quick growing fields in synthetic chemistry.
To date, many pioneering and intriguing works based on this
strategy have been accomplished by several groups such as
10
photogenerated electrons or holes. Therefore, the synthesis of
inorganic nanosheets as photocatalysts for efficient constructions
of complex organic compounds, especially molecules with
potential applications in pharmaceuticals and agrochemicals was
of great interest.
2
3
4
5
6
MacMillan, Yoon, Stephenson, Sanford, and Akita . Although
these works were very brilliant, the iridium(III) and ruthenium(II)
catalysts adopted were expensive, toxic, and sometimes air-
sensitive or water-sensitive. In addition to metal complexes,
some organic dyes such as eosin Y, fluorescein, nile red, and
triphenylpyrylium salts could also function as the favourable
Difunctionalization of alkenes, means introduction of two
different functional groups, particularly the CF
C=C double bond in a single operation, was an attractive protocol
moiety to the
3
7
photocatalysts in some organic reactions. Whereas, tedious
1
1
procedures were always needed for the preparation of some
organic dyes catalysts. These disadvantages of metal complexes
and organic dyes inspired researchers to search environmental-
friendly, economic, easy-prepared and efficient photocatalysts as
alternatives. Thus, recent attention has been focused on the
to
create
structural
complexity.
Recently,
the
arylation/trifluoromethylation of N-alkyl-N-arylmethacrylamides
substrates has been intensively investigated. Because through
such a procedure, not only a CF group was incorporated, but
also an oxindole framework bearing a quaternary carbon center
3
2 inorganic nanoscale semiconductor photocatalyts. These
3 materials found wide applications in the photocatalytic fields due
4 to their unique characteristics, e.g. the quantum confinement
5 effects, high surface-to-volume ratios, broad and intense
6 absorption spectra in the visible region and low cost, which
was formed. Both the CF
3
group and the oxindole skeleton were
ubiquitous in a number of biologically active compounds and
1
2
pharmaceuticals. To date, a wide variety of reaction conditions
have been applied in these transformations, however, the
transition-metal catalysts were mainly employed in the reaction
medias. For example, Liu and coworkers developed an efficient
oxidative aryltrifluoromethylation of N-aryl acrylamides by the
8
13
7 offered new and versatile ways to harvest light energy. Yet, the
8 applications of inorganic semiconductor nanostructures were
9 mainly restricted to the degradation of organic pollutants or dyes
0 or the photocatalytic splitting of water into hydrogen and oxygen.
1
4
combination of Pd(OAc) and Yb(OTf) as the co-catalysts. The
Sodeoka and Nevado groups reported the copper-catalyzed
2
3
aryltrifluoromethylation of activated alkenes using Togni’s
The examples for the organic synthesis of fine chemicals were
1
2
3
4
5

2
Tetrahedron
1
5
reagent as the trifluoromethylation reagent. AJuCst CrecEenPtlTy,EZDhu MABiNOBUrSnCanRoIshPeTets were one kind of efficient nanoscale
et al. firstly described a visible-light-induced intermolecular
arylation/trifluoromethylation of alkenes employed [Ru(bpy) Cl ]
as the photocatalyst and Togni’s reagent as the CF source.
Although these strategies were effective, they were tend to
require expensive catalysts and CF reagents, as well as the
relatively high temperature. To address these issues, the
development of an environment-benign, economic process
utilizing inexpensive catalysts and CF reagents was extremely
urgent. Herein, we reported a light-induced, simple and efficient
intermolecular trifluoromethylation/arylation of N-alkyl-N-
arylmethacrylamides using easily prepared, inexpensive BiOBr
photocatalysts, which could absorb light to generate electrons
20
and holes. We speculated that the electrons might transfer to
organic molecule to generate free radical, which might react with
alkenes. To validate the feasibility of this photocatalytic process,
we initially examined the reaction by treating 0.2 mmol 1a, 0.6
mmol 2 CF SO Cl, 0.6 mmol K HPO , 20.0 mg BiOBr
3
2
1
6
1
2
3
4
5
6
7
8
9
0
1
2
3
4
3
3
3
2
2
4
o
nanosheets, and 1.0 mL DMF at 0-10 C by light irradiation for 6
h. As expected, the reaction occurred and 88% yield of the
product was obtained (Table 1, entry 1). Encouraged by this
excited result, we further screened the other bases on the
efficiency of this reaction and observed that they were all inferior
to K HPO (Table 1, entries 2-5). Subsequent investigations on
3
17
nanosheets as photocatalysts and CF SO Cl as the CF reagent.
3
2
3
2
4
1
1
1
1
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6
6
6
6
6
To the best of our knowledge, transformations involving
the effect of the solvents to give a fact that DMF was the most
promising option, and the others were less effective or even
totally ineffective (Table 1, entries 6-12). Note that, reducing the
loading of BiOBr to 0.02 mmol still gave rise to 87% yield of 3a
simultaneous formations of C-C and C-CF bonds in one step
3
using inorganic nanosheets as the photocatalysts were still
untouched.
(Table 1, entry 13). The low loading of catalyst and the satisfied
5 2. Results/Discussion
6
7
result further proved that the BiOBr nanosheets were a kind of
photocatalysts with excellent catalytic activity for organic
reactions. Control experiment demonstrated that the light played
an important role in this tandem trifluoromethylation/arylation
reaction (Table 1, entry 14). Unexpectedly, 29% of the product
was obtained in the absence of BiOBr nanosheets, which might
be attributed to the homolysis of CF SO Cl under light irradiation
Table 1
Screening results of the aryltrifluoromethylation of N-methyl-
8
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0
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0
1
2
a
N-phenylmethacrylamide
3
2
(Table 1, entry 15). This defective result further indicated that the
photocatalysts were indispensable to this reaction.
Table 2
Entry
Photocatalyst
Additive
Solvent
DMF
Yield (%)
BiOBr nanosheets promoted synthesis of CF -containing
3
1
2
3
4
5
6
7
8
9
BiOBr nanosheets
BiOBr nanosheets
BiOBr nanosheets
BiOBr nanosheets
BiOBr nanosheets
BiOBr nanosheets
BiOBr nanosheets
BiOBr nanosheets
BiOBr nanosheets
BiOBr nanosheets
BiOBr nanosheets
BiOBr nanosheets
BiOBr nanosheets
BiOBr nanosheets
-
K
2
HPO
CO
PO
KOH
NEt
4
88
83
78
81
33
Trace
-
a
oxindoles derivates
K
2
3
DMF
K
3
4
DMF
DMF
3
DMF
K
2
HPO
HPO
HPO
HPO
HPO
HPO
HPO
HPO
HPO
HPO
4
4
4
4
4
4
4
4
4
4
DMSO
K
2
CH
THF
CH Cl
Toluene
CH OH
3
CN
K
2
21
-
K
2
2
2
1
1
0
1
K
2
-
K
2
3
-
12
K
2
NMP
DMF
DMF
DMF
53
87
-
b
c
1
1
3
4
5
K
2
K
2
1
K
2
29
a
3 2
Reaction conditions: 1a (0.2 mmol), 2 CF SO Cl (0.6 mmol), additive (0.6
mmol), photocatalysts (20 mg), solvent (1.0 mL), 300 W Xe arclamp, 0-10
o
C.
b
0.02 mmol BiOBr nanosheets were used.
c
In the dark.
The BiOBr nanosheets were prepared according to a previous
1
8
3 report (details see the supporting information). To monitor their
photocatalytic activity, the as-prepared BiOBr nanosheets were
used in the following organic transformations. The addition of
free radicals to C=C double bond was a key route for the
functionalization of alkenes, while the photoredox catalysis could
4
5
6
7
8
9
0
1
2
3
4
5
a
3 2 2 4
Reaction conditions: 1a (0.2 mmol), 2 CF SO Cl (0.6 mmol), K HPO (0.6
mmol), BiOBr nanosheets (0.02 mmol), DMF (1.0 mL), 300 W Xe arclamp,
o
0
-10 C. Isolated yields were reported.
1
a,19
trigger these transformations.
During the photocatalytic
course the free radical species could be generated through a
single-electron-transfer (SET) process. Consequently, searching
for suitable photocatalysts became a fundamental aim in this area.
With the optimal conditions in hand, the substrate scope was
evaluated for this reaction. We firstly examined the substitution
pattern at the N-aryl moiety, and found that both the electron-

3
donating and the electron-withdrawing groupsAinCtroCduEcePdTtoEtDhe MAScNheUmSeC1.RScIaPleTd-up of BiOBr nanosheets promoted
aromatic ring were well tolerated, and they all efficiently
transformed into the corresponding products respectively (Table
synthesis of CF -containing oxindole.
3
2
, entries 3a-l). Noteworthy, even potentially sensitive functional
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group cyano survived under the standard conditions (Table 2,
entry 3j). The existence of halogens and acetyl group could
enable us to conduct further transformations. Passably, compared
with para-position substrates, the substitutents at ortho-position
gave the products in slightly lower yields (Table 2, entries 3k-l).
Then the substrates bearing different N-protecting groups were
also investigated and the corresponding products were fabricated
in promising yields (Table 2, entries 3m-o). Additionally, the
alkenes with diversely functional groups at α-position were still
Table 4
a,b
Studies on recycling of BiOBr nanosheets
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
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3
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3
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6
amenable to this strategy, furnishing the CF -containing
oxindoles in acceptable to good yields (Table 2, entries 3p-s).
Interestingly, treatment of tetrahydroquinoline derivative 1t with
3
Cycle
Isolated Yield %
1
87
79
65
2
delivered the desired functionalized oxindole in 63% isolated
yield (Table 2, entry 3t). However, when we chose N-
unprotected-N-arylmethacrylamide as the reactant for this
trifluoromethylation/arylation, it did not work (not listed in table
2
3
a
2
).
Reaction conditions: 1a (0.2 mmol), 2 CF
mmol), BiOBr (0.02 mmol), DMF (1.0 mL), 300 W Xe arclamp, 0-10 C.
3
SO
2
Cl (0.6 mmol), K
2
HPO
4
(0.6
o
Table 3
b
1
3 2 2 4
a (0.2 mmol), 2 CF SO Cl (0.6 mmol), K HPO (0.2 mmol) were added per
BiOBr nanosheets promoted synthesis of CF -containing aza-
heterocycles
3
cycle.
a
The photocatalytic activity of the BiOBr nanosheets was also
studied by the cycling tests. After three cyclic experiments, the
yield of the product was decreased from 87% to 65% (Table 4).
