Sulfonation and trifluoromethylation of enol acetates with sulfonyl chlorides using visible-light photoredox catalysis

Article abstract of DOI:10.1002/ejoc.201300693

A mild, practical method to prepare α-sulfonyl and α-trifluoromethyl ketones from readily available enol acetates and sulfonyl chlorides has been developed using visible-light photoredox catalysis. The method could be used with a wide range of enol acetates and sulfonyl chlorides, and gave the desired products in satisfactory to excellent yields. A practical method to prepare α-sulfonyl and α-trifluoromethyl ketones from enol acetates and sulfonyl chlorides using visible-light photoredox catalysis is presented. Copyright

Full text of DOI:10.1002/ejoc.201300693

Job/Unit: O30693
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Date: 08-07-13 11:06:22
Pages: 9
FULL PAPER
Photoredox Catalysis
H. Jiang, Y. Cheng, Y. Zhang,*
S. Yu* ............................................... 1–9
Sulfonation and Trifluoromethylation of
Enol Acetates with Sulfonyl Chlorides
Using Visible-Light Photoredox Catalysis
A practical method to prepare α-sulfonyl
and α-trifluoromethyl ketones from enol
acetates and sulfonyl chlorides using vis-
ible-light photoredox catalysis is presented.
Keywords: Sulfonation / Trifluoromethyl-
ation / Enol acetates / Ketones / Photo-
chemistry / Photooxidation
0000, 0–0
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Job/Unit: O30693
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Date: 08-07-13 11:06:22
Pages: 9
H. Jiang, Y. Cheng, Y. Zhang, S. Yu
FULL PAPER
DOI: 10.1002/ejoc.201300693
Sulfonation and Trifluoromethylation of Enol Acetates with Sulfonyl Chlorides
Using Visible-Light Photoredox Catalysis
Heng Jiang,[a] Yuanzheng Cheng,[a] Yan Zhang,*[a,b] and Shouyun Yu*[a]
Keywords: Sulfonation / Trifluoromethylation / Enol acetates / Ketones / Photochemistry / Photooxidation
A mild, practical method to prepare α-sulfonyl and α-tri-
fluoromethyl ketones from readily available enol acetates
and sulfonyl chlorides has been developed using visible-light
photoredox catalysis. The method could be used with a wide
range of enol acetates and sulfonyl chlorides, and gave the
desired products in satisfactory to excellent yields.
Quite recently, our group reported the direct C–H sulfon-
ation and trifluoromethylation of enamides using sulfonyl
chlorides.[12] Li and co-workers reported that aryl sulfonyl
chlorides could be used as precursors of aryl radicals to
initiate cascade reactions.[13] Zheng and co-workers devel-
oped visible-light-induced sulfenylation of indole deriva-
tives with aryl sulfonyl chlorides.[14] Due to the wide avail-
ability of sulfonyl chlorides, the development of more useful
transformations using sulfonyl chlorides as radical precur-
sors is still highly desirable.
The α-functionalization of carbonyl compounds is one of
the most important and useful transformations in organic
synthesis. Recently, König and co-workers achieved the vis-
ible-light-mediated α-arylation of enol acetates using aryl
diazonium salts as aryl radical precursors.[15] Taking our
previous work into consideration, we envisioned that α-sulf-
onyl and α-trifluoromethyl ketones, which are not easily ac-
cessible,[16] could be generated from enol acetates and sulf-
onyl chlorides using visible-light photoredox catalysis (Fig-
ure 1).
Introduction
Visible-light photoredox catalysis, which takes advantage
of the redox ability of excited-state photosensitizers formed
upon irradiation by visible light, has attracted great interest
in the synthetic chemistry community since 2008.[1] The
catalytic cycle involves single-electron-transfer (SET) pro-
cesses, and the method has obvious advantages such as mild
conditions, easy handling, and environmentally friendly
properties. Oxidative quenching is one of the typical SET
processes in visible-light photoredox catalysis, and in this
process, the excited-state photosensitizer is quenched by an
oxidant.[2] Many reagents have been reported to participate
in oxaditive quenching processes as reaction substrates or
quenchers, including viologens, alkyl and aryl halides,[3]
aryldiazonium salts,[4] aryl ketones,[5] persulfates,[6] etc.[7]
Sulfonyl chlorides, including alkyl, aryl, and trifluoro-
methyl sulfonyl chlorides, have been used as common radi-
cal precursors in various transformations[8] leading to sulf-
onyl or trifluoromethyl functionalized compounds with en-
hanced biological properties.[9] Indeed, significant progress
has been achieved recently in the area of photoredox reac-
tions involving sulfonyl chlorides. For example, Stephenson
and co-workers reported a radical addition reaction be-
tween tosyl chloride and unfunctionalized alkenes.[10] Mac-
Millan and co-workers demonstrated the trifluoromethyl-
ation of arenes and heteroarenes using cheap and easy-to-
handle CF3SO2Cl as the trifluoromethyl radical source.[11]
[a] State Key Laboratory of Analytical Chemistry for Life Science,
Institute of Chemical Biology and Drug Innovation, School of
Chemistry and Chemical Engineering, Nanjing University,
22 Hankou Road, Nanjing 210093, China
E-mail: njuzy@nju.edu.cn
yushouyun@nju.edu.cn
Homepage: http://hysz.nju.edu.cn/yanzhang/
http://hysz.nju.edu.cn/yusy/
[b] Laboratory of Chemical Genomics, School of Chemical
Biology and Biotechnology, Peking University, Shenzhen
Graduate School,
Shenzhen 518055, China
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.201300693.
Figure 1. Sulfonation and trifluoromethylation of enamides and
enol acetates.
2
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Visible-Light Photoredox Catalysis
isfactory yields (79–82%). Electron-neutral and electron-
rich arenesulfonyl chlorides also smoothly underwent this
transformation to give 3i–3k in good to excellent yields.
Chlorobenzenesulfonyl chlorides with chloride in the ortho,
meta, or para positions all served as suitable substrates in
this reaction, and gave the corresponding α-sulfonyl aceto-
phenones (i.e., 3f–3h). Sulfone 3l could also be prepared in
55% yield using this reaction. Heteroarylsulfonyl chlorides
also smoothly underwent this transformation to give 3m
and 3n in good yields. In addition, the sulfonation of 2a
with alkylsulfonyl chlorides 2o–2q worked quite well, and
gave the corresponding α-sulfonyl acetophenones (i.e., 3o–
3q) in satisfactory to excellent yields.
Results and Discussion
To synthesize α-sulfonyl ketones, we chose phenylvinyl
acetate (1a) and tosyl chloride (2a) for our initial investiga-
tion (Table 1). When a solution of 1a and 2a in CH2Cl2 was
irradiated with visible light [13 W white LED (light-emit-
ting diode)] in the presence of Ir(ppy)3 [I, –1.73 V vs. satu-
rated calomel electrode (SCE)],[3a] 1-phenyl-2-tosylethanone
(3a) was obtained in 84% isolated yield (Table 1, entry 1).
