Synthesis of vinyl sulfides and vinylamines through catalytic intramolecular hydroarylation in the presence of FeCl3 and AgOTf

Article abstract of DOI:10.1002/ejoc.201201270

A synthetic method was developed for the preparation of vinyl sulfides and vinylamines from arylalkynyl phenyl sulfides and sulfonamides. Under mild conditions, a catalytic intramolecular hydroarylation reaction was carried out in the presence of FeCl₃ and AgOTf (OTf = trifluoromethanesulfonate) in 1,2-dichloroethane. A variety of 1,2-dihydronaphthalenes, 2H-chromenes, and 1,2-dihydroquinolines containing a phenylsulfenyl or N-phenyl-N-tosyl group on the sp²-hybridized benzylic carbon were prepared in good to excellent yields. The present method could be extended to the preparation of dihydropyrano[2,3-g]chromenes through a twofold Fe-catalyzed hydroarylation by a selective 6-endo mode. A synthetic method was developed for the preparation of vinyl sulfides and vinylamines. Arylalkynyl phenyl sulfides and sulfonamides underwent a catalytic intramolecular hydroarylation reaction to give 1,2-dihydronaphthalenes, 2H-chromenes, and 1,2-dihydroquinolines with a phenylsulfenyl or N-phenyl-N-tosyl group on the sp²-hybridized benzylic carbon. Copyright

Full text of DOI:10.1002/ejoc.201201270

FULL PAPER
DOI: 10.1002/ejoc.201201270
Synthesis of Vinyl Sulfides and Vinylamines through Catalytic Intramolecular
Hydroarylation in the Presence of FeCl3 and AgOTf
Dahan Eom,[a] Juntae Mo,[a] Phil Ho Lee,*[a] Zhiming Gao,[b] and Sunggak Kim*[b]
Keywords: Synthetic methods / Fused-ring systems / Cyclization / Iron / Substituent effects / Hydroarylation
A synthetic method was developed for the preparation of vin-
yl sulfides and vinylamines from arylalkynyl phenyl sulfides
and sulfonamides. Under mild conditions, a catalytic intra-
molecular hydroarylation reaction was carried out in the
presence of FeCl3 and AgOTf (OTf = trifluoromethanesulfon-
ate) in 1,2-dichloroethane. A variety of 1,2-dihydronaphth-
alenes, 2H-chromenes, and 1,2-dihydroquinolines containing
a phenylsulfenyl or N-phenyl-N-tosyl group on the sp2-hy-
bridized benzylic carbon were prepared in good to excellent
yields. The present method could be extended to the prepa-
ration of dihydropyrano[2,3-g]chromenes through a twofold
Fe-catalyzed hydroarylation by a selective 6-endo mode.
vinyl halides and triflates with thiols or amines [see
Scheme 1, Equation (3)].[8] Recently, the rare preparation of
vinylamines through an intramolecular Brønsted acid-cata-
lyzed hydroarylation was reported.[9] However, the hydro-
arylation of C-tethered arene-ynamides did not completely
translate to N-tethered arene-ynamides.
Introduction
Vinyl sulfides[1] and vinylamines[2] are important building
blocks in organic synthesis and are present in many biolo-
gically and pharmaceutically active compounds.[3] Thus, the
development of synthetic methods for these compounds is
a significant goal. Transition-metal-catalyzed hydrothiol-
ation[4] and hydroamination[5] reactions of alkynes are inter-
esting methods for the synthesis of vinyl sulfides and vin-
ylamines from the viewpoint of atom economy [see
Scheme 1, Equation (1)]. Although sulfur compounds are
often considered to be a poison to transition-metal cata-
lysts, the hydrothiolation of alkynes has been reported to
be catalyzed by Pd, Pt, Rh, Ni, Ir, and Au.[4] The hydro-
amination of alkynes is usually catalyzed by Ti, Zr, lantha-
nides, actinides, and late transition-metal catalysts such as
Pd, Ru, Rh, Ag, and Au.[5] However, both the hydrothiol-
ation and hydroamination of alkynes sometimes suffer from
the issue of regioselectivity, which leads to the formation of
undesired regioisomers. Vinyl sulfides and vinylamines can
also be prepared from the reaction between carbonyl com-
pounds and thiols or primary amines through an addition
followed by an elimination reaction [see Scheme 1, Equa-
tion (2)].[6,7] In addition, the preparation of these com-
pounds has been achieved through cross-coupling reactions
of the corresponding electrophilic coupling partners such as
Scheme 1. General synthetic methods towards vinyl sulfides and
vinylamines.
During the past decades, iron has been one of the most
useful metals in modern organic synthesis because of its
lower toxicity and ease of accessibility.[10] Recently, we be-
came interested in the transition-metal-catalyzed intramo-
lecular hydroarylation reaction of arenes functionalized by
alkynes.[11] Moreover, as part of a synthetic project, we
needed to develop a simple route to cyclic vinyl sulfides
and vinylamines through an intramolecular hydroarylation
reaction. In this regard, we envisaged that by activating the
triple bond, which has a sulfur or nitrogen on the sp-hy-
bridized carbon, with an appropriate iron catalyst, the π
system of the aryl group could initiate an intramolecular
attack on the iron-activated alkyne to give cyclic vinyl sulf-
ides and vinylamines. Herein, we describe an efficient syn-
thetic method for the preparation of vinyl sulfides and vin-
ylamines through a catalytic intramolecular hydroarylation
[a] Department of Chemistry, Kangwon National University,
Chuncheon 200-701, Republic of Korea
Fax: +82-33-253-7582
E-mail: phlee@kangwon.ac.kr
Homepage: http://indium.kangwon.ac.kr
[b] Division of Chemistry and Biological Chemistry, School of
Physical and Mathematical Sciences, Nanyang Technological
University,
Singapore 637371, Singapore
Fax: +65-6791-1961
E-mail: sgkim@ntu.edu.sg
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.201201270.