The TEM image showed that the structures of BiOBr were
transformed from nanosheets into nanoparticles after three cycles
not shown here), which suggested that the BiOBr nanosheets
photocatalysts were not very stable for this
trifluoromethylation/arylation of alkenes. It was reasonable to
expect that the development of more stable photocatalysts (e. g.
TiO nanosheets) or suitable catalytic systems might be a solution
(
2
9a,
ft,om,snolve the stability issue of inorganic nanoscale photocatalyts.
Scheme 2. Control experiments.
a
3 2
Reaction conditions: 1΄ (0.2 mmol), 2 CF SO Cl (0.6 mmol), base (0.6
mmol), BiOBr nanosheets (0.02 mmol), solvent (1.0 mL), 300 W Xe arclamp,
0-10 C. Isolated yields were reported.
o
In order to further test the efficiency of this one-pot sequential
trifluoromethylation/arylation
method,
N-methacryloyl-N-
methylbenzamide 1a΄ was used to replace 1a under the standard
conditions. It was found that the reaction could also proceed and
provide the desired product in 77% yield (Table 3, entry 3a΄).
Next, we investigated several N-substituted substrates, and 67%-
7
8% yields of the corresponding products were accomplished
(Table 3, entries 3b΄-f΄). It was worth noting that 3f΄ was
obtained as the sole product when benzyl was the protecting
group to nitrogen. In addition, the substrate with a methoxy on
the aryl ring could facilitate the reaction and a moderate yield of
the product was obtained (Table 3, entry 3g΄). These satisfactory
results again confirmed that our photocatalytic strategy was of
synthetic useful and which offered an important complementary
To determine whether our reaction proceeded according to a
radical process, the control experiments were conducted. When
introducing 3.0 equiv of TEMPO (a class of radical trapper)
under the optimal conditions, no desired product was formed
(Scheme 2a). This result revealed that a radical pathway was
involved in our photocatalytic transformation. To get insight into
the mechanism, two control experiments were carried out. The
yields of products were remarkably decreased when adding 3.0
4 to the existing methods for trifluoromethylation/arylation of
5 alkenes. It was reasonable to expect that this facile methodology
6 would be adopted in other types of organic transformations.
7
Remarkably, the efficiency of the photocatalytic tactics was
21
8
9
0
1
equiv of oxamide (a kind of scavenger for photogenerated
verified by a large-scale study. When the reaction of 1a with 2
was run on a 1.3 mmol sacle (Scheme 1), the product was also
isolated in 85% yield.
holes) and NaIO (a kind of scavenger for photogenerated
3
electrons) to the system, respectively (Scheme 2b, 2c). The
preliminary results demonstrated that the electrons and holes
2
3
4
5

4
Tetrahedron
generated by light illumination exerted a poAsitCiveCrEolePTonEthDis MAtriNfluUorSomCeRthyIlPatTion/arylation of N-alkyl-N-arylmethacrylamides
light-induced organic transformation.
was preferentially to carry out in accordance with pathway A.
These results were consistent with our experiments.
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1
2
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2
2
2
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2
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3
3
3
3
4
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4
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4
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5
5
5
5
5
6
6
6
6
6
6
Fig. 1. Proposed mechanism.
Based on the control experimental results and the previous
3 studies, a plausible mechanism was proposed in Fig. 1.
Irradiation of the BiOBr nanosheets provided the photogenerated
electrons and holes. Subsequent reduction of triflyl chloride by
photogenerated electrons via single electron transfer afforded free
radical anion of triflyl chloride, which experienced fast collapses
4
5
6
7
8
9
0
1
2
3
4
5
6
Fig. 2. Energy profile for the reaction pathways of the
trifluoromethylation/arylation of alkenes (Kcal/mol).
to form CF radical with sulfur dioxide and chloride anion. Then,
3
3
. Conclusion
the addition of CF3 radical to 1a giving rise to radical
intermediate INF1, which subsequently underwent an
intramolecular cyclization to fabricate INF2. Then, a single-
electron oxidation of INF2 by photoganerated holes provided
cyclohexadienyl cation INF3 and meanwhile completed the
catalytic cycle with the release of BiOBr nanosheets. Finally,
deprotonation of INF3 generated the desired products PRF.
In summary, we have developed a novel light-induced, BiOBr
nanosheets promoted trifluoromethylation/arylation of alkenes
using inexpensive CF SO Cl as the CF source. This efficient and
3
2
3
regioselective strategy allowed for a practical access to the CF3-
containing oxindoles bearing a quaternary carbon center with
diverse functional groups tolerated. Meanwhile, a number of six-
membered aza-heterocycles were also created, thus reflecting the
synthetic utility of this method. Additionally, the large-scale tests
illustrated that our as-prepared BiOBr nanosheets were of high
activation. Preliminary mechanistic investigations showed that
this efficient transformation might be ascribed to the synergistic
effect of photogenerated electrons and holes. Most significantly,
a DFT calculation was conducted to explain the high selectivity
Furthermore, details of reaction mechanism were studied by
7 the density functional theory calculation using the B3LYP/6-
2
2
8 31G(d, p) method. 1a and CF
9 free-energy profile, and two competitive pathways were
0 computed (Fig. 2). In pathway A, firstly, the addition of CF
1 radical to 1a generated the radical intermediate INF1 via a
2 transition-state TSF1 with a small energy barrier of 1.34
radical were set to zero in the
3
3
-
1
of
the
trifluoromethylation/arylation
of
N-alkyl-N-
kcal/mol . During following process, it is strongly exothermic by
3
4
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7
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9
0
1
2
3
4
5
6
7
8
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0
1
2
3
4
5
-
1
arylmethacrylamides.
4. Experimental Section
4.1. General
3
9.50 kcal/mol , which indicated that the formation of INF1 was
thermodynamically favourable. Then, a radical substitution at the
ortho-position of the N-aryl moiety forming INF2 with a 19.20
-
1
kcal/mol barrier. Although the energy barrier was a little big,
the energy released in the preceding steps from TSF1 to INF1
was enough to compensate the energy required. Subsequently,
INF2 experienced an oxidative process by photogenerated holes
to form INF3, which then underwent fast and irreversible
deprotonation to deliver the final product PRF. The overall
All purchased reagents were used without further purification.
Analytical thin layer chromatography was performed on 0.20 mm
Qingdao Haiyang silica gel plates. Silica gel (200-300 mesh)
(from Qingdao Haiyang Chem. Company, Ltd.) was used for
-
1
flash chromatography.
reaction was exothermic by 43.31 kcal/mol . For pathway B, the
process was similar with pathway A. Whereas, two fundamental
features were worth noting. Firstly, the energy for formation of
The reaction was irradiated with 300 W Xe arclamp (280 nm-
7
80 nm, CEL-HXF300/CEL-HXUV300, Beijing 10 Aulight Co.
-1
INS1 was approximately 5.21 kcal/mol more than INF1. The
Ltd.). The scanning electron microscopy (SEM) images were
taken with a Hitachi S-4800 scanning electron microscope (SEM,
difference was critical. From the energy point of view, this
process is unfavorable. On the other hand, the energy released in
the step of INF1 formation was almost twice of INS1. The much
higher energy for the former showed that INF1 was very stable
due to the delocalization of electrons between C=O and the α-C.
5
kV) equipped with the Thermo Scientific energy-dispersion X-
ray fluorescence analyzer. Transmission electron microscopy
TEM) and higher-magnification transmission electron
microscopy (HRTEM) were carried out with JEOL JEM-2100F
(
Both
the
two
aspects
confirmed
that
the

5
system equipped with the EDAX Genesis AXMC2C. EThPeTXE-rDay MA3.N82U(sS, 3CHR), 3I.P23T(s, 3H), 2.89 – 2.77 (m, 1H), 2.70 – 2.58 (m,
1
9
diffraction patterns (XRD) of the products were recorded with a
PANalytical X'Pert PRO X-ray diffractometer with Co Kα
radiation (λ = 1.78897 nm) at 40 kV and 40 mA. Then the data
was converted into corresponding Cu Kα radiation. The optical
properties of the samples were analyzed by a Shimadzu UV-2550
ultraviolet/visible diffuse reflectance spectroscopy (DRS), during
1H), 1.41 (s, 3H); F NMR (376 MHz, CDCl ) [ppm] δ -61.87 (t,
J = 10.6 Hz, 3F); C NMR (100 MHz, CDCl ) [ppm] δ 178.1,
3
1
3
3
156.1, 136.4, 132.4, 125.3 (q, J = 276.0 Hz), 112.6, 111.3, 108.7,
55.8, 44.2 (d, J = 1.0 Hz), 40.6 (q, J = 28.0 Hz), 26.5, 25.0; IR
(KBr) ν (cm ): 3058, 2979, 2942, 2840, 1712, 1628, 1470, 1436,
1363, 1284, 1258, 1125, 1083, 1040, 947, 913, 868, 803, 732,
693, 667, 613, 574, 523; HRMS (EI) found: m/z 273.0977 [M];
calcd. For C H F NO 273.0977.
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
-
1
which BaSO was employed as the internal reflectance standard.
4
1
13
19
H, C, F NMR were recorded on Varian Mercury Plus 400
1
3
14
3
2
1
13
instruments at 400 MHz ( H NMR), 100 MHz ( C NMR), as
1
9
4.2.4 5-(tert-butyl)-1,3-dimethyl-3-(2,2,2-trifluoroethyl)indolin-2-
one (3d) Yield: 82%; H NMR (400 MHz, CDCl ) [ppm] δ 7.37 –
well as 376 MHz ( F NMR). Chemical shifts were reported in
ppm down field from internal Me Si and external CCl F,
1
3
4
3
7.31 (m, 2H), 6.83 (d, J = 8.1 Hz, 1H), 3.24 (s, 3H), 2.87 – 2.76
respectively. Multiplicity was indicated as follows: s (singlet), d
doublet), t (triplet), q (quartet), m (multiplet), dd (doublet of
doublet), br (broad). Coupling constants were reported in Hertz
Hz). HRMS were recorded on an Agilent Q-TOF spectrometer
19
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
6
6
6
6
6
(m, 1H), 2.73 – 2.62 (m, 1H), 1.43 (s, 3H), 1.34 (s, 9H);
F
(
13
NMR (376 MHz, CDCl
NMR (100 MHz, CDCl
) [ppm] δ -61.87 (t, J = 10.6 Hz, 3F);
C
3
) [ppm] δ 178.7, 145.9, 140.4, 130.7,
3
(
125.0, 124.9 (q, J = 278.0 Hz), 120.9, 107.8, 44.6 (d, J = 2.0 Hz),
using the ESI method and Waters TOF spectrometer using the EI
method. IR spectra were recorded on an AVATAR 360 FT-IR
spectrometer.