The yield dropped to 46% when Ir(ppy)2(dtbbpy)PF6 (II,
–0.93 V vs. SCE)[3a] was used as the photocatalyst (Table 1,
entry 2). Hardly any reaction occurred when Ru(bpy)3-
(PF6)2 (III, –0.86 V vs. SCE)[3a] was used, due to the lower
reductive potential of its excited state (Table 1, entry 3). Sol-
vent screening showed that CH2Cl2 was superior to other
solvents such as CH3CN, toluene, and DMF (Table 1, en-
tries 4–6). A higher catalyst loading did not improve this
reaction further (Table 1, entry 7). Some control experi-
ments were also conducted. No reaction (n.r.) was observed
when either the irradiation or the photocatalyst were omit-
ted (Table 1, entries 8 and 9).
Table 2. Scope of the sulfonyl chlorides.[a,b]
Table 1. Optimization of reaction conditions for sulfonation.[a]
[a] Reaction conditions: 1a (0.2 mmol), sulfonyl chloride
(1.5 equiv., 0.3 mmol), and photocatalyst
I
(1.0 mol-%,
0.002 mmol) in CH2Cl2 (2.0 mL) were irradiated with a 13 W white
LED for 8–24 h. [b] Isolated yields. [c] 5.0 equiv. of methanesulf-
onyl chloride was used.
Entry
Catalyst
Solvent
Yield [%][b]
1
2
3
4
5
6
I
CH2Cl2
CH2Cl2
CH2Cl2
CH3CN
toluene
DMF
CH2Cl2
CH2Cl2
CH2Cl2
84
46
trace
60
17
55
84
n.r.
trace
We then explored the coupling reactions of various enol
acetates with tosyl chloride (2a). As shown in Table 3, when
enol acetates 1b–1f were used, the corresponding α-sulfonyl
ketones (i.e., 4b–4f) were obtained in good to excellent
yields. An electron-rich aryl enol acetate worked perfectly
well, while an electron-deficient one underwent this trans-
formation less efficiently. This is probably because an elec-
tron-rich aromatic ring can stabilize cationic intermediate 9
(for details, see Figure 2). Halogenated aryl enol acetates
gave the corresponding α-sulfonyl ketones (i.e., 4c–4f) in
quite good yields. Branched enol acetates 1g–1j also reacted
with 2a to give α-sulfonyl ketones 4g–4j in satisfactory
II
III
I
I
I
7[c]
8[d]
9[e]
I
I
I
[a] Reaction conditions: 1a (0.2 mmol), 2a (1.5 equiv., 0.3 mmol),
and photocatalyst (1.0 mol-%, 0.002 mmol) in CH2Cl2 (2.0 mL)
were irradiated with a 13 W white LED for 8 h. [b] Isolated yield.
[c] 5.0 mol-% of I was used. [d] No photocatalyst. [e] No irradia-
tion.
This transformation was next applied to a variety of sulf- yields.
onyl chlorides as shown in Table 2. To our delight, sulf-
We next turned our attention to the trifluoromethylation
onation of phenylvinyl acetate (1a) with various sulfonyl of enol acetates. Recently, MacMillan and co-workers re-
chlorides worked quite well. Electron-poor arenesulfonyl ported that the α-trifluoromethylation of carbonyl com-
chlorides coupled with phenylvinyl acetate (1a) to give the pounds could be achieved with a large excess of gaseous
corresponding α-sulfonyl acetophenones (i.e., 3b–3e) in sat- CF3I and enolsilanes using visible-light photoredox cataly-
Eur. J. Org. Chem. 0000, 0–0
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H. Jiang, Y. Cheng, Y. Zhang, S. Yu
FULL PAPER
Table 3. Scope of the vinyl acetates.[a,b]
Table 4. Optimization of reaction conditions for trifluoromethyla-
tion.[a]
Entry
Catalyst
Solvent
Yield [%][b]
1
2
3
4
I
CH2Cl2
CH2Cl2
CH3CN
DMF
toluene
CH3CN
CH3CN
CH3CN
43
50
87
55
trace
87
n.r.
trace
II
II
II
II
II
II
II
5
6[c]
7[d]
8[e]
[a] Reaction conditions: 1a (0.2 mmol), 5 (2.5 equiv., 0.5 mmol),
and photocatalyst (1.0 mol-%, 0.002 mmol) in solvent (2.0 mL)
were irradiated with a 13 W white LED for 5 h. [b] Isolated yields.
[c] 5.0 mol-% of II was used. [d] No photocatalyst. [e] No irradia-
tion.
[a] Reaction conditions: 1a (0.2 mmol), sulfonyl chloride
(1.5 equiv., 0.3 mmol), and photocatalyst (1.0 mol-%,
0.002 mmol) in CH2Cl2 (2.0 mL) were irradiated with a 13 W white
LED for 8–24 h. [b] Isolated yields. [c] 5.0 equiv. of methanesulf-
onyl chloride was used.
I
A dozen α-trifluoromethyl ketones were prepared by this
method, as shown in Table 5. The electronic properties of
the enol acetates did not significantly affect this transfor-
mation. Electron-rich, -neutral and -deficient aryl enol acet-
ates were all smoothly trifluoromethylated (to give 6a–6f).
Branched enol acetates also reacted with CF3SO2Cl to give
α-trifluoromethyl ketones (6g–6j, 6l) in satisfactory yields.
Remarkably, α-quaternary trifluoromethylated ketone 6k
could also be prepared by this method.
Table 5. Scope of the trifluoromethylation reaction.[a,b]
Figure 2. Proposed catalytic cycle.
sis.[17] To avoid the experimentally inconvenient gaseous
CF3I, we decided to use liquid CF3SO2Cl (–0.18V vs.
SCE)[11] as the trifluoromethyl radical source. As shown in
Table 4, trifluoromethylation of enol acetate 1a under the
optimized conditions for sulfonation only gave the corre-
sponding α-trifluoromethyl ketone (i.e., 6a) in moderate
yield (Table 4, entry 1). The yield was improved slightly
when II was used as the photocatalyst (Table 4, entry 2).
CH3CN proved to be the best solvent (87% yield; Table 4,
entries 3–5). When more of the photocatalyst was used
(5.0 mol-%), the same yield was obtained (Table 4, entry 6).
Control experiments also showed that both the irradiation
[a] Reaction conditions: 1 (0.2 mmol), 5 (2.5 equiv., 0.5 mmol), and
photocatalyst II (1.0 mol-%, 0.002 mmol) in CH3CN (2.0 mL) were
irradiated with a 13 W white LED for 5–24 h. [b] Isolated yields.