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© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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D. Eom, J. Mo, P. H. Lee, Z. Gao, S. Kim
FULL PAPER
of arylalkynyl phenyl sulfides and sulfonamides in the pres- (DCE, 80 °C, 20 min) through a 6-endo mode, without the
ence of FeCl3 and AgOTf (OTf = trifluoromethanesulf- contamination from hydrolysis (see Table 1, Entry 9). A
onate; see Scheme 2).
control experiment using 15 mol-% AgOTf in DCE at 80 °C
for 6 h gave 2a in 54% yield (see Table 1, Entry 10). How-
ever, formation of the hydrolyzed product 3 in 13% yield
was inevitable. To check the possibility of catalysis by a pro-
tic acid,[9,14] we attempted the hydroarylation reaction in
the presence of trifluoromethanesulfonic acid (5 mol-%) in
DCE at 80 °C, which produced 2a and 3 in 67 and 15%
yields, respectively (see Table 1, Entry 11). These results
indicate that using both FeCl3 and AgOTf are essential for
the catalytic system in this intramolecular hydroarylation
reaction for the selective synthesis of cyclic vinyl sulfide 2a.
Scheme 2. Preparation of vinyl sulfides and vinylamines through
catalytic intramolecular hydroarylation (Ts = para-toluenesulfonyl,
FG = functional group, EWG = electron-withdrawing group, EDG
= electron-donating group).
Results and Discussion
Table 1. Optimization of preparation of vinyl sulfide through cata-
lytic intramolecular hydroarylation.[a]
First, a variety of functionalized arylalkynyl phenyl sulf-
ides were prepared by treatment of phenol and N-phenyl
sulfonamide derivatives with propargyl bromide followed by
a reaction with phenyl disulfide or phenylsulfenyl chloride
(see Scheme 3). Arylalkynyl phenyl sulfonamides were also
produced by a Cu-catalyzed oxidative coupling reaction
with 4-methyl-N-phenylbenzenesulfonamide in the presence
of sodium carbonate and pyridine under oxygen.[12]
Entry
Catalyst [mol-%]
Solvent t [h]
% Yield[b]
2a
3
1a
1
2
3
4
5
6
7
8
9
FeBr2 (5)
FeCl2 (5)
Fe(acac)3 (5)
FeBr3 (5)
FeCl3 (5)
FeCl3 (5)
DCE
DCE
DCE
6
6
6
0
0
0
0
0
0
0
0
0
0
96
95
95
47
20
28
94
0
DCE
6
6
1
6
40
61
60
0
64 19
91
toluene
CH3CN
dioxane
DCE
FeCl3 (5)
FeCl3 (5)
FeCl3 (5), AgOTf (15)
AgOTf (15)
TfOH (5)
1
DCE
DCE
0.3
6
0
0
10
11
54 13
67 15
0
0
DCE
0.5
[a] Reactions were carried out at 80 °C. [b] Isolated yield.
To demonstrate the efficiency and scope of the present
method, we applied this catalytic system to a wide range of
arylalkynyl phenyl sulfides 1, and the results are summa-
rized in Scheme 4. The treatment of 1b with 5 mol-% FeCl3
and 15 mol-% AgOTf gave hydroarylated product 2b selec-
tively in 88% yield, without contamination from the α-
tetralone. The reactions of 1c and 1d, substituted by a 2- or
4-methyl group on the aromatic ring, with the Fe catalyst
afforded hydroarylated products 2c and 2d in 84 and 83%
Scheme 3. Preparation of arylalkynyl phenyl sulfides and sulfon-
amides.
Synthesis of Vinyl Sulfides from Arylalkynyl Phenyl
Sulfides
To examine the feasibility of the intramolecular hydro- yield, respectively. Under the optimized reaction conditions,
arylation of arylalkynyl phenyl sulfide 1a, the reaction was the diethyl malonate-tethered arylalkynyl phenyl sulfide 1e
carried out with either FeBr2, FeCl2, or Fe(acac)3 [5 mol-% underwent cyclization smoothly through a selective 6-endo
each, (acac = acetylacetonate)] and heated to reflux in DCE mode to produce 2e in 79% yield.
(1,2-dichloroethane). In these cases, the reaction did not
In contrast, an electron-rich aryl ring counter-intuitively
proceed, and most of 1a was recovered unchanged (see depressed the transformation. Thus, the hydroarylation re-
Table 1, Entries 1, 2, and 3). However, when 1a was treated action of substrate 1f, with an electron-donating 4-methoxy
with 5 mol-% FeCl3 in various solvents such as toluene, group, was slow and required a longer reaction time
acetonitrile, 1,4-dioxane, and DCE at 80 °C, the solvent of (120 min) to obtain the product in 71% yield. After 10 min
choice was DCE, although the formation of 3 was 19% in DCE at 25 °C, the exposure of oxygen-tethered 1g to the
yield (see Table 1, Entries 5–8). To conduct the hydroaryl- Fe catalyst provided cyclic vinyl sulfide 2g in 70% yield.
ation reaction of 1a more efficiently, we decided to use Although the intramolecular hydroarylation of N-tosyl-
FeCl3 activated with AgOTf.[13] Here, we found that the hy- amine-linked 1h proceeded smoothly at 25 °C to afford cy-
droarylation of 1a proceeded intramolecularly under the clic vinyl sulfide 2h (95%, 10 min), the hydroarylation of 1i
catalytic conditions to provide 2a selectively in 91% yield with a 3-methoxy group on the aromatic ring gave vinyl
534
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Synthesis of Vinyl Sulfides and Vinylamines
to the optimized reaction conditions, the seven-membered
cyclic vinyl sulfide 2l was selectively obtained through an
exclusive 7-endo mode in 77% yield. It was gratifying to
obtain 2m selectively in 79% yield, starting from diethyl
malonate-tethered arylalkynyl phenyl sulfide 1m. N-Tosyl-
amine-linked alkynyl sulfide 1n was compatible with the
present reaction conditions, although the reaction required
a higher temperature (80 °C) and gave a lower product yield
(45%).