-1
40.6 (q, J = 28.0 Hz), 34.6, 31.5, 26.4, 25.0; IR (KBr) ν (cm ):
2963, 2908, 2872, 1719, 1625, 1505, 1465, 1363, 1259, 1141,
+
1
054, 947, 841, 816; HRMS (ESI) found: m/z 322.1395 [M+Na] ;
4
.2 General procedure for light-induced BiOBr nanosheets
calcd. for C H F NO+Na 322.1395.
16 20 3
promoted trifluoromethylation/arylation of alkene
4
.2.6 5-fluoro-1,3-dimethyl-3-(2,2,2-trifluoroethyl)indolin-2-
1
1
a (0.2 mmol, 35.0 mg), BiOBr (0.02 mmol, 6.1 mg), K HPO4
one (3e) Yield: 76%; H NMR (400 MHz, CDCl ) [ppm] δ 7.07 –
2
3
(98%, 0.6 mmol, 106.6 mg) and DMF (1.0 mL) were added to a
7.01 (m, 2H), 6.82 (dd, J = 9.1, 4.1 Hz, 1H), 3.25 (s, 3H), 2.91 –
2.79 (m, 1H), 2.70 – 2.59 (m, 1H), 1.43 (s, 3H); F NMR (376
1
9
dried 10 mL Sclenk flask under air. After degassing under
vacuum and refilling with Ar (three times), the tube was sealed
well, and then immersed in an ice bathe maintaining for 5
minutes. After that, CF SO Cl (98%, 0.6 mmol, 103.2 mg) was
MHz, CDCl ) [ppm] δ -61.97 (t, J = 10.6 Hz, 3F), -120.34 – -
3
1
3
120.40 (m, 1F); C NMR (100 MHz, CDCl ) [ppm] δ 178.1,
3
159.3 (d, J = 239.0 Hz), 138.8 (d, J = 2.0 Hz), 132.6 (d, J = 8.0
Hz), 125.1 (q, J = 277.0 Hz), 114.9 (d, J = 23.0 Hz), 111.8 (dd, J
= 1.5, 23 Hz), 108.9 (d, J = 9.0 Hz), 44.8 (d, J = 2.0 Hz), 40.6 (q,
J = 27.5 Hz), 26.6, 24.9; IR (KBr) ν (cm ): 2959, 2926, 2857,
1723, 1590, 1496, 1445, 1358, 1263, 1186, 1148, 1119, 1082,
963, 812, 669, 561; HRMS (EI) found: m/z 261.0781 [M]; calcd.
3
2
5 added to the mixture via the microinjector. The Sclenk tube was
6 immediately moved to a distance of ca. 30 cm from the light
7 source and the resulting solution was stirred at no more than 10
-
1
o
8
C under light irradiation for 6 h. After the completion of the
9 reaction (by TLC), the reaction mixture was centrifuged and the
0 organic phases were diluted with water (4.0 mL) and extracted
For C12
H
11
F
NO 261.0777.
4
1 with CH
2 washed with brine, and dried over anhydrous MgSO
3 removal of the solvent, the residue was purified by flash column
Cl
(3 × 6.0 mL). The combined organic layers were
2
2
4
.2.7 5-chloro-1,3-dimethyl-3-(2,2,2-trifluoroethyl)indolin-2-one
. After
1
4
(3f) Yield: 82%; H NMR (400 MHz, CDCl ) [ppm] δ 7.31 (dd, J
3
=
8.3, 2.0 Hz, 1H), 7.26 (d, J = 1.7 Hz, 1H), 6.82 (d, J = 8.3 Hz,
chromatography on silica gel to give the desired product 3a.
4
5
6
7
8
9
0
1
2
1
H), 3.24 (s, 3H), 2.90 – 2.79 (m, 1H), 2.70 – 2.59 (m, 1H), 1.42
19
4
.2.1 1,3-dimethyl-3-(2,2,2-trifluoroethyl)indolin-2-one (3a)
(s, 3H); F NMR (376 MHz, CDCl ) [ppm] δ -61.96 (t, J = 10.6
Hz, 3F); C NMR (100 MHz, CDCl ) [ppm] δ 177.9, 141.5,
3
1
13
Yield: 87% yield; H NMR (400 MHz, CDCl ) [ppm] δ 7.34 (t, J
=
6
2
3
3
7.8 Hz, 1H), 7.29 (d, J = 5.2 Hz, 1H), 7.12 (t, J = 7.5 Hz, 1H),
132.7, 128.5, 128.1, 125.1 (q, J = 277.0 Hz), 124.1, 109.4, 44.6
-
.91 (d, J = 7.8 Hz, 1H), 3.26 (s, 3H), 2.92 – 2.76 (m, 1H), 2.75 –
(d, J = 2.0 Hz), 40.6 (q, J = 28.0 Hz), 26.6, 24.9; IR (KBr) ν (cm
1
9
1
.60 (m, 1H), 1.43 (s, 3H); F NMR (376 MHz, CDCl ) [ppm] δ
): 2975, 2939, 2884, 1721, 1648, 1610, 1490, 1429, 1357, 1303,
3
1
3
-61.95 (t, J = 10.5, 3F); C NMR (100 MHz, CDCl ) [ppm] δ
1258, 1184, 1141, 1078, 946, 883, 814, 755; HRMS (EI) found:
3
1
1
78.5, 142.9, 131.0, 128.5, 125.2 (q, J = 277.0 Hz), 123.6, 122.6,
08.4, 44.4 (d, J = 2.0 Hz), 40.6 (q, J = 28.0 Hz), 26.4, 25.0; IR
m/z 277.0479 [M]; calcd. For C H ClF NO 277.0481.
1
2
11
3
-
1
4.2.8 5-bromo-1,3-dimethyl-3-(2,2,2-trifluoroethyl)indolin-2-one
1
3 (KBr) ν (cm ): 2927, 2857, 1728, 1594, 1495, 1464, 1429, 1365,
4 1260, 1185, 1085, 966, 801, 752, 703; HRMS (EI) found: m/z
5 243.0874 [M]; calcd. For C H F NO 243.0871.
(3g) Yield: 81%; H NMR (400 MHz, CDCl ) [ppm] δ 7.45 (dd,
3
J = 8.3, 1.8 Hz, 1H), 7.39 (d, J = 1.3 Hz, 1H), 6.78 (d, J = 8.3 Hz,
H), 3.23 (s, 3H), 2.90 – 2.78 (m, 1H), 2.70 – 2.58 (m, 1H), 1.42
1
2
12 3
1
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
1
9
4
.2.2 1,3,5-trimethyl-3-(2,2,2-trifluoroethyl)indolin-2-one (3b)
(s, 3H); F NMR (376 MHz, CDCl ) [ppm] δ -61.95 (t, J = 10.6
3
1
13
Yield: 88%; H NMR (400 MHz, CDCl ) [ppm] δ 7.27 – 7.21 (m,
1
3
Hz, 3F); C NMR (100 MHz, CDCl ) [ppm] δ 177.8, 142.0,
3
3
H), 7.17 (d, J = 6.2 Hz, 1H), 6.79 (d, J = 7.8 Hz, 1H), 3.23 (s,
133.1, 131.4, 126.8, 125.0 (q, J = 277.0 Hz), 115.3, 109.9, 44.5
-
H), 2.87 – 2.75 (m, 1H), 2.71 – 2.60 (m, 1H), 2.37 (s, 3H), 1.41
(d, J = 2.0 Hz), 40.6 (q, J = 28.0 Hz), 26.5, 24.9; IR (KBr) ν (cm
19
1
(s, 3H); F NMR (376 MHz, CDCl ) [ppm] δ -61.90 (t, J = 10.6
): 2976, 2939, 2883, 1722, 1664, 1609, 1489, 1427, 1359 1304,
3
13
Hz, 3F); C NMR (100 MHz, CDCl ) [ppm] δ 178.4, 140.5,
1
1259, 1185, 1141, 1078, 1057, 946, 883, 811, 664, 620, 535;
HRMS (EI) found: m/z 320.9976 [M]; calcd. For C H BrF NO
320.9977.
3
32.2, 131.1, 128.8, 125.3 (q, J = 276.0 Hz), 124.3, 108.1, 44.4
1
2
11
3
(d, J = 2.0 Hz), 40.6 (q, J = 29.0 Hz), 26.4, 25.0, 21.1; IR (KBr) ν
-1
(cm ): 2969, 2930, 2873, 1718, 1654, 1626, 1503, 1462, 1432,
4.2.9 5-iodo-1,3-dimethyl-3-(2,2,2-trifluoroethyl)indolin-2-one
1
5
360, 1259, 1182, 1138, 1081, 1055, 948, 888, 810, 667, 627,
57; HRMS (EI) found: m/z 257.1026 [M]; calcd. For
1
(
3h) Yield: 89%; H NMR (400 MHz, CDCl ) [ppm] δ 7.64 (dd,
3
J = 8.1, 1.1 Hz, 1H), 7.56 (s, 1H), 6.68 (d, J = 8.2 Hz, 1H), 3.22
C H F NO 257.1027.