We next carried out control experiments to elucidate the
and the photocatalyst were necessary (Table 4, entries 7 and reaction mechanism. The reaction between 1a and 2a could
8).
be terminated by the introduction of TEMPO, which indi-
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Visible-Light Photoredox Catalysis
1
Figure 3. H NMR spectrum of the reaction between 1a and 5 when CD3CN was used as the solvent.
cated the operation of a single-electron-transfer pathway. A the biological activities of the functionalized ketone prod-
mixture of 1a and 2a was irradiated under the standard ucts, including their inhibition of cancer-cell growth and
conditions until about 50% conversion was reached (4 h), their regulation of microRNA[18] is now underway.
and then the light source was removed. No further progress
was observed after the reaction was stirred in the dark over-
night. When irradiation was reintroduced, the reaction went
Experimental Section
to completion within 8 h. Based on these experimental re-
sults and on literature precedent, we propose the catalytic
cycle shown in Figure 2. The key steps include (i) visible-
light excitation of the Ir3+ complex to generate Ir3+*;
(ii) oxidative quenching of Ir3+* by 2 or 5 to give Ir4+ and
radical 7;[10,11] (iii) radical addition of trifluoromethyl or
sulfonyl radical 7 to 1a to provide radical species 8;[15]
(iv) oxidation of 8 by Ir4+ to give cationic intermediate 9
and regenerate Ir3+ (8 is probably also oxidized by 5 or 2 to
generate radical 7);[15] and finally (v) cationic intermediate 9
loses an acetyl cation 10 to generate the desired product
(i.e., 3 or 6a), and acetyl cation 10 is captured by Cl– to
give acetyl chloride, which could be observed by NMR
spectroscopy (Figure 3).
General Methods: All solvents used in this article were dried ac-
cording to ref.[31] Other commercially sourced reagents were used
without further purification. Thin-layer chromatography (TLC)
plates were visualized by fluorescence quenching under UV light
and by staining with phosphomolybdic acid or potassium perman-
ganate. Column chromatography was performed on silica gel (300–
400 mesh) using a forced flow of 0.5–1.0 bar. NMR spectroscopy
was carried out with a 400 MHz spectrometer (1H, 400 MHz; 13C,
100 MHz; 19F, 376 MHz). Chemical shifts are expressed in parts
per million (ppm) and were calibrated using the residual solvent
peak. Coupling constants are reported in Hertz (Hz). Signal shapes
and splitting patterns are indicated as follows: br, broad; s, singlet;
d, doublet; t, triplet; q, quartet; m, multiplet. Enol acetates[19] were
prepared according to published literature procedures, other rea-
gents were sourced commercially.
General Procedure 1, Sulfonation of Enol Acetates: A round-bot-
tomed flask (10 mL) was equipped with a rubber septum and mag-
netic stirrer bar, and enol acetate (0.2 mmol, 1.0 equiv.), sulfonyl
Conclusions
In summary, we have described a mild, practical, and en-
vironmentally friendly method to prepare α-sulfonyl and
trifluoromethyl ketones using visible-light photoredox ca-
talysis. The starting materials (enol acetates and sulfonyl
chlorides) are commercially available and inexpensive, and
the reactions were performed at room temperature without
any additives. In addition, CF3SO2Cl is a stable liquid at
room temperature, unlike gaseous CF3I, and this may make
chloride (0.3 mmol, 1.5 equiv.), and Ir(ppy)3
I (0.002 mmol,
0.01 equiv.) were added. The flask was evacuated and back-filled
with argon three times. CH2Cl2 (2.0 mL) was added by syringe un-
der argon. The mixture was then irradiated under a 13 W white
LED strip at a distance of 5 cm. After the reaction was complete
(as judged by TLC analysis), the mixture was concentrated under
reduced pressure. The crude product was purified by flash
chromatography (hexanes/EtOAc) on silica gel to give the desired
this method potentially useful in industry. Exploration on product.
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H. Jiang, Y. Cheng, Y. Zhang, S. Yu
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General Procedure 2, Trifluoromethylation of Enol Acetates: A
round-bottomed flask (10 mL) was equipped with a rubber septum
and magnetic stirrer bar, and enol acetate (0.2 mmol, 1.0 equiv.)
and Ir(ppy)2(dtbbpy)PF6 II (0.002 mmol, 0.01 equiv.) were added.
The flask was evacuated and back-filled with argon three times.
1437, 1376, 1312, 1210, 1135, 1038, 991, 752, 731, 691, 679 cm–1.
1H NMR (400 MHz, CDCl3): δ = 8.06–8.05 (m, 1 H), 7.93 (d, J =
7.2 Hz, 2 H), 7.63–7.56 (m, 3 H), 7.49–7.41 (m, 3 H), 5.05 (s, 2 H)
ppm. 13C NMR (100 MHz, CDCl3): δ = 187.8, 136.5, 135.8, 135.2,
134.4, 132.7, 132.1, 131.9, 129.2, 128.9, 127.5, 61.0 ppm. HRMS
CH3CN (2.0 mL) and CF3SO2Cl (0.5 mmol, 2.5 equiv.) were added (ESI): calcd. for C14H11ClO3SNa 317.0015 [M + Na]+; found
by syringe under argon. The mixture was then irradiated using a
13 W white LED strip at a distance of 5 cm. After the reaction was
complete (as judged by TLC analysis), the mixture was concen-
trated under reduced pressure. The crude product was purified by
flash chromatography (hexanes/CH2Cl2) on silica gel to give the
desired product.
1-Phenyl-2-tosylethanone (3a):[20] White solid (46.0 mg, 84%). 1H
NMR (400 MHz, CDCl3): δ = 7.95 (d, J = 7.2 Hz, 2 H), 7.76 (d,
J = 8.3 Hz, 2 H), 7.62 (t, J = 7.4 Hz, 1 H), 7.48 (t, J = 7.4 Hz, 2
H), 7.33 (d, J = 8.0 Hz, 2 H), 4.71 (s, 2 H), 2.44 (s, 3 H) ppm. 13C
NMR (100 MHz, CDCl3): δ = 188.2, 145.4, 135.9, 135.8, 134.3,
129.8, 129.3, 128.8, 128.6, 63.6, 21.7 ppm.
317.0060.
2-(4-Chlorophenylsulfonyl)-1-phenylethanone (3h):[23] White solid
(43.0 mg, 73%). 1H NMR (400 MHz, CDCl3): δ = 7.93 (d, J =
7.4 Hz, 2 H), 7.83 (d, J = 8.6 Hz, 2 H), 7.63 (t, J = 7.4 Hz, 1 H),
7.52–7.47 (m, 4 H), 4.74 (s, 2 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 187.9, 141.1, 137.1, 135.6, 134.5, 130.2, 129.5, 129.3,
129.0, 63.3 ppm.
2-(Biphenyl-4-ylsulfonyl)-1-phenylethanone (3i): White solid
(63.8 mg, 95%). IR (thin film): ν = 3001, 2942, 1672, 1593, 1454,
˜
1315, 1307, 1276, 1226, 1152, 1089, 1004, 905, 822, 774, 739 cm–1.
1H NMR (400 MHz, CDCl3): δ = 7.88–7.86 (m, 4 H), 7.64 (d, J =
8.4 Hz, 2 H), 7.55–7.50 (m, 3 H), 7.41–7.32 (m, 5 H), 4.70 (s, 2 H)
ppm. 13C NMR (100 MHz, CDCl3): δ = 188.1, 147.2, 139.1, 137.3,
135.8, 134.4, 129.3, 129.2, 129.1, 128.9, 128.8, 127.8, 127.4,
63.6 ppm. HRMS (ESI): calcd. for C20H16O3SNa 359.0718 [M +
Na]+; found 359.0717.