Next, a twofold intramolecular hydroarylation was
briefly examined. When aryl bis(alkynyl phenyl sulfide) 1o
was subjected in one reaction vessel to 5 mol-% FeCl3 and
15 mol-% AgOTf in DCE at 25 °C for 60 min, 2,7-dihy-
dropyrano[2,3-g]chromene (2o) with a phenylsulfenyl group
on the sp2-hybridized benzylic carbon was isolated in 72%
yield [see Equation (4)].
(4)
Synthesis of Vinylamines from Arylalkynyl Phenyl
Sulfonamides
On the basis of the catalytic hydroarylation of arylalk-
ynyl phenyl sulfides, we next turned our attention to the
hydroarylation of arylalkynyl phenyl sulfonamides (see
Scheme 5). The treatment of 4a with 5 mol-% FeCl3 and
15 mol-% AgOTf in DCE at 25 °C for 20 min selectively
provided hydroarylated product 5a in 85% yield, without
the contamination from the α-tetralone. When oxygen-teth-
ered arylalkynyl phenyl sulfonamides 4b and 4c were sub-
jected to the optimized reaction conditions, cyclic vin-
ylamines 5b and 5c were selectively obtained in 87 and 86%
yields, respectively, through a 6-endo mode. Although a
longer reaction time was needed, the hydroarylation of
arylalkynyl phenyl sulfonamide 4d, with an electron-donat-
ing 4-methoxy group on the aromatic ring, proceeded
smoothly to provide the corresponding cyclic vinylamine 5d
Scheme 4. Synthesis of vinyl sulfides from arylalkynyl phenyl sulf-
ides.[a]
sulfide 2i in a lower yield (65%), even after a longer reac- in 81% yield, albeit in a slightly lower yield than obtained
tion time (60 min). These results indicate that the progress for 5b and 5c. This tendency is similar to that observed
of the iron-catalyzed hydroarylation strongly depended on in the catalytic hydroarylations of the arylalkynyl phenyl
the electronic character of aryl ring, that is, the electron sulfides. Under the optimum reaction conditions, N-tosyl-
deficiency of the aryl ring accelerated the reaction. In the amine-linked 4e underwent a clean intramolecular hydro-
presence of an electron-withdrawing bromo group on aro- arylation to give cyclic vinylamine 5e in 81% yield. The
matic ring, the reaction of 1j with the Fe catalyst selectively present method worked equally well with arylalkynyl phenyl
provided, through a 6-endo mode, the desired cyclic vinyl sulfonamides 4f and 4g, containing an electron-donating 2-
sulfide 2j in 86% yield. However, the hydroarylation of 1k, isopropyl or 3-methoxy group on the aromatic ring, to pro-
containing an electron-withdrawing nitrile group on the vide the selective formation of cyclic vinylamines 5f and 5g
aromatic ring, required a higher reaction temperature in 92 and 85% yields, respectively. The reaction of 4h, with
(80 °C) and afforded the desired cyclic vinyl sulfide 2k in an electron-withdrawing bromo group, and the Fe catalyst
71% yield, indicating that the iron catalyst could be form- afforded, through a 6-endo mode, the desired product 5h in
ing a complex with the nitrile group. When 1l was subjected 93% yield. Because of the complexation of the nitrile group
Eur. J. Org. Chem. 2013, 533–540
© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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535

D. Eom, J. Mo, P. H. Lee, Z. Gao, S. Kim
FULL PAPER
with the iron catalyst, arylalkynyl phenyl sulfonamide 4i, pot to the standard conditions, bis(cyclic vinylamine) 5j was
with a nitrile group on the aromatic ring, required a longer produced in 60% yield [see Equation (5)].
reaction time and gentle heating to achieve completion.
(5)
Mechanism
Although, at the present stage, the mechanism for the
reaction has not been fully established, a possible reaction
pathway is shown in Scheme 6. The coordination of the iron
catalyst to the arylalkynyl phenyl sulfide (1) or sulfonamide
(4) results in the formation of alkyne–iron complex A or
arene–iron complex B. Moreover, the progress of the iron-
catalyzed hydroarylation depended on the electronic char-
acter of the aromatic ring, that is, an electron-rich aromatic
ring depressed the reaction. By considering these results, we
envisage that the present hydroarylation might employ vinyl
cationic intermediate E, which is generated in situ from A
because of the π-electron delocalization occurring between
the heteroatom and the conjugated alkyne as shown in alk-
ynyl chromium–arene complexes.[15] An intramolecular hy-
droarylation through the addition of an aromatic C–H
bond across a π bond might give intermediate G. Subse-
quent deprotonation of G followed by protodemetallation
of H to release the iron catalyst back into the catalytic cycle
might afford cyclic vinyl sulfide 2 or vinylamine 5. The ex-
Scheme 5. Synthesis of vinylamines from arylalkynyl sulfonamides.
Likewise, a twofold intramolecular hydroarylation of clusive formation of 2 or 5 through a 6- or 7-endo mode
arylalkynyl phenyl sulfonamide was attempted. When oxy- rules out the formation of intermediate vinyl cation C in
gen-tethered alkynyl sulfonamide 4j was subjected in one the catalytic cycle.
Scheme 6. Plausible mechanism for synthesis of vinyl sulfides and vinylamines through catalytic hydroarylation.
536
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Synthesis of Vinyl Sulfides and Vinylamines
(3,4-Dihydronaphthalen-1-yl)(phenyl)sulfane (2b):[8h] Colorless oil,
Rf = 0.3 (hexane). H NMR (400 MHz, CDCl3): δ = 7.57 (d, J =
Conclusions
1
6.9 Hz, 2 H), 7.28–7.22 (m, 4 H), 7.14–7.10 (m, 4 H), 6.57 (t, J =
4.8 Hz, 1 H), 2.88 (t, J = 8.0 Hz, 2 H), 2.47–2.45 (m, 2 H) ppm.
13C NMR (100 MHz, CDCl3): δ = 143.2, 137.2, 133.9, 133.2, 129.1,
128.4, 128.1, 127.8, 127.7, 127.3, 127.1, 53.7, 29.4, 26.8 ppm. IR
In summary, we developed an efficient synthetic method
for the preparation of cyclic vinyl sulfides and vinylamines
containing 1,2-dihydronaphthalene, 2H-chromene, and 1,2-
dihydroquinoline ring systems with a phenylsulfenyl or N-
phenyl-N-tosyl group on the sp2-hybridized benzylic
carbon. The intramolecular hydroarylation of arylalkynyl
phenyl sulfides and sulfonamides proceeded smoothly in a
selective 6- or 7-endo mode in the presence of FeCl3 and
AgOTf. The present method could be further extended to
the preparation of dihydropyrano[2,3-g]chromene deriva-
tives through a twofold Fe-catalyzed hydroarylation by a
selective 6-endo mode. Of special importance, the cationic
iron catalyst permits the participation of electron-deficient
aryl nucleophiles, which provide useful examples of hydro-
arylation.