1
3
14 3
(
s, 3H), 2.89 – 2.77 (m, 1H), 2.69 – 2.57 (m, 1H), 1.41 (s, 3H);
1
9
4
.2.3 5-methoxy-1,3-dimethyl-3-(2,2,2-trifluoroethyl)indolin-2-
F NMR (376 MHz, CDCl ) [ppm] δ -61.94 (t, J = 10.6 Hz, 3F);
3
1
13
one (3c) Yield: 92%; H NMR (400 MHz, CDCl ) [ppm] δ 6.90
C NMR (100 MHz, CDCl ) [ppm] δ 177.6, 137.4, 133.4, 132.4,
3
3
(s, 1H), 6.85 (dd, J = 8.4, 2.1 Hz, 1H), 6.80 (d, J = 8.4 Hz, 1H),
129.2, 125.0 (q, J = 277.0 Hz), 120.9, 110.5, 44.4 (d, J = 2.0 Hz),

6
Tetrahedron
-
1
4
0.6 (q, J = 28.0 Hz), 26.5, 24.9; IR (KBr) ν (AcmC)C: 2E97P4T, 2E93D6, MA4.N2.1U5 SC1R-bIePnzTyl-3-methyl-3-(2,2,2-trifluoroethyl)indolin-2-one
1
1
1
721, 1659, 1605, 1487, 1463, 1423, 1360, 1304, 1259, 1186,
140, 1079, 1054, 1023, 945, 884, 809, 748, 667, 562, 528;
(3n) Yield: 75%; H NMR (400 MHz, CDCl ) [ppm] δ 7.37 –
3
7.29 (m, 6H), 7.21 (t, J = 7.7 Hz, 1H), 7.08 (t, J = 7.4 Hz, 1H),
6.78 (d, J = 7.8 Hz, 1H), 4.96 (q, J = 16.0 Hz, 2H), 2.98 – 2.90
HRMS (EI) found: m/z 368.9836 [M]; calcd. For C H IF NO
1
2
3
4
5
6
7
8
9
12 11
3
1
9
3
68.9837.
(m, 1H), 2.77 – 2.69 (m, 1H), 1.49 (s, 3H); F NMR (376 MHz,
CDCl ) [ppm] δ -61.71 (t, J = 10.6 Hz, 3F); C NMR (100 MHz,
CDCl
13
3
4
.2.10 5-acetyl-1,3-dimethyl-3-(2,2,2-trifluoroethyl)indolin-2-one
1
3
) [ppm] δ 178.6, 142.0, 135.7, 131.0, 129.7, 128.8, 128.4,
(3i) Yield: 71%; H NMR (400 MHz, CDCl ) [ppm] δ 7.99 (dd, J
3
1
2
27.7, 127.2, 125.3 (q, J = 272.0 Hz), 123.6, 109.6, 44.4 (d, J =
.0 Hz), 44.0, 40.5 (q, J = 38.0 Hz), 25.7; IR (KBr) ν (cm ):
=
8.2, 1.4 Hz, 1H), 7.93 (s, 1H), 6.95 (d, J = 8.2 Hz, 1H), 3.30 (s,
-1
3H), 2.95 – 2.83 (m, 1H), 2.79 – 2.69 (m, 1H), 2.61 (s, 3H), 1.44
(d, J = 9.9 Hz, 3H); F NMR (376 MHz, CDCl ) [ppm] δ -62.08
(t, J = 10.6 Hz, 3F); C NMR (100 MHz, CDCl ) [ppm] δ 196.6,
178.7, 147.2, 132.3, 131.3, 130.5, 125.0 (q, J = 276.0 Hz), 123.4,
1
9
2971, 2930, 2871, 1718, 1661, 1491, 1458, 1360, 1260, 1192,
1134, 1073, 1028, 941, 801, 747, 700; HRMS (ESI) found: m/z
3
1
3
3
+
3
42.1081 [M+Na] ; calcd. for C H F NO+Na 342.1082.
1
8
16 3
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
6
6
6
6
6
0 107.9, 44.2 (d, J = 2.0 Hz), 40.7 (q, J = 28.5 Hz), 26.7, 26.4, 25.0;
1 IR (KBr) ν (cm ): 2964, 2931, 1725, 1676, 1605, 1498, 1453,
2 1435, 1392, 1360, 1261, 1232, 1183, 1131, 1080, 1048, 940, 868,
3 801, 700, 668, 604, 537; HRMS (ESI) found: m/z 286.1058
4 [M+H] ; calcd. for C14
5
4.2.16 1-ethyl-3-methyl-3-(2,2,2-trifluoroethyl)indolin-2-one (3o)
1
-
1
Yield: 83%; H NMR (400 MHz, CDCl ) [ppm] δ 7.36 – 7.25 (m,
3
2H), 7.10 (t, J = 7.5 Hz, 1H), 6.92 (d, J = 7.8 Hz, 1H), 3.90 (dq, J
= 14.5, 7.2 Hz, 1H), 3.71 (dq, J = 14.3, 7.2 Hz, 1H), 2.92 – 2.80
(m, 1H), 2.72 – 2.60 (m, 1H), 1.41 (s, 3H), 1.27 (t, J = 7.2 Hz,
+
H F NO +H 286.1055.
14 3 2
1
9
3H); F NMR (376 MHz, CDCl
) [ppm] δ -61.92 (t, J = 10.6 Hz,
3
4
.2.11
1,3-dimethyl-2-oxo-3-(2,2,2-trifluoroethyl)indoline-5-
carbonitrile (3j) Yield: 73%; H NMR (400 MHz, CDCl ) [ppm]
δ 7.67 (d, J = 8.1 Hz, 1H), 7.54 (s, 1H), 6.98 (d, J = 8.1 Hz, 1H),
.29 (s, 3H), 2.94 – 2.83 (m, 1H), 2.75 – 2.64 (m, 1H), 1.45 (s,
H); F NMR (376 MHz, CDCl ) [ppm] δ -62.03 (t, J = 10.6 Hz,
F); C NMR (100 MHz, CDCl ) [ppm] δ 178.1, 146.8, 133.9,
32.0, 127.0, 124.9 (q, J = 276.0 Hz), 119.0, 109.0, 106.0, 44.2
d, J = 2.0 Hz), 40.6 (q, J = 28.0 Hz), 26.7, 24.9; IR (KBr) ν (cm
13
1
3
1
2
2
F); C NMR (100 MHz, CDCl ) [ppm] δ 178.1, 141.9, 131.2,
3
6
7
8
9
0
1
2
3
4
3
28.4, 125.3 (q, J = 276.0 Hz), 123.7, 122.4, 108.6, 44.3 (d, J =
.0 Hz), 40.7 (q, J = 28.5 Hz), 34.8, 25.1, 12.2; IR (KBr) ν (cm ):
980, 2938, 2878, 1716, 1613, 1492, 1463, 1364, 1260, 1217,
-1
3
3
3
1
19
3
1
3
1185, 1139, 1073, 836, 752, 701, 614; HRMS (ESI) found: m/z
3
+
2
80.0927 [M+Na] ; calcd. for C H F NO+Na 280.0925.
13 14 3
-
(
4.2.17
(1-methyl-2-oxo-3-(2,2,2-trifluoroethyl)indolin-3-
1
1
)
: 2974, 2938, 2223, 1725, 1612, 1496, 1459, 1334, 1256, 1176,
136, 1078, 1051, 1022, 947, 822, 667, 629, 582; HRMS (ESI)
yl)methyl acetate (3p) Yield: 86%; H NMR (400 MHz, CDCl )
3
1
[ppm] δ 7.37 (t, J = 7.7 Hz, 1H), 7.33 – 7.27 (m, 2H), 7.11 (t, J =
7.5 Hz, 1H), 6.92 (d, J = 7.8 Hz, 1H), 4.41 (d, J = 10.9 Hz, 1H),
4.09 (d, J = 10.9 Hz, 1H), 3.27 (s, 3H), 2.97 – 2.80 (m, 2H), 1.99
+
5 found: m/z 291.0721 [M+Na] ; calcd. for C H F N O+Na
1
3
11
3
2
6 291.0721.
7
1
9
(s, 3H); F NMR (376 MHz, CDCl ) [ppm] δ -61.37 (t, J = 10.6
3
4
.2.12 7-methoxy-1,3-dimethyl-3-(2,2,2-trifluoroethyl)indolin-2-
one (3k) Yield: 65%; H NMR (400 MHz, CDCl ) [ppm] δ 7.05
t, J = 8.0 Hz, 1H), 6.94 (t, J = 8.0 Hz, 1H), 6.89 (d, J = 7.9 Hz,
H), 3.89 (s, 3H), 3.52 (s, 3H), 2.87 – 2.78 (m, 1H), 2.71 – 2.58
m, 1H), 1.40 (s, 3H); F NMR (376 MHz, CDCl ) [ppm] δ -
2.03 (t, J = 10.6 Hz, 3F); C NMR (100 MHz, CDCl ) [ppm] δ
78.4, 140.5, 132.2, 131.1, 128.8, 125.3 (q, J = 276.0 Hz), 124.3,
13
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
Hz, 3F); C NMR (100 MHz, CDCl ) [ppm] δ 175.1, 170.0,
1
3
3
143.6, 129.3, 126.6, 125.3 (q, J = 299.0 Hz), 124.6, 122.7, 108.6,
67.0, 44.2 (d, J = 2.0 Hz), 36.8 (q, J = 29.0 Hz), 26.5, 20.5; IR
(
1
(
6
1
1
-1
19
(KBr) ν (cm ): 3060, 2962, 1720, 1648, 1613, 1493, 1469, 1430,
3
13
1374, 1261, 1230, 1118, 1045, 919, 866, 800, 754, 703, 669, 608;
3
HRMS (EI) found: m/z 301.0923 [M]; calcd. For C14
01.0926.