1-Phenyl-2-[2-(trifluoromethyl)phenylsulfonyl]ethanone (3b): White
solid (51.8 mg, 79%). IR (thin film): ν = 2921, 1678, 1596, 1448,
˜
1330, 1308, 1268, 1142, 1113, 1094, 1035, 1001, 890, 776, 748, 726,
688, 669 cm–1. 1H NMR (400 MHz, CDCl3): δ = 8.17 (d, J =
7.8 Hz, 1 H), 7.94–7.92 (m, 3 H), 7.78 (t, J = 7.5 Hz, 1 H), 7.72 (t,
J = 7.5 Hz, 1 H), 7.60 (t, J = 7.4 Hz, 1 H), 7.48 (t, J = 7.8 Hz, 2
H), 4.91 (s, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 187.8,
137.6, 135.8, 134.5, 134.3, 133.7, 132.5, 129.2, 129.0, 128.9 (q, J =
33.1 Hz), 128.4 (q, J = 6.3 Hz), 122.8 (q, J = 272.2 Hz), 63.3 (q, J
= 2.7 Hz) ppm. 19F NMR (376 MHz, [D6]DMSO): δ = –56.5 ppm.
HRMS (ESI): calcd. for C15H11F3O3SNa 351.0279 [M + Na]+;
found 351.0322.
2-(4-Methoxyphenylsulfonyl)-1-phenylethanone (3j):[21] White solid
(47.6 mg, 82%). 1H NMR (400 MHz, CDCl3): δ = 7.95 (d, J =
7.4 Hz, 2 H), 7.80 (d, J = 8.9 Hz, 2 H), 7.62 (t, J = 7.4 Hz, 1 H),
7.48 (t, J = 7.4 Hz, 2 H), 6.98 (d, J = 8.9 Hz, 2 H), 4.71 (s, 2 H),
3.87 (s, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 188.3, 164.2,
135.8, 134.3, 130.9, 130.2, 129.3, 128.8, 114.4, 63.8, 55.7 ppm.
1-Phenyl-2-[4-(trifluoromethoxy)phenylsulfonyl]ethanone
(3k):
1-Phenyl-2-[4-(trifluoromethyl)phenylsulfonyl]ethanone
(3c):[21]
White solid (52.3 mg, 76%). IR (thin film): ν = 3010, 2956, 1680,
˜
White solid (45.3 mg, 69%). 1H NMR (400 MHz, CDCl3): δ = 8.05
(d, J = 8.2 Hz, 2 H), 7.92 (d, J = 7.6 Hz, 2 H), 7.82 (d, J = 8.2 Hz,
2 H), 7.64 (t, J = 7.6 Hz, 1 H), 7.49 (t, J = 7.6 Hz, 2 H), 4.79 (s, 2
H) ppm. 13C NMR (100 MHz, CDCl3): δ = 187.7, 142.1, 135.8 (q,
J = 33.0 Hz), 135.5, 134.7, 129.4, 129.2, 129.0, 126.3 (q, J =
3.6 Hz), 123.1 (q, J = 271.6 Hz), 63.1 ppm. 19F NMR (376 MHz,
[D6]DMSO): δ = –63.3 ppm.
1558, 1449, 1304, 1269, 1207, 1170, 1145, 1086, 1006, 930, 845,
1
810, 751, 678 cm–1. H NMR (400 MHz, CDCl3): δ = 7.96 (d, J =
8.9 Hz, 2 H), 7.92 (d, J = 7.4 Hz, 2 H), 7.63 (t, J = 7.4 Hz, 1 H),
7.48 (t, J = 7.4 Hz, 2 H), 7.35 (d, J = 8.9 Hz, 2 H), 4.76 (s, 2 H)
ppm. 13C NMR (100 MHz, CDCl3): δ = 187.9, 153.4 (q, J =
1.9 Hz), 136.9, 135.6, 134.6, 131.1, 129.2, 129.0, 120.8, 120.2 (q,
J = 258.5 Hz), 63.3 ppm. 19F NMR (376 MHz, [D6]DMSO): δ =
–57.6 ppm. HRMS (ESI): calcd. for C15H11F3O3SNa 367.0228 [M
+ Na]+; found 367.0287.
2-(Naphthalen-1-ylsulfonyl)-1-phenylethanone (3l):[21] White solid
(34.1 mg, 55%). 1H NMR (400 MHz, CDCl3): δ = 8.79 (dd, J =
8.5, 0.9 Hz, 1 H), 8.22 (dd, J = 7.4, 1.4 Hz, 1 H), 8.13 (d, J =
8.2 Hz, 1 H), 7.98 (d, J = 8.2 Hz, 1 H), 7.87 (d, J = 7.4 Hz, 2 H),
7.75 (t, J = 7.8 Hz, 1 H), 7.64 (t, J = 7.4 Hz, 1 H), 7.57 (t, J =
7.4 Hz, 1 H), 7.54 (t, J = 7.7 Hz, 1 H), 7.41 (t, J = 7.4 Hz, 2 H),
4.90 (s, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 187.8, 135.9,
135.8, 134.3, 134.2, 133.9, 131.4, 129.5, 129.2, 129.1, 128.8, 128.7,
127.2, 124.3, 123.7, 62.9 ppm.
4-(2-Oxo-2-phenylethylsulfonyl)benzonitrile (3d):[22] White solid
(46.7 mg, 82%). 1H NMR (400 MHz, CDCl3): δ = 8.04 (d, J =
8.2 Hz, 2 H), 7.92 (d, J = 7.5 Hz, 2 H), 7.85 (d, J = 8.2 Hz, 2 H),
7.65 (t, J = 7.5 Hz, 1 H), 7.50 (t, J = 7.5 Hz, 2 H), 4.80 (s, 2 H)
ppm. 13C NMR (100 MHz, CDCl3): δ = 187.7, 142.6, 135.4, 134.8,
132.9, 129.5, 129.2, 129.1, 118.0, 117.1, 62.9 ppm.
2-(4-Nitrophenylsulfonyl)-1-phenylethanone (3e):[23] White solid
1
(46.4 mg, 76%). H NMR (400 MHz, [D6]DMSO): δ = 8.46 (d, J
= 8.9 Hz, 2 H), 8.22 (d, J = 8.9 Hz, 2 H), 7.97 (d, J = 7.4 Hz, 2
H), 7.69 (t, J = 7.4 Hz, 1 H), 7.54 (t, J = 7.4 Hz, 2 H), 5.62 (s, 2
H) ppm. 13C NMR (100 MHz, [D6]DMSO): δ = 189.0, 150.5,
144.8, 135.4, 134.4, 129.9, 128.9, 128.8, 124.3, 61.7 ppm.