(film): ν = 3060, 2936, 1682, 1438, 1348, 1302, 1144, 1084, 1024,
˜
739 cm–1.
5-Methyl-3,4-dihydronaphthalen-1-yl(phenyl)sulfane (2c): Yellow oil,
1
Rf = 0.4 (hexane). H NMR (400 MHz, CDCl3): δ = 7.48 (dd, J =
6.8, 1.9 Hz, 1 H), 7.24–7.16 (m, 4 H), 7.10–7.06 (m, 1 H), 7.03–
6.97 (m, 2 H), 6.55 (t, J = 4.8 Hz, 1 H), 2.80 (t, J = 8.0 Hz, 2 H),
2.42 (td, J = 8.0, 4.8 Hz, 2 H), 2.29 (s, 3 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 137.8, 137.3, 135.2, 135.1, 133.4, 131.0,
130.4, 129.3, 128.3, 126.4, 126.0, 123.8, 24.8, 23.9, 20.2 ppm. IR
(film): ν = 2923, 2853, 1681, 1595, 1464, 1439, 1282, 1070, 897,
˜
794, 742, 690, 632 cm–1. HRMS (EI): calcd. for C17H16S 252.0973;
found 252.0970.
(7-Methyl-3,4-dihydronaphthalen-1-yl)(phenyl)sulfane (2d): Yellow
1
oil, Rf = 0.4 (hexane). H NMR (400 MHz, CDCl3): δ = 7.41 (s, 1
H), 7.27–7.24 (m, 2 H), 7.19 (t, J = 7.6 Hz, 2 H), 7.12–7.07 (m, 1
H), 7.02 (d, J = 7.5 Hz, 1 H), 6.94 (d, J = 7.5 Hz, 1 H), 6.48 (t, J
= 4.7 Hz, 1 H), 2.80 (t, J = 8.0 Hz, 2 H), 2.41–2.36 (m, 2 H), 2.21
(s, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 137.7, 137.0,
136.6, 133.8, 133.5, 131.0, 129.4, 128.8, 128.7, 127.8, 126.2, 126.17,
Experimental Section
General Methods: Many chemical reagents were purchased com-
mercially and used without further purification. Analytical TLC
was carried out with precoated plates and visualized by using UV
light or staining with potassium permanganate. The 1H and 13C
NMR spectroscopic data were recorded at 298 K with a 400 Fou-
rier Transform NMR spectrometer. Chemical shifts were reported
in δ (ppm), relative to the internal standard of TMS. The signals
observed were described as s (singlet), d (doublet), t (triplet), q
(quartet), and m (multiplets). The number of protons (n) for a given
resonance was indicated as n H. Coupling constants were reported
as J values in Hz. The 13C NMR spectroscopic data were reported
in δ (ppm), downfield from TMS and relative to the signal of
CDCl3 (δ = 77.00 ppm, triplet). Mass spectrometry was performed
with a GC–HRMS spectrometer under electron impact (EI) ioniza-
tion (magnetic sector/electric sector double-focusing mass ana-
lyzer). FeCl2 (99.5%), FeBr2 (98%), Fe(acac)2 (99.9%), Fe(OTf)3
(90%), FeBr3 (98%), and FeCl3 (98%) were used.
27.8, 25.4, 21.7 ppm. IR (film): ν = 2934, 1682, 1614, 1583, 1489,
˜
1478, 1281, 1084, 813, 739, 690, 632 cm–1. HRMS (EI): calcd. for
C17H16S 252.0973; found 252.0974.
Diethyl 4-(Phenylthio)naphthalene-1,1(2H)-dicarboxylate (2e): Yel-
low oil, Rf = 0.3 (EtOAc/hexane, 1:20). 1H NMR (400 MHz,
CDCl3): δ = 7.67–7.65 (m, 1 H), 7.25–7.10 (m, 8 H), 6.50 (t, J =
4.7 Hz, 1 H), 4.32–4.22 (m, 4 H), 3.15 (d, J = 4.7 Hz, 2 H), 1.27
(t, J = 7.1 Hz, 6 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 170.7,
135.8, 133.5, 132.8, 132.1, 130.9, 128.9, 128.4, 128.2, 128.1, 127.2,
125.9, 125.8, 62.1, 58.9, 31.9, 14.0 ppm. IR (film): ν = 3058, 2979,
˜
1730, 1261, 1235, 1027, 738 cm–1. HRMS (EI): calcd. for
C22H22O4S 382.1239; found 382.1236.
Diethyl 6-Methoxy-4-(phenylthio)naphthalene-1,1(2H)-dicarboxyl-
ate (2f): Colorless oil, Rf = 0.3 (EtOAc/hexane, 1:20). 1H NMR
(400 MHz, CDCl3): δ = 7.23 (d, J = 2.6 Hz, 1 H), 7.21–7.15 (m, 4
H), 7.13–7.08 (m, 2 H), 6.77 (dd, J = 8.5, 2.7 Hz, 1 H), 6.55 (t, J
= 4.5 Hz, 1 H), 4.31–4.21 (m, 4 H), 3.67 (s, 3 H), 3.14 (d, J =
3.2 Hz, 2 H), 1.26 (t, J = 7.1 Hz, 6 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 170.9, 159.4, 135.7, 134.2, 133.4, 130.9, 128.9, 128.4,
128.2, 125.9, 124.9, 113.6, 111.4, 62.0, 58.3, 55.2, 32.2, 14.0 ppm.