H F NO
14 3 3
3
08.1, 44.4 (d, J = 2.0 Hz), 40.6 (q, J = 29.0 Hz), 26.4, 25.0, 21.1;
-1
IR (KBr) ν (cm ): 3059, 2929, 1703, 1613, 1495, 1470, 1430,
4.2.18
(1-methyl-2-oxo-3-(2,2,2-trifluoroethyl)indolin-3-
1
1
(
378, 1290, 1260, 1142, 1068, 935, 800, 752, 700, 617; HRMS
EI) found: m/z 273.0977 [M]; calcd. For C H F NO 273.0977.
yl)methyl benzoate (3q) Yield: 80%; H NMR (400 MHz, CDCl )
3
[ppm] δ 7.89 (d, J = 7.5 Hz, 2H), 7.58 (t, J = 7.2 Hz, 1H), 7.44 (t,
J = 7.5 Hz, 2H), 7.37 (t, J = 8.8 Hz, 2H), 7.10 (t, J = 7.5 Hz, 1H),
1
3
14
3
2
4
.2.13
7-bromo-1,3-dimethyl-3-(2,2,2-trifluoroethyl)indolin-2-
1
one (3l) Yield: 68%; H NMR (400 MHz, CDCl ) [ppm] δ 7.43
d, J = 7.9 Hz, 1H), 7.18 (d, J = 7.3 Hz, 1H), 6.94 (t, J = 7.8 Hz,
H), 3.63 (s, 3H), 2.92 – 2.81 (m, 1H), 2.68 – 2.58 (m, 1H), 1.41
6.94 (d, J = 7.7 Hz, 1H), 4.60 (d, J = 10.8 Hz, 1H), 4.40 (d, J =
3
19
1
0.8 Hz, 1H), 3.30 (s, 3H), 3.08 – 2.89 (m, 2H); F NMR (376
(
1
(
13
MHz, CDCl ) [ppm] δ -61.24 (t, J = 10.6 Hz, 3F); C NMR (100
3
1
9
MHz, CDCl ) [ppm] δ 175.2, 165.4, 143.6, 133.4, 129.5, 129.4,
3
s, 3H); F NMR (376 MHz, CDCl ) [ppm] δ -61.94 (t, J = 10.6
3
13
129.3, 128.5, 126.7, 125.2 (q, J = 276.0 Hz), 124.7, 122.8, 108.6,
67.7, 41.5 (d, J = 2.0 Hz), 36.8 (q, J = 31.0 Hz), 26.6; IR (KBr) ν
Hz, 3F); C NMR (100 MHz, CDCl ) [ppm] δ 178.9, 140.3,
3
1
34.2, 134.0, 125.0 (q, J = 277.0 Hz), 123.8, 122.6, 102.7, 44.1
d, J = 2.0 Hz), 40.9 (q, J = 28.5 Hz), 30.1, 25.5; IR (KBr) ν (cm
: 3066, 2939, 1725, 1634, 1581, 1467, 1361, 1261, 1149, 1088,
059, 948, 889, 840, 770, 738, 666, 614; HRMS (EI) found: m/z
20.9976 [M]; calcd. For C H BrF NO 320.9977.
-1
-
(cm ): 3061, 3004, 2944, 1721, 1608, 1467, 1359, 1282, 1146,
(
1
1116, 1078, 1044, 990, 856, 747, 705, 619; HRMS (ESI) found:
)
+
m/z 386.0985 [M+Na] ; calcd. for C H F NO +Na 386.0980.
1
9
16
3
3
1
3
4.2.19
yl)methyl)isoindoline-1,3-dione (3r) Yield: 82%; H NMR (400
MHz, CDCl ) [ppm] δ 7.85 (dd, J = 5.3, 3.1 Hz, 2H), 7.74 (dd, J
5.4, 3.1 Hz, 2H), 7.34 (t, J = 7.7 Hz, 1H), 7.25 (d, J = 7.4 Hz,
H), 7.06 (t, J = 7.5 Hz, 1H), 6.90 (d, J = 7.8 Hz, 1H), 4.01 (d, J
14.2 Hz, 1H), 3.90 (d, J = 14.2 Hz, 1H), 3.26 (s, 3H), 3.12 –
2-((1-methyl-2-oxo-3-(2,2,2-trifluoroethyl)indolin-3-
1
2
11
3
1
0 4.2.14
1 (3m) Yield: 85%; H NMR (400 MHz, CDCl
3-methyl-1-phenyl-3-(2,2,2-trifluoroethyl)indolin-2-one
1
3
) [ppm] δ 7.56 (t, J
3
=
1
2 = 7.7 Hz, 2H), 7.42 (d, J = 7.4 Hz, 2H), 7.35 (d, J = 7.3 Hz, 2H),
3 7.25 (d, J = 7.8 Hz, 1H), 7.15 (t, J = 7.5 Hz, 1H), 6.86 (d, J = 7.8
4 Hz, 1H), 3.06 – 2.94 (m, 1H), 2.80 – 2.68 (m, 1H), 1.56 (s, 3H);
=
19
1
1
9
3
2.97 (m, 2H); F NMR (376 MHz, CDCl
10.6 Hz, 3F); C NMR (100 MHz, CDCl
3
) [ppm] δ -61.48 (t, J =
) [ppm] δ 175.5, 168.0,
5
6
7
8
9
0
1
2
3
4
5
F NMR (376 MHz, CDCl
C NMR (100 MHz, CDCl ) [ppm] δ 178.0, 143.0, 134.4, 130.7,
3
) [ppm] δ -61.86 (t, J = 10.6 Hz, 3F);
13
3
3
1
1
43.4, 134.3, 131.6, 129.3, 126.7, 125.1 (q, J = 269.0 Hz), 124.4,
23.6, 122.5, 108.7, 44.4 (d, J = 2.0 Hz), 44.0, 38.1 (q, J = 28.0
1
1
29.7, 128.4, 128.3, 126.6, 125.3 (q, J = 276.0 Hz), 123.8, 123.1,
09.8, 44.5 (d, J = 2.0 Hz), 41.1 (q, J = 28.0 Hz), 25.4; IR (KBr)
ν (cm ): 2976, 2934, 2874, 1724, 1608, 1497, 1459, 1370, 1329,
286, 1260, 1204, 1147, 1070, 973, 756, 698, 595; HRMS (EI)
found: m/z 305.1024 [M]; calcd. For C H F NO 305.1027.
-1
-
1
Hz), 26.6; IR (KBr) ν (cm ): 2958, 2933, 1776, 1719, 1612, 1493,
1
8
469, 1426, 1386, 1344, 1294, 1263, 1139, 1080, 1023, 963, 928,
00, 753, 720, 603; HRMS (EI) found: m/z 388.1031 [M]; calcd.
1
1
7
14 3
For C H F N O 388.1035.
2
0
15
3
2
3

7
4
.2.20
3-(hydroxymethyl)-A1-mCeCthyEl-P3-T(2E,2D,2- MA4.N2.2U5 SC2R-bIuPtyTl-4-methyl-4-(2,2,2-trifluoroethyl)isoquinoline-
1
1
trifluoroethyl)indolin-2-one (3s) Yield: 51%; H NMR (400 MHz,
1,3(2H,4H)-dione (3d') Yield: 70%; H NMR (400 MHz, CDCl )
3
CDCl ) [ppm] δ 7.38 (t, J = 7.6 Hz, 1H), 7.30 (d, J = 7.5 Hz, 1H),
[ppm] δ 8.30 (d, J = 7.9 Hz, 1H), 7.73 – 7.64 (m, 1H), 7.50 (t, J =
7.7 Hz, 1H), 7.43 (d, J = 8.0 Hz, 1H), 4.08 – 3.98 (m, 2H), 3.39
(dq, J = 15.1, 10.4 Hz, 1H), 2.82 (dq, J = 15.1, 9.8 Hz, 1H), 1.67
3
7
1
.14 (t, J = 7.5 Hz, 1H), 6.94 (d, J = 7.8 Hz, 1H), 3.77 (d, J =
0.5 Hz, 1H), 3.69 (d, J = 11.1 Hz, 1H), 3.27 (s, 3H), 3.16 – 3.04
1
2
3
4
5
6
7
8
9
0
1
9
(m, 1H), 2.88 – 2.77 (m, 1H), 2.63 (s, 1H); F NMR (376 MHz,
(s, 3H), 1.61 (q, J = 6.0 Hz, 2H), 1.41 (q, J = 8.0 Hz, 2H), 0.97 (t,
1
3
19
CDCl ) [ppm] δ -61.47 (t, J = 10.6 Hz, 3F); C NMR (100 MHz,
J = 7.3 Hz, 3H); F NMR (376 MHz, CDCl ) [ppm] δ -61.37 (t,
3
3
1
3
CDCl ) [ppm] δ 177.1, 143.6, 129.2, 126.8, 125.6 (q, J = 277.0
J = 10.6 Hz, 3F); C NMR (100 MHz, CDCl ) [ppm] δ 174.2,
3
3
Hz), 124.1, 122.9, 108.7, 67.4, 49.8 (d, J = 2.0 Hz), 36.4 (q, J =
163.4, 140.4, 133.7, 129.3, 128.0, 125.6, 125.0 (q, J = 278.0 Hz),
124.4, 44.2 (q, J = 28.0 Hz), 43.6 (d, J = 2.0 Hz), 40.6, 31.4, 29.6,
20.2, 13.8; IR (KBr) ν (cm ): 2962, 2934, 2872, 1714, 1669,
-
1
2
1
8.0 Hz), 26.4; IR (KBr) ν (cm ): 3058, 2929, 1712, 1614, 1495,
470, 1431, 1375, 1260, 1143, 1118, 1071, 938, 753, 700, 616;
-
1
HRMS (EI) found: m/z 259.0818 [M]; calcd. For C H F NO
1464, 1435, 1359, 1258, 1181, 1141, 1069, 947, 771, 704;
1
2
12
3
2
+
2
59.0820.
HRMS (ESI) found: m/z 336.1191 [M+Na] ; calcd. for
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
6
6
6
6
6
C H F NO +Na 336.1187.
1
6
18
3
2
1 4.2.21
2 pyrrolo[3,2,1-ij]quinolin-2(4H)-one (3t) Yield: 63%; H NMR
3 (400 MHz, CDCl ) δ 7.13 (d, J = 7.3 Hz, 1H), 7.08 (d, J = 7.5 Hz,
1-methyl-1-(2,2,2-trifluoroethyl)-5,6-dihydro-1H-
1
4.2.26
dihydroisoquinolin-2(1H)-yl)acetonitrile (3e') Yield: 71%;
NMR (400 MHz, CDCl ) [ppm] δ 8.33 (d, J = 7.9 Hz, 1H), 7.80
2-(4-methyl-1,3-dioxo-4-(2,2,2-trifluoroethyl)-3,4-
1
H
3
4 1H), 7.00 (t, J = 7.5 Hz, 1H), 3.75 (t, J = 6.0 Hz, 2H), 2.87 – 2.76
3
5 (m, 3H), 2.71 – 2.60 (m, 1H), 2.04 (dt, J = 11.9, 6.0 Hz, 2H),
– 7.71 (m, 1H), 7.56 (t, J = 7.6 Hz, 1H), 7.48 (d, J = 8.0 Hz, 1H),
1
9
1
1
1
.44 (s, 3H); F NMR (376 MHz, CDCl ) [ppm] δ -61.81 (t, J =
4.93 (d, J = 2.2 Hz, 2H), 3.43 – 3.32 (m, 1H), 2.93 – 2.82 (m,
6
7
8
9
0
1
2
3
4
3
1
3
19
0.6 Hz, 3F); C NMR (100 MHz, CDCl ) [ppm] δ 177.4, 138.6,
1H), 1.74 (s, 3H); F NMR (376 MHz, CDCl ) [ppm] δ -61.61 (t,
3
3
1
3
29.7, 127.3, 125.4 (q, J = 276.0 Hz), 122.1, 121.5, 120.5, 45.6
J = 10.6 Hz, 3F); C NMR (100 MHz, CDCl ) [ppm] δ 173.4,
3
(
d, J = 2.0 Hz), 40.5 (q, J = 28.0 Hz), 39.1, 26.6, 26.5, 21.1; IR
162.2, 140.2, 134.8, 129.8, 128.5, 125.9, 124.8 (q, J = 277.0 Hz),
123.2, 114.1, 44.5 (q, J = 27.0 Hz), 44.1 (d, J = 2.0 Hz), 30.9,
-
1
(
KBr) ν (cm ): 2932, 2875, 1714, 1626, 1603, 1483, 1387, 1355,
259, 1142, 1069, 749, 666; HRMS (EI) found: m/z 269.1031
M]; calcd. For C H F NO 269.1027.