1-Phenyl-2-(thiophen-2-ylsulfonyl)ethanone (3m): Yellow solid
(32.5 mg, 61%). IR (thin film): ν = 2943, 2921, 1672, 1595, 1446,
˜
2-(2-Chlorophenylsulfonyl)-1-phenylethanone (3f): White solid
1401, 1311, 1233, 1153, 1122, 1003, 856, 827, 757, 732, 689,
(44.1 mg, 76%). IR (thin film): ν = 2997, 2940, 1671, 1598, 1581,
˜
1
676 cm–1. H NMR (400 MHz, CDCl3): δ = 7.95 (d, J = 7.4 Hz, 2
1449, 1410, 1314, 1279, 1230, 1157, 1110, 1078, 1003, 996, 903,
880, 790, 742, 682, 660 cm–1. 1H NMR (400 MHz, CDCl3): δ =
7.93 (d, J = 7.2 Hz, 2 H), 7.89 (t, J = 1.8 Hz, 1 H), 7.79 (d, J =
7.8 Hz, 1 H), 7.65–7.61 (m, 2 H), 7.51–7.47 (m, 3 H), 4.75 (s, 2 H)
ppm. 13C NMR (100 MHz, CDCl3): δ = 187.7, 140.4, 135.6, 135.5,
134.6, 134.4, 130.5, 129.2, 129.0, 128.7, 126.9, 63.3 ppm. HRMS
(ESI): calcd. for C14H11ClO3SNa 317.0015 [M + Na]+; found
317.0043.
H), 7.74 (dd, J = 4.9, 1.3 Hz, 1 H), 7.69 (dd, J = 3.8, 1.2 Hz, 1 H),
7.63 (t, J = 7.4 Hz, 1 H), 7.49 (t, J = 7.4 Hz, 2 H), 7.13 (dd, J =
4.9, 3.9 Hz, 1 H), 4.83 (s, 2 H) ppm. 13C NMR (100 MHz, CDCl3):
δ = 187.8, 139.4, 135.7, 135.5, 135.0, 134.5, 129.2, 128.9, 127.9,
64.4 ppm. HRMS (ESI): calcd. for C12H10O3S2Na 289.0002 [M +
Na]+; found 289.0013.
1-Phenyl-2-(pyridin-3-ylsulfonyl)ethanone (3n): Pale oil (37.1 mg,
2-(3-Chlorophenylsulfonyl)-1-phenylethanone (3g): White solid
61%). IR (thin film): ν = 2900, 1695, 1595, 1576, 1448, 1418, 1321,
˜
(41.1 mg, 70%). IR (thin film): ν = 3092, 2981, 1684, 1578, 1455,
1302, 1198, 1174, 1141, 1100, 979, 881, 783, 753, 695, 686 cm–1. 1H
˜
6
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© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 0000, 0–0

Job/Unit: O30693
/KAP1
Date: 08-07-13 11:06:22
Pages: 9
Visible-Light Photoredox Catalysis
NMR (400 MHz, CDCl3): δ = 9.11 (d, J = 1.9 Hz, 1 H), 8.88 (dd,
J = 4.8, 1.5 Hz, 1 H), 8.23–8.20 (m, 1 H), 7.93 (d, J = 7.4 Hz, 2
H), 7.65 (t, J = 7.4 Hz, 1 H), 7.53–7.48 (m, 3 H), 4.81 (s, 2 H) ppm.
13C NMR (100 MHz, CDCl3): δ = 187.8, 154.6, 149.5, 136.8, 135.5,
135.3, 134.7, 129.2, 129.0, 123.7, 63.3 ppm. HRMS (ESI): calcd.
for C13H11NO3SNa 284.0357 [M + Na]+; found 284.0380.
CDCl3): δ = 187.3, 145.6, 135.6, 134.5, 132.2, 130.8, 130.0, 129.9,
128.6, 63.7, 21.7 ppm.
2-Tosyl-2,3-dihydro-1H-inden-1-one (4g): White solid (44.0 mg,
77%). IR (thin film): ν = 2908, 1705, 1595, 1464, 1446, 1432, 1318,
˜
1303, 1289, 1277, 1146, 1084, 1001, 842, 755, 702, 677, 651 cm–1.
1H NMR (400 MHz, CDCl3): δ = 7.81 (d, J = 8.4 Hz, 2 H), 7.72
(d, J = 7.6 Hz, 1 H), 7.63 (t, J = 7.7 Hz, 1 H), 7.50 (d, J = 7.7 Hz,
1 H), 7.40–7.53 (m, 3 H), 4.26 (dd, J = 8.4, 3.4 Hz, 1 H), 3.83 (dd,
J = 18.2, 3.3 Hz, 1 H), 3.53 (dd, J = 18.3, 8.4 Hz, 1 H), 2.45 (s, 3
H) ppm. 13C NMR (100 MHz, CDCl3): δ = 194.6, 151.9, 145.4,
135.9, 135.8, 134.6, 129.7, 129.3, 128.2, 126.4, 124.8, 68.7, 28.2,
21.7 ppm. HRMS (ESI): calcd. for C16H14O3SNa 309.0561 [M +
Na]+; found 309.0600.
2-(Methylsulfonyl)-1-phenylethanone (3o):[20] Pale oil (33.7 mg,
85%). 1H NMR (400 MHz, CDCl3): δ = 8.00 (d, J = 7.4 Hz, 2 H),
7.67 (t, J = 7.4 Hz, 1 H), 7.53 (t, J = 7.4 Hz, 2 H), 4.60 (s, 2 H),
3.16 (s, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 189.2, 135.6,
134.7, 129.2, 129.1, 61.3, 41.8 ppm.
2-(Octylsulfonyl)-1-phenylethanone (3p): White solid (52.0 mg,
88%). IR (thin film): ν = 2923, 2854, 1655, 1595, 1449, 1322, 1309,
˜
1221, 1193, 1134, 998, 902, 763, 689, 677 cm–1. 1H NMR
(400 MHz, CDCl3): δ = 8.01 (d, J = 7.4 Hz, 2 H), 7.65 (t, J =
7.4 Hz, 1 H), 7.52 (t, J = 7.4 Hz, 2 H), 4.56 (s, 2 H), 3.27–3.23 (m,
2 H), 1.93–1.85 (m, 2 H), 1.48–1.42 (m, 2 H), 1.36–1.27 (m, 8 H),
0.88 (t, J = 6.76 Hz, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ =
189.3, 135.8, 134.6, 129.3, 129.0, 59.5, 53.8, 31.7, 29.0, 28.9, 28.3,
22.6, 21.9, 14.1 ppm. HRMS (ESI): calcd. for C16H24O3SNa
319.1344 [M + Na]+; found 319.1413.
2-Tosyl-3,4-dihydronaphthalen-1(2H)-one (4h):[24] White solid
(53.4 mg, 89%). 1H NMR (400 MHz, CDCl3): δ = 7.98 (dd, J =
7.9, 1.0 Hz, 1 H), 7.79 (d, J = 8.3 Hz, 2 H), 7.51 (t, J = 7.5 Hz, 1
H), 7.36 (d, J = 8.1 Hz, 2 H), 7.31 (t, J = 7.6 Hz, 1 H), 7.26 (d, J
= 8.1 Hz, 1 H), 4.08 (t, J = 5.6 Hz, 1 H), 3.56–3.48 (m, 1 H), 3.02–
2.95 (m, 1 H), 2.91–2.83 (m, 1 H), 2.69–2.60 (m, 1 H), 2.45 (s, 3
H) ppm. 13C NMR (100 MHz, CDCl3): δ = 188.8, 145.1, 143.6,
136.0, 134.5, 131.8, 129.7, 129.1, 129.0, 127.9, 127.0, 69.7, 26.6,
23.7, 21.7 ppm.