Preparation of (3,4-Dihydronaphthalen-1-yl)(phenyl)sulfane: A sus-
pension of FeCl3 (2.4 mg, 1.5ϫ10–2 mmol, 5 mol-%) and AgOTf
(11.6 mg, 4.5ϫ10–2 mmol, 15 mol-%) in DCE (0.8 mL) was stirred
at 25 °C for 5 min. Then, a solution of 4-methyl-N-phenyl-N-[3-
(phenylthio)prop-2-ynyl]benzenesulfonamide (118.1 mg, 0.3 mmol)
in DCE (0.7 mL) was added under nitrogen. After the reaction mix-
ture was stirred at 80 °C for 20 min, it was quenched with water.
The aqueous layer was extracted with dichloromethane (DCM,
2ϫ15 mL), and the combined organic layers were washed with
water and brine, filtered, and then dried under reduced pres-
sure. Silica gel column chromatography (EtOAc/hexane, 1:15)
gave 4-(phenylthio)-1-tosyl-1,2-dihydroquinoline (2a, 107.4 mg,
0.273 mmol, 91%).
IR (film): ν = 2981, 2938, 1731, 1488, 1291, 1235, 1178, 1049 cm–1.
˜
HRMS (EI): calcd. for C23H24O5S 412.1344; found 412.1341.
4-(Phenylthio)-2H-chromene (2g): White solid, m.p. 125–128 °C. Rf
= 0.3 (EtOAc/hexane, 1:60). 1H NMR (400 MHz, CDCl3): δ =
7.43–7.34 (m, 3 H), 7.30–7.20 (m, 4 H), 7.12 (m, 1 H), 6.84–6.81
(m, 2 H), 5.89 (t, J = 4.1 Hz, 1 H), 4.79 (d, J = 4.1 Hz, 2 H) ppm.
13C NMR (100 MHz, CDCl3): δ = 154.5, 133.9, 130.6, 130.1, 130.0,
4-(Phenylthio)-1-tosyl-1,2-dihydroquinoline (2a): Yellow solid, m.p.
75–80 °C. Rf = 0.2 (EtOAc/hexane, 1:10). 1H NMR (400 MHz,
CDCl3): δ = 7.77 (dd, J = 1.1, 8.0 Hz, 1 H), 7.42–7.38 (m, 3 H),
7.34–7.30 (m, 1 H), 7.21–7.14 (m, 6 H), 6.87–6.84 (m, 2 H) 5.60 (t,
J = 4.5 Hz, 1 H), 4.48 (d, J = 4.5 Hz, 2 H), 2.41 (s, 3 H) ppm. 13C
NMR (100 MHz, CDCl3): δ = 143.6, 136.6, 135.3, 133.0, 131.3,
130.7, 129.4, 129.1, 128.8, 128.4, 127.7, 127.4, 126.9, 125.5, 125.2,
129.4, 127.2, 125.4, 122.0, 121.7, 116.2, 66.1 ppm. IR (solid): ν =
˜
1690, 1605, 1477, 1308, 1265, 1215, 1148, 1034, 737, 691 cm–1.
HRMS [FAB (fast atom bombardment)]: calcd. for C15H13OS [M
+ H]+ 241.0687; found 241.0689.
8-Isopropyl-4-(phenylthio)-1-tosyl-1,2-dihydroquinoline (2h): White
1
solid, m.p. 140–145 °C. Rf = 0.3 (EtOAc/hexane, 1:10). H NMR
46.1, 21.6 ppm. IR (solid): ν = 3061, 1689, 1597, 1476, 1354, 1164, (400 MHz, CDCl3): δ = 7.40 (dd, J = 7.8, 1.6 Hz, 1 H), 7.34–7.24
˜
1088 cm–1. HRMS (EI): calcd. for C22H19NO2S2 393.0857; found
393.0856.
(m, 7 H), 7.19 (d, J = 8.2 Hz, 2 H), 7.07 (m, 2 H), 5.17 (dd, J =
18.2, 6.0 Hz, 1 H) 3.97–3.90 (m, 2 H), 2.46 (s, 3 H), 1.44 (d, J =
Eur. J. Org. Chem. 2013, 533–540
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537

D. Eom, J. Mo, P. H. Lee, Z. Gao, S. Kim
FULL PAPER
6.9 Hz, 3 H), 1.11 (d, J = 6.9 Hz, 3 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 149.1, 144.0, 136.7, 133.5, 133.0, 132.6, 132.57, 131.0,
129.8, 129.6, 128.4, 128.2, 127.8, 124.9, 122.4, 47.3, 29.1, 26.4, 22.2,
J = 7.6 Hz, 1 H), 7.31–7.26 (m, 3 H), 7.24–7.15 (m, 7 H), 5.77 (t,
J = 7.4 Hz, 1 H), 4.19 (s, 2 H), 3.60 (d, J = 7.4 Hz, 2 H), 2.44 (s,
3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 143.4, 142.3, 137.7,
135.8, 133.8, 132.6, 130.1, 129.7, 129.2, 129.0, 128.5, 128.0, 127.96,
22.1 ppm. IR (solid): ν = 2976, 1695, 1583, 1477, 1354, 1340, 1162,
˜
1069, 818, 739, 706, 679 cm–1. HRMS (EI): calcd. for C25H25NO2S2
435.1327; found 435.1326.
127.6, 122.6, 49.8, 43.9, 21.6 ppm. IR (solid): ν = 3061, 2923, 1336,
˜
1157, 1091, 934, 814, 719, 690, 656 cm–1. HRMS (EI): calcd. for
C23H21NO2S2 407.1014; found 407.1016.