-
1
1
[
27.7; IR (KBr) ν (cm ): 2923, 2855, 1724, 1684, 1597, 1463,
1376, 1340, 1254, 1162, 1141, 1073, 973, 945, 772, 707, 582,
1
4
14 3
+
5
44; HRMS (ESI) found: m/z 319.0673 [M+Na] ; calcd. for
4
1
.2.22
2,4-dimethyl-4-(2,2,2-trifluoroethyl)isoquinoline-
1
C
H
11
F
N
2
O
2
+Na 319.0671.
12
3
,3(2H,4H)-dione (3a') Yield: 77%; H NMR (400 MHz, CDCl )
3
5 [ppm] δ 8.31 (d, J = 7.8 Hz, 1H), 7.68 (t, J = 7.5 Hz, 1H), 7.51 (t,
4.2.27
2-benzyl-4-methyl-4-(2,2,2-trifluoroethyl)isoquinoline-
1
6 J = 7.6 Hz, 1H), 7.44 (d, J = 7.9 Hz, 1H), 3.43 (s, 3H), 3.42 –
1,3(2H,4H)-dione (3f') Yield: 78%; H NMR (400 MHz, CDCl )
3
1
9
7 3.31 (m, 1H), 2.89 – 2.75 (m, 1H), 1.68 (s, 3H); 1 F NMR (376
[ppm] δ 8.31 (dd, J = 7.9, 0.8 Hz, 1H), 7.68 (td, J = 7.9, 1.2 Hz,
1H), 7.50 (t, J = 7.3 Hz, 1H), 7.44 (d, J = 7.5 Hz, 3H), 7.33 –
7.25 (m, 3H), 5.24 (q, J = 13.9 Hz, 2H), 3.47 – 3.35 (m, 1H),
3
8 MHz, CDCl ) [ppm] δ -61.66 (t, J = 9.4 Hz, 3F); C NMR (100
3
9 MHz, CDCl ) [ppm] δ 174.6, 163.7, 140.4, 133.8, 129.3, 128.1,
0 125.6, 125.4 (q, J = 278.0 Hz), 124.3, 44.4 (q, J = 27.5 Hz), 43.6
1 (d, J = 2.0 Hz), 31.2, 27.4; IR (KBr) ν (cm ): 2956, 2928, 2856,
2 1715, 1671, 1603, 1466, 1421, 1364, 1308, 1255, 1140, 1056,
3 768, 701, 579; HRMS (ESI) found: m/z 272.0895 [M+H] ; calcd.
3
1
9
2.89 – 2.78 (m, 1H), 1.65 (s, 3H); F NMR (376 MHz, CDCl
)
)
3
-
1
13
[ppm] δ -61.61 (t, J = 10.6 Hz, 3F); C NMR (100 MHz, CDCl
3
[ppm] δ 174.3, 163.4, 140.4, 136.8, 133.9, 129.5, 128.6, 128.4,
128.1, 127.5, 125.7, 125.0 (q, J = 278.0 Hz), 124.3, 44.0, 43.9 (q,
+
-
1
for C H F NO +H 272.0898.
J = 27.0 Hz), 43.8 (d, J = 2.0 Hz), 31.5; IR (KBr) ν (cm ): 3035,
4
5
6
7
8
9
0
1
2
13 12
3
2
2
1
962, 1716, 1673, 1602, 1497, 1462, 1430, 1386, 1354, 1317,
4
1
.2.23
2-ethyl-4-methyl-4-(2,2,2-trifluoroethyl)isoquinoline-
1
258, 1149, 1072, 1039, 967, 835, 802, 762, 704, 668; HRMS
,3(2H,4H)-dione (3b') Yield: 67%; H NMR (400 MHz, CDCl )
+
3
(ESI) found: m/z 370.1032 [M+Na] ; calcd. for C H F NO +Na
19 16
3
2
δ 8.30 (d, J = 7.9 Hz, 1H), 7.67 (t, J = 7.5 Hz, 1H), 7.50 (t, J =
3
70.1030.
7
2
3
.6 Hz, 1H), 7.43 (d, J = 8.0 Hz, 1H), 4.09 (dt, J = 7.3, 5.2 Hz,
H), 3.42 – 3.32 (m, 1H), 2.81 (dq, J = 15.3, 9.8 Hz, 1H), 1.67 (s,
4.2.28
6-methoxy-2,4-dimethyl-4-(2,2,2-
1
9
H), 1.23 (t, J = 7.1 Hz, 3H); F NMR (376 MHz, CDCl ) [ppm]
trifluoroethyl)isoquinoline-1,3(2H,4H)-dione (3g') Yield: 63%;
3
1
3
1
δ -61.46 (t, J = 9.4 Hz, 3F); C NMR (100 MHz, CDCl ) [ppm]
H NMR (400 MHz, CDCl ) δ 8.25 (d, J = 8.8 Hz, 1H), 7.02 (dd,
3
3
δ 174.0, 163.2, 140.4, 133.7, 129.3, 128.0, 125.6, 125.0 (q, J =
J = 8.8, 2.3 Hz, 1H), 6.86 (d, J = 2.2 Hz, 1H), 3.92 (s, 3H), 3.40
3 277.0 Hz), 124.4, 44.3 (q, J = 27.5 Hz), 43.5 (d, J = 2.0 Hz), 35.9,
(s, 3H), 3.35 (dt, J = 15.1, 8.1 Hz, 1H), 3.38 – 3.30 (m, 1H), 2.83
-
1
19
4 31.2, 12.7; IR (KBr) ν (cm ): 2923, 2855, 1724, 1684, 1597,
5 1463, 1376, 1340, 1254, 1162, 1141, 1073, 973, 945, 772, 707,
6 582; HRMS (ESI) found: m/z 308.0873 [M+Na] ; calcd. for
– 2.72 (m, 1H), 1.66 (s, 3H); F NMR (376 MHz, CDCl ) [ppm]
3
1
3
δ -61.61 (t, J = 10.6 Hz, 3F); C NMR (100 MHz, CDCl ) [ppm]
3
+
δ 174.6, 164.0, 163.4, 142.6, 131.7, 125.0 (q, J = 279.0 Hz),
117.3, 113.6, 111.1, 55.6, 44.4 (q, J = 27.5 Hz), 43.7 (d, J = 1.0
7 C H F NO +Na 308.0874.
1
4
14
3
2
-
1
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
Hz), 31.3, 27.2; IR (KBr) ν (cm ): 2961, 2847, 1712, 1666, 1609,
4
1
.2.24
4-methyl-2-propyl-4-(2,2,2-trifluoroethyl)isoquinoline-
1
1504, 1435, 1361, 1257, 1184, 1140, 1096, 1033, 833, 778, 701;
,3(2H,4H)-dione (3c') Yield: 70%; H NMR (400 MHz, CDCl )
+
3
HRMS (ESI) found: m/z 302.1000 [M+H] ; calcd. for
[ppm] δ 8.30 (d, J = 7.9 Hz, 1H), 7.68 (t, J = 7.6 Hz, 1H), 7.50 (t,
C H F NO +H 301.1004.
14 14 3 3
J = 7.6 Hz, 1H), 7.43 (d, J = 7.9 Hz, 1H), 4.07 – 3.93 (m, 2H),
3
1
.39 (dq, J = 15.1, 10.4 Hz, 1H), 2.82 (dq, J = 15.1, 9.8 Hz, 1H),
19
Acknowledgments
.74 – 1.63 (m, 5H), 0.98 (t, J = 7.4 Hz, 3H); F NMR (376
13
MHz, CDCl ) [ppm] δ -61.37 (t, J = 10.6 Hz, 3F); C NMR (100
3
This work was financially supported by the National Natural
Science Foundation of China (No. 21422104).
MHz, CDCl ) [ppm] δ 174.2, 163.4, 140.4, 133.7, 129.4, 128.0,
3
1
25.6, 125.0 (q, J = 277.0 Hz), 124.4, 44.2 (q, J = 27.0 Hz), 43.6
-1
(d, J = 1.0 Hz), 42.3, 31.4, 20.9, 11.3; IR (KBr) ν (cm ): 2964,
References and notes
2
1
875, 1714, 1670, 1516, 1462, 1434, 1391, 1357, 1256, 1182,
140, 1069, 704, 581; HRMS (ESI) found: m/z 332.1031
+
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1
5
16
3
2

8
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ACCEPTED MANUSCRIPT
Supporting Information
Light-Induced BiOBr Nanosheets Accelerated Highly
Regioselective Intermolecular Trifluoromethylation/Arylation of
Alkenes to Synthesize CF -Containing Aza-Heterocycles
3
a
a
a
b
,a
Cuibo Liu, Weiwei Zhao, Yi Huang, Hongming Wang, Bin Zhang*
a
Department of Chemistry, School of Science, Tianjin University, and Collaborative Innovation
Center of Chemical Science and Engineering (Tianjin), Tianjin 300072, China. Fax&Tel: +86 22
2
b
7403475; E-mail: bzhang@tju.edu.cn
Institute for Advanced Study, Nanchang University, Nanchang 330031, China
Table of Contents
I. General information and materials
…
………………………………………………………………………………………2
II. Synthesis and characterizations of BiOBr nanosheets
……………………………………………………………………………………....3
III. Typical procedures for the synthesis of substrates
………………………………………………………………………………………4
…
…
IV. General procedure for light-induced BiOBr nanosheets promoted
trifluoromethylation/arylation of alkenes
…………………………………………………………………………………………5
V. Control experiments
…
……………………………………………………………………………………....6―7
VI. Copies of NMR Spectra
…
………………………………………………………………………………………8―61
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I. General Information:
Materials
All purchased reagents were used without further purification. Analytical thin layer
chromatography was performed on 0.20 mm Qingdao Haiyang silica gel plates. Silica gel
(
200-300 mesh) (from Qingdao Haiyang Chem. Company, Ltd.) was used for flash
chromatography.