2-(Cyclopropylsulfonyl)-1-phenylethanone
(3q):
White
solid
(44.0 mg, 98%). IR (thin film): ν = 2967, 2916, 1691, 1596, 1446,
˜
6-Tosyl-6,7,8,9-tetrahydro-5H-benzo[7]annulen-5-one (4i): White so-
1315, 1297, 1281, 1202, 1165, 1119, 1069, 979, 882, 829, 776, 757,
684, 671 cm–1. 1H NMR (400 MHz, CDCl3): δ = 8.02 (d, J =
7.4 Hz, 2 H), 7.65 (t, J = 7.4 Hz, 1 H), 7.52 (t, J = 7.4 Hz, 2 H),
4.65 (s, 2 H), 2.79–2.73 (m, 1 H), 1.30–1.26 (m, 2 H), 1.12–1.06 (m,
2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 188.9, 135.8, 134.5,
129.3, 129.0, 61.0, 30.9, 5.5 ppm. HRMS (ESI): calcd. for
C11H12O3SNa 247.0405 [M + Na]+; found 247.0399.
lid (28.9 mg, 46%). IR (thin film): ν = 2952, 2911, 1689, 1596,
˜
1438, 1317, 1285, 1272, 1207, 1132, 1082, 976, 811, 778, 736, 726,
705, 633 cm–1. 1H NMR (400 MHz, CDCl3): δ = 7.87 (d, J =
8.3 Hz, 2 H), 7.50 (dd, J = 7.6, 1.1 Hz, 1 H), 7.43–7.39 (m, 1 H),
7.35 (d, J = 8.1 Hz, 2 H), 7.26 (t, J = 7.4 Hz, 1 H), 7.18 (d, J =
7.6 Hz, 1 H), 4.35 (dd, J = 10.8, 4.9 Hz, 1 H), 3.06–3.00 (m, 1 H),
2.93–2.85 (m, 1 H), 2.59–2.50 (m, 1 H), 2.45 (s, 3 H), 2.23–2.10 (m,
2 H), 1.95–1.84 (m, 1 H) ppm. 13C NMR (100 MHz, CDCl3): δ =
197.0, 144.9, 140.6, 138.4, 135.8, 132.4, 129.8, 129.6, 129.5, 128.6,
126.9, 73.2, 32.7, 24.3, 24.1, 21.7 ppm. HRMS (ESI): calcd. for
C18H18O3SNa 337.0874 [M + Na]+; found 337.0917.
1-(4-Methoxyphenyl)-2-tosylethanone (4b):[20] White solid (55.3 mg,
91%.). 1H NMR (400 MHz, CDCl3): δ = 7.94 (d, J = 8.9 Hz, 2 H),
7.75 (d, J = 8.3 Hz, 2 H), 7.33 (d, J = 8.3 Hz, 2 H), 6.95 (d, J =
8.9 Hz, 2 H), 4.66 (s, 2 H), 3.89 (s, 3 H), 2.44 (s, 3 H) ppm. 13C
NMR (100 MHz, CDCl3): δ = 186.4, 164.5, 145.2, 135.9, 131.9,
129.8, 128.9, 128.6, 114.1, 63.5, 55.6, 21.7 ppm.
1-Phenyl-2-tosylpropan-1-one (4j):[25] White solid (30.5 mg, 53%).
1H NMR (400 MHz, CDCl3): δ = 7.98 (d, J = 7.3 Hz, 2 H), 7.66
(d, J = 8.4 Hz, 2 H), 7.61 (t, J = 7.4 Hz, 1 H), 7.48 (t, J = 7.4 Hz,
2 H), 7.31 (d, J = 8.0 Hz, 2 H), 5.15 (q, J = 6.9 Hz, 1 H), 2.43 (s,
3 H), 1.56 (d, J = 6.9 Hz, 3 H) ppm. 13C NMR (100 MHz, CDCl3):
δ = 192.6, 145.4, 136.3, 134.0, 133.0, 129.9, 129.5, 129.2, 128.7,
65.0, 21.7, 13.2 ppm.
1-(4-Nitrophenyl)-2-tosylethanone (4c):[20] White solid (33.8 mg,
1
53%). H NMR (400 MHz, CDCl3): δ = 8.33 (d, J = 8.8 Hz, 2 H),
8.15 (d, J = 8.8 Hz, 2 H), 7.75 (d, J = 8.2 Hz, 2 H), 7.37 (d, J =
8.2 Hz, 2 H), 4.75 (s, 2 H), 2.47 (s, 3 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 187.0, 150.9, 145.9, 140.0, 135.4, 130.5, 130.1, 128.5,
124.0, 64.2, 21.7 ppm.
3,3,3-Trifluoro-1-phenylpropan-1-one (6a):[17] White solid (32.7 mg,
87%). 1H NMR (400 MHz, CDCl3): δ = 7.94 (d, J = 7.4 Hz, 2 H),
7.64 (t, J = 7.4 Hz, 1 H), 7.51 (t, J = 7.4 Hz, 2 H), 3.80 (q, J =
10.0 Hz, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 189.7 (q, J
= 2.7 Hz), 135.8 (q, J = 1.6 Hz), 134.2, 128.9, 128.4, 124.0 (q, J =
275.3 Hz), 42.1 (q, J = 28.0 Hz) ppm. 19F NMR (376 MHz,
CDCl3): δ = –62.0 ppm.
1-(4-Fluorophenyl)-2-tosylethanone (4d):[20] White solid (40.9 mg,
1
70%). H NMR (400 MHz, CDCl3): δ = 8.00 (dd, J = 9.0, 5.4 Hz,
2 H), 7.75 (d, J = 8.3 Hz, 2 H), 7.34 (d, J = 8.0 Hz, 2 H), 7.16 (t,
J = 8.6 Hz, 2 H), 4.68 (s, 2 H), 2.45 (s, 3 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 186.6, 166.5 (d, J = 255.9 Hz), 145.5, 135.7,
132.3 (d, J = 9.5 Hz), 132.2, 129.9, 128.6, 116.1 (d, J = 22.1 Hz),
63.7, 21.7 ppm. 19F NMR (376 MHz, [D6]DMSO):
–103.5 ppm.
δ
=
3,3,3-Trifluoro-1-(4-methoxyphenyl)propan-1-one (6b):[17] White so-
1
lid (40.5 mg, 93%). H NMR (400 MHz, CDCl3): δ = 7.92 (d, J =
1-(4-Chlorophenyl)-2-tosylethanone (4e):[20] White solid (45.0 mg,
73%). 1H NMR (400 MHz, CDCl3): δ = 7.90 (d, J = 8.7 Hz, 2 H),
7.74 (d, J = 8.3 Hz, 2 H), 7.46 (d, J = 8.7 Hz, 2 H), 7.34 (d, J =
8.0 Hz, 2 H), 4.67 (s, 2 H), 2.45 (s, 3 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 187.1, 145.5, 141.1, 135.6, 134.1, 130.8, 129.9, 129.2,
128.6, 63.7, 21.7 ppm.