7-Methoxy-4-(phenylthio)-1-tosyl-1,2-dihydroquinoline (2i): White
solid, m.p. 140–145 °C. Rf = 0.7 (EtOAc/hexane, 1:4). 1H NMR 4,9-Bis(phenylthio)-2,7-dihydropyrano[2,3-g]chromene (2o): White
(400 MHz, CDCl3): δ = 7.43 (d, J = 8.3 Hz, 2 H), 7.36 (d, J =
2.6 Hz, 1 H), 7.29 (d, J = 8.6 Hz, 1 H), 7.20–7.14 (m, 5 H), 6.83–
6.80 (m, 2 H), 6.69 (dd, J = 8.8, 2.7 Hz, 1 H), 5.55 (t, J = 4.5 Hz,
1 H), 4.47 (d, J = 4.5 Hz, 2 H), 3.85 (s, 3 H), 2.41 (s, 3 H) ppm.
13C NMR (100 MHz, CDCl3): δ = 159.7, 143.6, 136.74, 136.7,
133.5, 130.8, 130.3, 129.4, 129.0, 127.4, 126.9, 126.5, 123.1, 121.4,
solid, m.p. 208–212 °C. Rf = 0.7 (DCM/hexane, 1:1). 1H NMR
(400 MHz, CDCl3): δ = 7.38–7.25 (m, 10 H), 6.72 (s, 2 H), 6.22 (t,
J = 3.9 Hz, 2 H), 4.72 (d, J = 3.9 Hz, 4 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 148.5, 133.6, 130.9, 129.9, 129.5, 127.5,
126.7, 123.0, 112.2, 65.9 ppm. IR (solid): ν = 3055, 2919, 1694,
˜
1471, 1439, 1248, 1132, 1022, 745, 691, 632 cm–1. HRMS (EI):
112.9, 111.7, 55.6, 46.2, 21.6 ppm. IR (solid): ν = 2926, 1680, 1597, calcd. for C24H18O2S2 402.0748; found 402.0748.
˜
1440, 1351, 1247, 1161, 1087, 1032, 813, 706, 659 cm–1. HRMS
(EI): calcd. for C23H21NO3S2 423.0963; found 423.0963.
N-(3,4-Dihydronaphthalen-1-yl)-4-methyl-N-phenylbenzenesulfon-
amide (5a): Yellow solid, m.p. 150–154 °C. Rf = 0.5 (EtOAc/hexane,
1
6-Bromo-4-(phenylthio)-1-tosyl-1,2-dihydroquinoline (2j): White so-
1:5). H NMR (400 MHz, CDCl3): δ = 7.63 (d, J = 8.2 Hz, 2 H),
lid, m.p. 138–142 °C. Rf = 0.3 (EtOAc/hexane, 1:10). 1H NMR 7.56 (d, J = 7.4 Hz, 1 H), 7.47–7.45 (m, 2 H), 7.30–7.05 (m, 8 H),
(400 MHz, CDCl3): δ = 7.63 (d, J = 8.6 Hz, 1 H), 7.55 (d, J =
5.98 (t, J = 4.6 Hz, 1 H), 2.76 (t, J = 8.2 Hz, 2 H), 2.43–2.38 (m,
2.3 Hz, 1 H), 7.43–7.37 (m, 3 H), 7.23–7.17 (m, 5 H), 6.89–6.86 (m, 5 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 143.7, 140.5, 138.4,
2 H), 5.55 (t, J = 4.5 Hz, 1 H), 4.43 (d, J = 4.5 Hz, 2 H), 2.42 (s, 137.7, 136.7, 132.8, 129.6, 129.2, 129.1, 128.1, 127.6, 127.2, 127.1,
3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 144.3, 136.8, 134.7,
132.5, 132.1, 131.7, 131.2, 130.7, 130.0, 129.7, 128.9, 128.4, 128.1,
126.8, 123.8, 27.3, 23.3, 21.8 ppm. IR (solid): ν = 2953, 2853, 1458,
˜
1377, 1350, 1167, 1094, 962, 768, 691, 665, 619, 567 cm–1. HRMS
(FAB): calcd. for C23H22NO2S [M + H]+ 376.1371; found 376.1371.
127.8, 126.4, 120.7, 46.4, 22.1 ppm. IR (solid): ν = 3062, 2923,
˜
1589, 1474, 1382, 1230, 1158, 1087, 1008, 816, 683, 660 cm–1.
HRMS (EI): calcd. for C22H18BrNO2S2 470.9962; found 470.9964.
N-(2H-Chromen-4-yl)-4-methyl-N-phenylbenzenesulfonamide (5b):
Yellow solid, m.p. 153–158 °C. Rf = 0.3 (EtOAc/hexane, 1:5). 1H
NMR (400 MHz, CDCl3): δ = 7.63 (d, J = 8.7 Hz, 2 H), 7.44–7.42
(m, 2 H), 7.38–7.36 (m, 1 H), 7.31–7.22 (m, 5 H), 7.10–7.06 (m, 1
H), 6.86–6.82 (m, 1 H), 6.74 (d, J = 8.2 Hz, 1 H), 5.75 (t, J =
4.1 Hz, 1 H), 4.84 (d, J = 4.1 Hz, 2 H), 2.41 (s, 3 H) ppm. 13C
NMR (100 MHz, CDCl3): δ = 155.5, 144.1, 139.6, 137.3, 135.8,
4-(Phenylthio)-1-tosyl-1,2-dihydroquinoline-6-carbonitrile (2k): Yel-
1
low solid, m.p. 88–92 °C. Rf = 0.3 (EtOAc/hexane, 1:4). H NMR
(400 MHz, CDCl3): δ = 7.88 (d, J = 8.4 Hz, 1 H), 7.70 (d, J =
1.9 Hz, 1 H), 7.56 (dd, J = 8.4, 1.9 Hz, 1 H), 7.44 (d, J = 8.3 Hz,
2 H), 7.27–7.16 (m, 5 H), 6.85–6.83 (m, 2 H), 5.81 (t, J = 4.5 Hz,
1 H), 4.53 (d, J = 4.5 Hz, 2 H), 2.44 (s, 3 H) ppm. 13C NMR 130.2, 129.8, 129.3, 128.1, 127.6, 127.4, 124.4, 121.7, 121.5, 121.4,
(100 MHz, CDCl3): δ = 144.8, 139.9, 136.7, 132.6, 132.4, 131.0, 116.2, 65.4, 21.8 ppm. IR (solid): ν = 2953, 2853, 1456, 1377, 1348,
˜
130.5, 130.2, 129.8, 129.6, 129.4, 128.4, 128.1, 127.6, 127.3, 118.7,
1304, 1223, 1167, 1090, 1065, 957, 756, 692, 660, 567 cm–1. HRMS
(FAB): calcd. for C22H20NO3S [M + H]+ 378.1164; found 378.1164.