Characterization
The scanning electron microscopy (SEM) images were taken with a Hitachi S-4800 scanning
electron microscope (SEM, 5 kV) equipped with the Thermo Scientific energy-dispersion X-ray
fluorescence analyzer. Transmission electron microscopy (TEM), and higher-magnification
transmission electron microscopy (HRTEM) were carried out with JEOL JEM-2100F system
equipped with the EDAX Genesis XM2. The X-ray diffraction patterns (XRD) of the products
were recorded with a PANalytical X'Pert PRO X-ray diffractometer with Co Kα radiation (λ =
1
.78897 nm) at 40 kV and 40 mA. Then the data was converted into corresponding Cu Kα
radiation. The optical properties of the samples were analyzed by a Shimadzu UV-2550
ultraviolet/visible diffuse reflectance spectroscopy (DRS), during which BaSO was employed as
4
1
13
19
the internal reflectance standard. H, C, F NMR were recorded on Varian Mercury Plus 400
1
13
19
instruments at 400 MHz ( H NMR), 100 MHz ( C NMR), as well as 376 MHz ( F NMR).
Chemical shifts were reported in ppm down field from internal Me Si and external CCl F,
4
3
respectively. Multiplicity was indicated as follows: s (singlet), d (doublet), t (triplet), q (quartet),
m (multiplet), dd (doublet of doublet), br (broad). Coupling constants were reported in Hertz (Hz).
HRMS were recorded on an Agilent Q-TOF spectrometer using the ESI method and Waters TOF
spectrometer using the EI method. IR spectra were recorded on an AVATAR 360 FT-IR
spectrometer.
Page - 2 - of 61

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II. Synthesis and characterizations of BiOBr nanosheets
1
The procedure was according with the previous literature.
Typically, 0.97 g Bi(NO ) ·5H O was dissolved in 3.0 ml acetic acid, and the resulting solution
3
3
2
was added to 30 ml de-ionized water containing 0.24 g KBr under vigorous stirring. Upon the
adding of Bi(NO ) /HAc solution, yellow precipitates were immediately observed which then
3
3
became light yellow as addition was completed. After stirring for 20 min at room temperature, the
suspension was transferred into a Teflon-lined stainless steel autoclave (40 ml capacity) and
◦
heated at 120 C for 6.0 h. The resulting precipitate was filtrated, washed thoroughly with distilled
◦
water to remove any possible ionic species in the product, and then dried at 60 C overnight.
Fig. S1. a) SEM image, b) TEM image, c and its inset) HRTEM image and SAED pattern;nanosheets, d) XRD pattern, e) UV-vis
1/2
diffuse reflectance spectra (DRS), f) The plots of (ahν) versus the energy of light (Eg) of the BiOBr nanosheets.
The morphology and structure of the as-prepared BiOBr nanostructures are characterized by using
scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The
corresponding SEM image (Fig. S1a) and TEM image (Fig. S1b) show that the obtained samples
are sheet-like structures with a thickness below 50 nm. High resolution transmission electron
microscopy (HRTEM) (Fig. S1c) and selected area electron diffraction (SAED) pattern (the inset
of Fig. S1c) of BiOBr demonstrate that the as-prepared BiOBr nanosheets are single-crystalline.
The X-ray diffraction data of BiOBr samples is shown in Fig. S1d. All of the detectable reflection
peaks can be assigned to a pure tetragonal phase of BiOBr (JCPDS No. 73-2061). The UV-vis
diffuse reflectance spectra (DRS) of the BiOBr samples (Fig. S1e) displays its absorption range
to 440 nm, corresponding to band-gap energy (Eg) of approximately 2.82 eV (Fig. S1f). To
monitor the photocatalytic activity of the synthesized BiOBr nanosheets, the as-prepared BiOBr
nanosheets are used in the following organic transformations.
Page - 3 - of 61

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2
-4
III. Typical procedures for the synthesis of substrates
Substrates 1a-1o, and 1t were synthesized according to the literature 2; substrates 1p-1r were
synthesized according to the literature 3; substrates 1a΄-1g΄ were synthesized according to the
literature 4.
Reference:
1
. Z. Jiang, F. Yang, G. D. Yang, L. Kong, M. O. Jones, T. C. Xiao, P. P. Edwards, J. Photochem.
Photobiol. A 2010, 212, 8-13.
2. D. C. Fabry, M. Stodulski, D.-C. S. Hoerner, T. Gulder, Chem. Eur. J. 2012, 18, 10834-10838.
3. X. Mu, T. Wu, H.-Y. Wang, Y,-L. Guo, G. S. Liu, J. Am. Chem. Soc. 2012, 134, 878-881.
4. M. P. Sibi, N. Prabagaran, S. G. Ghorpade, C. P. Jasperse, J. Am. Chem. Soc. 2003, 125,
11796-11797.
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IV. General procedure for light-induced BiOBr nanosheets promoted
trifluoromethylation/arylation of alkene
1
a (0.2 mmol, 35.0 mg), BiOBr (0.02 mmol, 6.1 mg), K HPO (98%, 0.6 mmol, 106.6 mg) and
2 4
DMF (1.0 mL) were added to a dried 10 mL Sclenk flask under air. After degassing under vacuum
and refilling with Ar (three times), the tube was sealed well, and then immersed in an ice bathe
maintaining for 5 minutes. After that, CF SO Cl (98%, 0.6 mmol, 103.2 mg) was added to the
3
2
mixture via the microinjector. The Sclenk tube was immediately moved to a distance of ca. 30 cm
o
from the light source and the resulting solution was stirred at no more than 10 C under light
irradiation for 6 h. After the completion of the reaction (by TLC), the reaction mixture was
centrifuged and the organic phases were diluted with water (4.0 mL) and extracted with CH Cl (3
2
2
×
6.0 mL). The combined organic layers were washed with brine, and dried over anhydrous
MgSO . After removal of the solvent, the residue was purified by flash column chromatography
4
1
on silica gel to give the desired product 3a. 87% yield, H NMR (400 MHz, CDCl ) [ppm] δ 7.34
3
(
t, J = 7.8 Hz, 1H), 7.29 (d, J = 5.2 Hz, 1H), 7.12 (t, J = 7.5 Hz, 1H), 6.91 (d, J = 7.8 Hz, 1H),
1
9
3
.26 (s, 3H), 2.92 – 2.76 (m, 1H), 2.75 – 2.60 (m, 1H), 1.43 (s, 3H); F NMR (376 MHz, CDCl )
3
1
3
[ppm] δ -61.95 (t, J = 10.5, 3F); C NMR (100 MHz, CDCl ) [ppm] δ 178.5, 142.9, 131.0, 128.5,
3
1
25.2 (q, J = 277.0 Hz), 123.6, 122.6, 108.4, 44.4 (d, J = 2.0 Hz), 40.6 (q, J = 28.0 Hz), 26.4, 25.0;
-1
IR (KBr) ν (cm ): 2927, 2857, 1728, 1594, 1495, 1464, 1429, 1365, 1260, 1185, 1085, 966, 801,
52, 703; HRMS (EI) found: m/z 243.0874 [M]; calcd. For C H F NO 243.0871.
7
1
2
12 3
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V. Control experiments
The addition of TEMPO to the reaction system under standard conditions
1
a (0.1 mmol, 17.5 mg), BiOBr (0.01 mmol, 3.0 mg), K HPO (98%, 0.3 mmol, 53.3 mg), and
2 4
TEMPO (98%, 0.3 mmol, 47.8 mg) were added to a dried 10 mL Sclenk flask under air. After
degassing under vacuum and refilling with Ar (three times), the tube was sealed well, and then
immersed in an ice bathe maintaining for 5 minutes. After that, CF SO Cl (98%, 0.3 mmol, 51.6
3
2
mg) was added to the mixture via the microinjector. The Sclenk tube was immediately moved to a
distance of ca. 30 cm from the light source and the resulting solution was stirred at no more than
o
1
0 C under light irradiation for 6 h. After that, the Sclenk tube was moved to room temperature,
1
9
and α,α,α-trifluorotoluene (internal standard, 98%, 0.1 mmol, 14.3 mg) was added. F NMR
analysis of this reaction mixture showed that the product 3a was not detected. This indicated that
the difunctionalized process of alkenes by our photocatalic strategy was indeed through a radical
pathway.
The addition of oxamide to the reaction system under standard conditions
1
a (0.1 mmol, 17.5 mg), BiOBr (0.01 mmol, 3.0 mg), K HPO (98%, 0.3 mmol, 53.3 mg), and
2 4
oxamide (0.3 mmol, 26.4 mg) were added to a dried 10 mL Sclenk flask under air. After degassing
under vacuum and refilling with Ar (three times), the tube was sealed well, and then immersed in
an ice bathe maintaining for 5 minutes. After that, CF SO Cl (98%, 0.3 mmol, 51.6 mg) was
3
2
added to the mixture via the microinjector. The Sclenk tube was immediately moved to a distance
o
of ca. 30 cm from the light source and the resulting solution was stirred at no more than 10 C
under light irradiation for 6 h. After that, the Sclenk tube was moved to room temperature, and
1
9
α,α,α-trifluorotoluene (internal standard, 98%, 0.1 mmol, 14.3 mg) was added. F NMR
analysis of this reaction mixture showed that the product 3a was obtained in 36% yield. This
lower yield might be attributed to the consumption of photogenerated holes by oxamide. The
reduction of holes directly hampered the oxidation of the intermediate of the later stage and the
regeneration of the photocatalyst. This result indicated that the generated holes were indispensible
for the trifluoromethylation/arylation of alkenes.