8.9 Hz, 2 H), 6.97 (d, J = 8.9 Hz, 2 H), 3.89 (s, 3 H), 3.73 (q, J =
10.0 Hz, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 188.1 (q, J
= 2.3 Hz), 164.4, 130.8, 128.9 (q, J = 1.8 Hz), 124.2 (q, J =
275.3 Hz), 114.1, 55.6, 41.8 (q, J = 28.0 Hz) ppm. 19F NMR
(376 MHz, CDCl3): δ = –61.9 ppm.
3,3,3-Trifluoro-1-(4-nitrophenyl)propan-1-one (6c):[26] White solid
(39.1 mg, 84%). 1H NMR (400 MHz, CDCl3): δ = 8.37 (d, J =
1-(4-Bromophenyl)-2-tosylethanone (4f):[20] White solid (57.0 mg,
81%). 1H NMR (400 MHz, CDCl3): δ = 7.82 (d, J = 8.5 Hz, 2 H), 8.9 Hz, 2 H), 8.11 (d, J = 8.9 Hz, 2 H), 3.86 (q, J = 9.8 Hz, 2 H)
7.74 (d, J = 8.3 Hz, 2 H), 7.63 (d, J = 8.5 Hz, 2 H), 7.34 (d, J = ppm. 13C NMR (100 MHz, CDCl3): δ = 188.4 (q, J = 2.6 Hz),
8.3 Hz, 2 H), 4.67 (s, 2 H), 2.45 (s, 3 H) ppm. 13C NMR (100 MHz,
150.9, 139.9 (q, J = 2.2 Hz), 129.5, 124.2, 123.5 (q, J = 275.5 Hz),
Eur. J. Org. Chem. 0000, 0–0
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
7

Job/Unit: O30693
/KAP1
Date: 08-07-13 11:06:22
Pages: 9
H. Jiang, Y. Cheng, Y. Zhang, S. Yu
FULL PAPER
42.7 (q, J = 28.9 Hz) ppm. 19F NMR (376 MHz, CDCl3): δ = –61.9 3,3,3-Trifluoro-2,2-dimethyl-1-phenylpropan-1-one (6k):[29] Color-
1
ppm.
less oil (28.5 mg, 66%). H NMR (400 MHz, CDCl3): δ = 7.64 (d,
J = 7.3 Hz, 2 H), 7.50 (t, J = 7.4 Hz, 1 H), 7.42 (t, J = 7.8 Hz, 2
H), 1.56 (s, 6 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 200.7,
138.1 (q, J = 0.9 Hz), 131.5, 128.2, 127.7 (q, J = 0.9 Hz), 126.8 (q,
J = 284.0 Hz), 53.3 (q, J = 24.5 Hz), 41.5 (q, J = 2.7 Hz) ppm. 19F
NMR (376 MHz, CDCl3): δ = –72.7 ppm.
3,3,3-Trifluoro-1-(4-fluorophenyl)propan-1-one (6d):[17] White solid
(30.1 mg, 73%). 1H NMR (400 MHz, CDCl3): δ = 7.97 (dd, J =
8.9, 5.2 Hz, 2 H), 7.18 (t, J = 8.6 Hz, 2 H), 3.77 (q, J = 9.9 Hz, 2
H) ppm. 13C NMR (100 MHz, CDCl3): δ = 188.2 (q, J = 2.5 Hz),
166.4 (d, J = 255.5 Hz), 132.3 (q, J = 1.2 Hz), 131.1 (d, J = 9.5 Hz),
123.9 (q, J = 275.3 Hz), 116.2 (d, J = 21.7 Hz), 42.1 (q, J = 28.4 Hz)
ppm. 19F NMR (376 MHz, CDCl3): δ = –62.0, –102.9 ppm.
3,3,3-Trifluoro-1,2-diphenylpropan-1-one (6l):[30] Colorless oil
(33.3 mg, 63%). 1H NMR (400 MHz, CDCl3): δ = 7.90 (d, J =
7.3 Hz, 2 H), 7.52 (t, J = 7.4 Hz, 1 H), 7.47–7.35 (m, 7 H), 5.28 (q,
J = 8.2 Hz, 1 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 191.1 (q,
J = 1.2 Hz), 135.4 (q, J = 1.8 Hz), 133.8, 129.9, 129.7 (q, J =
1.8 Hz), 129.3, 129.2, 128.8, 128.7, 124.3 (q, J = 280.0 Hz), 56.6 (q,
J = 26.8 Hz) ppm. 19F NMR (376 MHz, CDCl3): δ = –66.5 ppm.
1-(4-Chlorophenyl)-3,3,3-trifluoropropan-1-one (6e):[17] White solid
(39.5 mg, 89%.). 1H NMR (400 MHz, CDCl3): δ = 7.88 (d, J =
8.8 Hz, 2 H), 7.49 (d, J = 8.8 Hz, 2 H), 3.77 (q, J = 9.9 Hz, 2 H)
ppm. 13C NMR (100 MHz, CDCl3): δ = 187.8 (q, J = 2.5 Hz),
140.9, 134.1 (q, J = 1.6 Hz), 129.7, 129.3, 123.9 (q, J = 275.3 Hz),
42.1 (q, J = 28.4 Hz) ppm. 19F NMR (376 MHz, CDCl3): δ =
–62.0 ppm.
Supporting Information (see footnote on the first page of this arti-
cle): Copies of the 1H and 13C NMR spectra for all final products.
1-(4-Bromophenyl)-3,3,3-trifluoropropan-1-one (6f):[17] White solid
(39.5 mg, 74%). 1H NMR (400 MHz, CDCl3): δ = 7.80 (d, J =
8.6 Hz, 2 H), 7.66 (d, J = 8.6 Hz, 2 H), 3.76 (q, J = 9.9 Hz, 2 H)
ppm. 13C NMR (100 MHz, CDCl3): δ = 188.7 (q, J = 2.5 Hz),
134.5 (q, J = 1.6 Hz), 132.3, 129.8, 129.7, 123.8 (q, J = 275.4 Hz),
42.1 (q, J = 28.4 Hz) ppm. 19F NMR (376 MHz, CDCl3): δ =
–62.0 ppm.
Acknowledgments
Financial support from the National Basic Research Program of
China (grant number 2011CB935800), the National Natural Sci-
ence Foundation of China (NSFC) (grant numbers 21121091,
21102072), the Natural Science Foundation of Jiangsu Province
(grant number BK2012012), and the Research Fund for the Doc-
toral Program of Higher Education of China (grant number
20110091120008) is acknowledged.