110.3, 46.3, 22.1 ppm. IR (solid): ν = 3060, 2230, 1595, 1479, 1354,
˜
1163, 1085, 814, 742, 670 cm–1. HRMS (EI): calcd. for
C23H18N2O2S2 418.0810; found 418.0813.
N-(2H-Benzo[h]chromen-4-yl)-4-methyl-N-phenylbenzenesulfon-
amide (5c): White solid, m.p. 153–157 °C. Rf = 0.3 (EtOAc/hexane,
1
(6,7-Dihydro-5H-benzo[7]annulen-9-yl)(phenyl)sulfane (2l): Yellow
1:4). H NMR (400 MHz, CDCl3): δ = 8.06 (t, J = 4.8 Hz, 1 H),
solid, m.p. 64–66 °C. Rf = 0.3 (hexane). 1H NMR (400 MHz, 7.68–7.66 (m, 3 H), 7.50–7.45 (m, 3 H), 7.41–7.38 (m, 2 H), 7.32–
CDCl3): δ = 7.65–7.63 (m, 1 H), 7.26–7.04 (m, 8 H), 6.61 (t, J =
7.3 Hz, 1 H), 2.70 (t, J = 7.0 Hz, 2 H), 2.22–2.18 (m, 2 H), 1.98–
7.18 (m, 6 H), 5.80 (t, J = 4.1 Hz, 1 H), 5.02 (d, J = 4.1 Hz, 2 H),
2.41 (s, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 151.8, 144.1,
1.93 (m, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 141.7, 138.4, 139.7, 137.4, 136.6, 134.8, 129.8, 129.3, 128.1, 127.8, 127.5, 127.3,
135.9, 135.3, 134.6, 129.6, 129.1, 128.8, 128.1, 127.5, 126.2, 126.1,
127.1, 125.8, 124.5, 122.0, 121.6, 120.9, 119.0, 116.1, 65.9,
35.4, 32.7, 26.0 ppm. IR (solid): ν = 3059, 2931, 2855, 1681, 1163,
21.8 ppm. IR (solid): ν = 2953, 2853, 1640, 1462, 1377, 1352, 1198,
˜
˜
1582, 1478, 1438, 767, 748 cm–1. HRMS (EI): calcd. for C17H16S
252.0973; found 252.0972.
1165, 1088, 1009, 962, 806, 692, 604, 556 cm–1. HRMS (FAB):
calcd. for C26H22NO3S [M + H]+ 428.1320; found 428.1319.
Diethyl 2-Methyl-9-(phenylthio)-5H-benzo[7]annulene-6,6(7H)-di-
carboxylate (2m): Colorless oil, Rf = 0.2 (EtOAc/hexane, 1:30). H
NMR (400 MHz, CDCl3): δ = 7.45 (s, 1 H), 7.29–7.27 (m, 2 H), 1:5). H NMR (400 MHz, CDCl3): δ = 7.63 (d, J = 8.3 Hz, 2 H),
N-(6-Methoxy-2H-chromen-4-yl)-4-methyl-N-phenylbenzenesulfon-
1
amide (5d): White solid, m.p. 115–120 °C. Rf = 0.3 (EtOAc/hexane,
1
7.22–7.14 (m, 4 H), 6.97 (dd, J = 7.7, 1.2 Hz, 1 H), 6.39 (t, J =
7.3 Hz, 1 H), 4.23–4.16 (m, 4 H), 3.16 (s, 2 H), 2.40 (d, J = 7.3 Hz,
7.43 (d, J = 7.1 Hz, 2 H), 7.31–7.20 (m, 5 H), 6.89 (d, J = 2.9 Hz,
1 H), 6.68 (d, J = 8.7 Hz, 1 H), 6.63 (dd, J = 8.7, 2.9 Hz, 1 H),
2 H) 2.27 (s, 3 H), 1.26 (t, J = 7.1 Hz, 6 H) ppm. 13C NMR 5.82 (t, J = 4.0 Hz, 1 H), 4.78 (d, J = 4.0 Hz, 2 H), 3.67 (s, 3 H),
(100 MHz, CDCl3): δ = 171.4, 138.1, 137.8, 137.2, 135.2, 134.6, 2.41 (s, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 154.6, 149.7,
131.2, 130.9, 130.2, 129.3, 129.2, 129.0, 127.2, 68.8, 64.0, 38.0, 32.3,
144.4, 139.9, 137.6, 136.0, 130.0, 129.5, 128.3, 127.9, 127.6, 122.4,
21.6, 14.5 ppm. IR (film): ν = 2979, 1731, 1439, 1267, 1211,
122.3, 117.1, 116.0, 109.6, 65.6, 56.0, 22.0 ppm. IR (solid): ν =
˜
˜
1074 cm–1. HRMS (EI): calcd. for C24H26O4S 410.1552; found
410.1551.
3064, 1595, 1578, 1429, 1354, 1208, 1165, 1092, 1062, 662 cm–1.
HRMS (FAB): calcd. for C23H22NO4S [M + H]+ 408.1270; found
408.1267.