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The addition of benzoquinone to the reaction system under standard conditions
1
a (0.1 mmol, 17.5 mg), BiOBr (0.01 mmol, 3.0 mg), K HPO (98%, 0.3 mmol, 53.3 mg), and
2 4
NaIO (0.3 mmol, 59.4 mg) were added to a dried 10 mL Sclenk flask under air. After degassing
3
under vacuum and refilling with Ar (three times), the tube was sealed well, and then immersed in
an ice bathe maintaining for 5 minutes. After that, CF SO Cl (98%, 0.3 mmol, 51.6 mg) was
3
2
added to the mixture via the microinjector. The Sclenk tube was immediately moved to a distance
o
of ca. 30 cm from the light source and the resulting solution was stirred at no more than 10 C
under light irradiation for 6 h. After that, the Sclenk tube was moved to room temperature, and
1
9
α,α,α-trifluorotoluene (internal standard, 98%, 0.1 mmol, 14.3 mg) was added. F NMR
analysis of this reaction mixture showed that only 20% of the product 3a was obtained. This
unsatisfactory result might be resulted from the decrease of photogenerated eletrons caused by
benzoquinone. The reduction of photogenerated electrons led to the small amount of CF free
3
radical and the regeneration of photocatalyst. This result indicated that the generated electrons
were essential for the trifluoromethylation/arylation of alkenes.
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VI. Copies of NMR Spectra
1
,3-dimethyl-3-(2,2,2-trifluoroethyl)indolin-2-one
CF3
O
N
3a
1
H NMR (400 MHz, CDCl ) [ppm] δ 7.34 (t, J = 7.8 Hz, 1H), 7.29 (d, J = 5.2 Hz, 1H), 7.12 (t, J =
3
7
.5 Hz, 1H), 6.91 (d, J = 7.8 Hz, 1H), 3.26 (s, 3H), 2.92 – 2.76 (m, 1H), 2.75 – 2.60 (m, 1H), 1.43
1
9
13
(
s, 3H); F NMR (376 MHz, CDCl ) [ppm] δ -61.95 (t, J = 10.5, 3F); C NMR (100 MHz,
3
CDCl ) [ppm] δ 178.5, 142.9, 131.0, 128.5, 125.2 (q, J = 277.0 Hz), 123.6, 122.6, 108.4, 44.4 (d, J
3
-
1
=
2.0 Hz), 40.6 (q, J = 28.0 Hz), 26.4, 25.0; IR (KBr) ν (cm ): 2927, 2857, 1728, 1594, 1495,
464, 1429, 1365, 1260, 1185, 1085, 966, 801, 752, 703; HRMS (EI) found: m/z 243.0874 [M];
calcd. For C H F NO 243.0871.
1
1
2
12 3
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1
,3,5-trimethyl-3-(2,2,2-trifluoroethyl)indolin-2-one
1
H NMR (400 MHz, CDCl ) [ppm] δ 7.27 – 7.21 (m, 1H), 7.17 (d, J = 6.2 Hz, 1H), 6.79 (d, J =
3
1
9
7
.8 Hz, 1H), 3.23 (s, 3H), 2.87 – 2.75 (m, 1H), 2.71 – 2.60 (m, 1H), 2.37 (s, 3H), 1.41 (s, 3H); F
1
3
NMR (376 MHz, CDCl ) [ppm] δ -61.90 (t, J = 10.6 Hz, 3F); C NMR (100 MHz, CDCl ) [ppm]
3
3
δ 178.4, 140.5, 132.2, 131.1, 128.8, 125.3 (q, J = 276.0 Hz), 124.3, 108.1, 44.4 (d, J = 2.0 Hz),
-
1
4
1
0.6 (q, J = 29.0 Hz), 26.4, 25.0, 21.1; IR (KBr) ν (cm ): 2969, 2930, 2873, 1718, 1654, 1626,
503, 1462, 1432, 1360, 1259, 1182, 1138, 1081, 1055, 948, 888, 810, 667, 627, 557; HRMS (EI)
found: m/z 257.1026 [M]; calcd. For C H F NO 257.1027.
13
14 3
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-methoxy-1,3-dimethyl-3-(2,2,2-trifluoroethyl)indolin-2-one
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H NMR (400 MHz, CDCl ) [ppm] δ 6.90 (s, 1H), 6.85 (dd, J = 8.4, 2.1 Hz, 1H), 6.80 (d, J = 8.4
3
1
9
Hz, 1H), 3.82 (s, 3H), 3.23 (s, 3H), 2.89 – 2.77 (m, 1H), 2.70 – 2.58 (m, 1H), 1.41 (s, 3H);
F
1
3
NMR (376 MHz, CDCl ) [ppm] δ -61.87 (t, J = 10.6 Hz, 3F); C NMR (100 MHz, CDCl ) [ppm]
3
3
δ 178.1, 156.1, 136.4, 132.4, 125.3 (q, J = 276.0 Hz), 112.6, 111.3, 108.7, 55.8, 44.2 (d, J = 1.0
-
1
Hz), 40.6 (q, J = 28.0 Hz), 26.5, 25.0; IR (KBr) ν (cm ): 3058, 2979, 2942, 2840, 1712, 1628,
470, 1436, 1363, 1284, 1258, 1125, 1083, 1040, 947, 913, 868, 803, 732, 693, 667, 613, 574, 523;
HRMS (EI) found: m/z 273.0977 [M]; calcd. For C H F NO 273.0977.
1
1
3
14
3
2
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-(tert-butyl)-1,3-dimethyl-3-(2,2,2-trifluoroethyl)indolin-2-one
1
H NMR (400 MHz, CDCl ) [ppm] δ 7.37 – 7.31 (m, 2H), 6.83 (d, J = 8.1 Hz, 1H), 3.24 (s, 3H),
3
1
9
2
.87 – 2.76 (m, 1H), 2.73 – 2.62 (m, 1H), 1.43 (s, 3H), 1.34 (s, 9H); F NMR (376 MHz, CDCl )
3
1
3
[
ppm] δ -61.87 (t, J = 10.6 Hz, 3F); C NMR (100 MHz, CDCl ) [ppm] δ 178.7, 145.9, 140.4,
3
1
30.7, 125.0, 124.9 (q, J = 278.0 Hz), 120.9, 107.8, 44.6 (d, J = 2.0 Hz), 40.6 (q, J = 28.0 Hz),
-1
3
4.6, 31.5, 26.4, 25.0; IR (KBr) ν (cm ): 2963, 2908, 2872, 1719, 1625, 1505, 1465, 1363, 1259,
+
1
141, 1054, 947, 841, 816; HRMS (ESI) found: m/z 322.1395 [M+Na] ; calcd. for
C H F NO+Na 322.1395.
1
6
20 3
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-fluoro-1,3-dimethyl-3-(2,2,2-trifluoroethyl)indolin-2-one
1
H NMR (400 MHz, CDCl ) [ppm] δ 7.07 – 7.01 (m, 2H), 6.82 (dd, J = 9.1, 4.1 Hz, 1H), 3.25 (s,
3
1
9
3
H), 2.91 – 2.79 (m, 1H), 2.70 – 2.59 (m, 1H), 1.43 (s, 3H); F NMR (376 MHz, CDCl ) [ppm] δ
3
1
3
-
61.97 (t, J = 10.6 Hz, 3F), -120.34 – -120.40 (m, 1F); C NMR (100 MHz, CDCl ) [ppm] δ
3
1
78.1, 159.3 (d, J = 239.0 Hz), 138.8 (d, J = 2.0 Hz), 132.6 (d, J = 8.0 Hz), 125.1 (q, J = 277.0
Hz), 114.9 (d, J = 23.0 Hz), 111.8 (dd, J = 1.5, 23 Hz), 108.9 (d, J = 9.0 Hz), 44.8 (d, J = 2.0 Hz),
-1
4
0.6 (q, J = 27.5 Hz), 26.6, 24.9; IR (KBr) ν (cm ): 2959, 2926, 2857, 1723, 1590, 1496, 1445,
1
358, 1263, 1186, 1148, 1119, 1082, 963, 812, 669, 561; HRMS (EI) found: m/z 261.0781 [M];
calcd. For C H F NO 261.0777.
1
2
11 4
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-chloro-1,3-dimethyl-3-(2,2,2-trifluoroethyl)indolin-2-one
1
H NMR (400 MHz, CDCl ) [ppm] δ 7.31 (dd, J = 8.3, 2.0 Hz, 1H), 7.26 (d, J = 1.7 Hz, 1H), 6.82
3
1
9
(
d, J = 8.3 Hz, 1H), 3.24 (s, 3H), 2.90 – 2.79 (m, 1H), 2.70 – 2.59 (m, 1H), 1.42 (s, 3H); F NMR
1
3
(
376 MHz, CDCl ) [ppm] δ -61.96 (t, J = 10.6 Hz, 3F); C NMR (100 MHz, CDCl ) [ppm] δ
3
3
1
77.9, 141.5, 132.7, 128.5, 128.1, 125.1 (q, J = 277.0 Hz), 124.1, 109.4, 44.6 (d, J = 2.0 Hz), 40.6
-
1
(
q, J = 28.0 Hz), 26.6, 24.9; IR (KBr) ν (cm ): 2975, 2939, 2884, 1721, 1648, 1610, 1490, 1429,
357, 1303, 1258, 1184, 1141, 1078, 946, 883, 814, 755; HRMS (EI) found: m/z 277.0479 [M];
calcd. For C H ClF NO 277.0481.
1
1
2
11
3
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-bromo-1,3-dimethyl-3-(2,2,2-trifluoroethyl)indolin-2-one
1
H NMR (400 MHz, CDCl ) [ppm] δ 7.45 (dd, J = 8.3, 1.8 Hz, 1H), 7.39 (d, J = 1.3 Hz, 1H), 6.78
3
1
9
(
d, J = 8.3 Hz, 1H), 3.23 (s, 3H), 2.90 – 2.78 (m, 1H), 2.70 – 2.58 (m, 1H), 1.42 (s, 3H); F NMR
1
3
(
376 MHz, CDCl ) [ppm] δ -61.95 (t, J = 10.6 Hz, 3F); C NMR (100 MHz, CDCl ) [ppm] δ
3
3
1
77.8, 142.0, 133.1, 131.4, 126.8, 125.0 (q, J = 277.0 Hz), 115.3, 109.9, 44.5 (d, J = 2.0 Hz), 40.6
-1
(
q, J = 28.0 Hz), 26.5, 24.9; IR (KBr) ν (cm ): 2976, 2939, 2883, 1722, 1664, 1609, 1489, 1427,
1
3
359 1304, 1259, 1185, 1141, 1078, 1057, 946, 883, 811, 664, 620, 535; HRMS (EI) found: m/z
20.9976 [M]; calcd. For C H BrF NO 320.9977.
1
2
11
3
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