2-(Trifluoromethyl)-2,3-dihydro-1H-inden-1-one (6g):[27] White solid
(29.2 mg, 73%). 1H NMR (400 MHz, CDCl3): δ = 7.82 (d, J =
7.6 Hz, 1 H), 7.66 (td, J = 7.7, 1.0 Hz, 1 H), 7.52 (d, J = 7.8 Hz, 1
H), 7.44 (t, J = 7.7 Hz, 1 H), 3.49–3.28 (m, 3 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 196.8 (q, J = 2.1 Hz), 152.1, 135.9 (q, J =
2.2 Hz), 135.8, 128.2, 126.5, 124.9 (q, J = 279.3 Hz), 124.7, 49.8 (q,
J = 27.8 Hz), 27.6 (q, J = 2.4 Hz) ppm. 19F NMR (376 MHz,
CDCl3): δ = –67.8 ppm.
[1] For recent reviews about visible-light photoredox catalysis, see:
a) C. K. Prier, D. A. Rankic, D. W. C. Macmillan, Chem. Rev.
2013, DOI: 10.1021/cr300503r; b) J. Xuan, W.-J. Xiao, Angew.
Chem. 2012, 124, 6934–6944; Angew. Chem. Int. Ed. 2012, 51,
6828–6838; c) M. A. Ischay, T. P. Yoon, Eur. J. Org. Chem.
2012, 18, 3359–3372; d) J. W. Tucker, C. R. J. Stephenson, J.
Org. Chem. 2012, 77, 1617–1622; e) J. M. R. Narayanam,
C. R. J. Stephenson, Chem. Soc. Rev. 2011, 40, 102–113; f) T. P.
Yoon, M. A. Ischay, J. Du, Nature Chem. 2010, 2, 527–532; g)
K. Zeitler, Angew. Chem. 2009, 121, 9969–9974; Angew. Chem.
Int. Ed. 2009, 48, 9785–9789; for recent selected examples of
visible-light photoredox catalysis, see: h) J. Xie, Q. Xue, H. Jin,
H. Li, Y. Cheng, C. Zhu, Chem. Sci. 2013, 4, 1281–1286; i) H.
Sun, C. Yang, F. Gao, Z. Li, W. Xia, Org. Lett. 2013, 15, 624–
627; j) S. Cai, X. Zhao, X. Wang, Q. Liu, Z. Li, D. Z. Wang,
Angew. Chem. 2012, 124, 8174–8177; Angew. Chem. Int. Ed.
2012, 51, 8050–8053; k) Y.-Q. Zou, J.-R. Chen, X.-P. Liu, L.-
Q. Lu, R. L. Davis, K. A. Jorgensen, W.-J. Xiao, Angew. Chem.
2012, 124, 808–812; Angew. Chem. Int. Ed. 2012, 51, 784–788;
l) Y.-Q. Zou, L.-Q. Lu, L. Fu, N.-J. Chang, J. Rong, J.-R. Chen,
W.-J. Xiao, Angew. Chem. 2011, 123, 7309–7313; Angew. Chem.
Int. Ed. 2011, 50, 7171–7175; m) C. Dai, J. M. R. Narayanam,
C. R. J. Stephenson, Nat. Chem. 2011, 3, 140–145; n) Y. Su, L.
Zhang, N. Jiao, Org. Lett. 2011, 13, 2168–2171; o) J. M. R.
Narayanam, J. W. Tucker, C. R. J. Stephenson, J. Am. Chem.
Soc. 2009, 131, 8756–8757; p) D. A. Nicewicz, D. W. C. Mac-
Millan, Science 2008, 322, 77–80; q) M. A. Ischay, M. E. Anzo-
vino, J. Du, T. P. Yoon, J. Am. Chem. Soc. 2008, 130, 12886–
12887.
2-(Trifluoromethyl)-3,4-dihydronaphthalen-1(2H)-one (6h):[28] White
1
solid (35.0 mg, 82%). H NMR (400 MHz, CDCl3): δ = 8.07 (dd,
J = 8.0, 1.1 Hz, 1 H), 7.52 (td, J = 7.6, 1.4 Hz, 1 H), 7.35 (t, J =
7.8 Hz, 1 H), 7.27 (d, J = 7.8 Hz, 1 H), 3.33–3.22 (m, 1 H), 3.16–
3.03 (m, 2 H), 2.54–2.47 (m, 1 H), 2.33–2.23 (m, 1 H) ppm. 13C
NMR (100 MHz, CDCl3): δ = 190.2 (q, J = 1.1 Hz), 143.1, 134.2,
131.9 (q, J = 1.5 Hz), 128.8, 127.9, 127.1, 125.1 (q, J = 280.1 Hz),
50.9 (q, J = 25.4 Hz), 27.5, 23.4 (q, J = 2.7 Hz) ppm. 19F NMR
(376 MHz, CDCl3): δ = –67.5 ppm.
6-(Trifluoromethyl)-6,7,8,9-tetrahydro-5H-benzo[7]annulen-5-one
(6i): White solid (35.6 mg, 78%). IR (thin film): ν = 2967, 1881,
˜
1633, 1428, 1466, 1354, 1286, 1115, 1101, 963, 855, 814, 736, 678,
659 cm–1. 1H NMR (400 MHz, CDCl3): δ = 7.77 (dd, J = 7.8,
1.3 Hz, 1 H), 7.44 (td, J = 7.5, 1.4 Hz, 1 H), 7.32 (t, J = 7.4 Hz, 1
H), 7.25 (d, J = 7.3 Hz, 1 H), 3.67–3.56 (m, 1 H), 3.09–2.97 (m, 2
H), 2.27–2.17 (m, 2 H), 2.10–1.99 (m, 1 H), 1.84–1.73 (m, 1 H)
ppm. 13C NMR (100 MHz, CDCl3): δ = 196.8 (q, J = 1.2 Hz),
141.9, 138.3 (q, J = 1.8 Hz), 132.3, 130.3, 128.9, 126.8, 125.2 (q, J
= 279.7 Hz), 53.2 (q, J = 25.1 Hz), 33.2, 24.5, 23.9 (q, J = 2.7 Hz)
ppm. 19F NMR (376 MHz, CDCl3): δ = –67.6 ppm. HRMS (ESI):
calcd. for C12H11F3ONa 251.0660 [M + Na]+; found 251.0673.
[2] J. D. Nguyen, J. W. Tucker, M. D. Konieczynska, C. R. J. Ste-
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3,3,3-Trifluoro-2-methyl-1-phenylpropan-1-one (6j):[28] Colorless oil
(28.3 mg, 70%). 1H NMR (400 MHz, CDCl3): δ = 7.95 (d, J =
7.3 Hz, 2 H), 7.62 (t, J = 7.4 Hz, 1 H), 7.50 (t, J = 7.5 Hz, 2 H),
4.31–4.20 (m, 1 H), 1.47 (d, J = 7.2 Hz, 3 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 194.4 (q, J = 1.8 Hz), 135.7 (q, J = 1.1 Hz),
134.0, 128.9, 128.6, 125.3 (q, J = 280 Hz), 44.3 (q, J = 26.4 Hz),
11.7 (q, J = 3.2 Hz) ppm. 19F NMR (376 MHz, CDCl3): δ =
–68.3 ppm.
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Job/Unit: O30693
/KAP1
Date: 08-07-13 11:06:22
Pages: 9
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Received: May 11, 2013
Published Online: ᭿
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