5-(Phenylthio)-2-tosyl-2,3-dihydro-1H-benzo[c]azepine (2n): Brown
solid, m.p. 78–82 °C. Rf = 0.3 (DCM/EtOAc/hexane, 1:1:9). 1H 4-Methyl-N-phenyl-N-(1-tosyl-1,2-dihydroquinolin-4-yl)benzenesulf-
NMR (400 MHz, CDCl3): δ = 7.69 (d, J = 8.3 Hz, 2 H), 7.65 (d,
onamide (5e): White solid, m.p. 80–85 °C. Rf = 0.3 (EtOAc/hexane,
538
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© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2013, 533–540

Synthesis of Vinyl Sulfides and Vinylamines
1
1:4). H NMR (400 MHz, CDCl3): δ = 7.73 (dd, J = 8.0, 0.9 Hz, N,NЈ-(2,7-Dihydropyrano[2,3-g]chromen-4,9-diyl)bis(4-methyl-N-
1 H), 7.53 (dd, J = 7.7, 1.4 Hz, 1 H), 7.44 (d, J = 8.3 Hz, 2 H),
7.30–7.13 (m, 9 H), 6.97–6.95 (m, 2 H), 6.91 (t, J = 8.1 Hz, 2 H),
5.73 (t, J = 4.4 Hz, 1 H), 4.60 (s, 2 H), 2.42 (s, 3 H), 2.25 (s, 3
H) ppm. 13C NMR (100 MHz, CDCl3): δ = 144.3, 143.7, 139.6,
137.4, 137.3, 137.1, 136.4, 129.9, 129.8, 129.5, 129.3, 128.2, 127.9,
127.8, 127.7, 127.3, 126.7, 125.0, 123.9, 45.5, 22.1, 22.0 ppm. IR
phenylbenzenesulfonamide) (5j): Pale yellow solid, m.p. 279–283 °C.
Rf = 0.4 (DCM). H NMR (300 MHz, [D6]DMSO): δ = 7.60 (d, J
= 8.3 Hz, 4 H), 7.40 (d, J = 8.3 Hz, 4 H), 7.36 (d, J = 6.9 Hz, 8
H), 7.32–7.26 (m, 2 H), 6.64 (s, 2 H), 5.99 (t, J = 3.9 Hz, 2 H), 4.77
(d, J = 3.9 Hz, 4 H), 2.39 (s, 6 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 149.8, 144.9, 140.2, 134.3, 130.7, 130.1, 128.4, 128.1,
1
(solid): ν = 2924, 2853, 2360, 1637, 1597, 1490, 1453, 1354, 1164,
127.3, 126.4, 125.7, 123.3, 111.5, 66.0, 21.8 ppm. IR (solid): ν =
˜
˜
1090, 1068, 814 cm–1. HRMS (EI): calcd. for C29H26N2O4S2
530.1334; found 530.1334.
2923, 2834, 1489, 1354, 1208, 1165, 695, 574 cm–1. HRMS (FAB):
calcd. for C38H32N2O6S2 [M + H]+ 677.1780; found 677.1777.
Supporting Information (see footnote on the first page of this arti-
N-(8-Isopropyl-1-tosyl-1,2-dihydroquinolin-4-yl)-4-methyl-N-phenyl-
benzenesulfonamide (5f): Yellow solid, m.p. 185–190 °C. Rf = 0.5
(EtOAc/hexane, 1:3). H NMR (400 MHz, CDCl3): δ = 7.55–7.53
1
cle): H and 13C NMR spectra for the compounds synthesized.
1
(m, 1 H), 7.41 (d, J = 8.2 Hz, 2 H), 7.36–7.30 (m, 4 H), 7.28–7.18
(m, 5 H), 7.07 (d, J = 7.3 Hz, 2 H), 6.86 (d, J = 7.8 Hz, 2 H), 5.73–
5.71 (m, 1 H), 4.65 (dd, J = 18.5, 5.9 Hz, 1 H), 4.14 (dd, J = 18.5,
2.2 Hz, 1 H), 3.70 (sept, J = 6.8 Hz, 1 H), 2.39 (s, 3 H), 2.23 (s, 3
H), 1.37 (d, J = 6.8 Hz, 3 H), 1.08 (d, J = 6.8 Hz, 3 H) ppm. 13C
NMR (100 MHz, CDCl3): δ = 147.0, 142.8, 142.3, 138.1, 137.1,
135.8, 135.6, 131.4, 128.8, 128.4, 128.3,127.9, 127.3, 126.9, 126.7,
126.6, 126.5, 124.1, 121.2, 44.6, 27.8, 24.9, 20.74, 20.7, 20.5 ppm.
Acknowledgments
S. K. acknowledges Nanyang Technological University for finan-
cial support (SUG M58110000). This work was funded by the
National Research Foundation of Korea through the NCRL (2012-
0001245) and BRL programs (2009-0087013). We thank Dr. Sung
Hong Kim at the KBSI (Daegu) for obtaining the HRMS data.
P. H. thanks Prof. S. Chang (KAIST) for the helpful discussions.
IR (solid): ν = 2926, 1726, 1344, 1158, 1109, 1088, 1068, 1030, 961,
˜
819, 696, 668 cm–1. HRMS (EI): calcd. for C32H32N2O4S2
572.1803; found 572.1806.
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N-(7-Methoxy-1-tosyl-1,2-dihydroquinolin-4-yl)-4-methyl-N-phenyl-
benzenesulfonamide (5g): White solid, m.p. 192–196 °C. Rf = 0.4
(EtOAc/hexane, 1:3). 1H NMR (400 MHz, CDCl3): δ = 7.44 (dd, J
= 8.3, 1.7 Hz, 3 H), 7.33–7.31 (m, 3 H), 7.22–7.12 (m, 5 H), 6.95
(d, J = 7.9 Hz, 2 H), 6.91 (d, J = 8.1 Hz, 2 H), 6.70 (dd, J = 8.6,
2.5 Hz, 1 H), 5.58 (t, J = 4.5 Hz, 1 H), 4.57 (s, 2 H), 3.79 (s, 3 H),
2.40 (s, 3 H), 2.24 (s, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ
= 160.4, 144.3, 143.8, 139.7, 137.8, 137.3, 137.2, 137.1, 129.9,
129.85, 129.3, 128.2, 127.8, 127.6, 127.3, 126.1, 120.7, 120.6, 112.6,
111.5, 56.0, 45.6, 22.1, 22.0 ppm. IR (solid): ν = 3661, 1607, 1492,
˜
1344, 1157, 1089, 1062, 985, 918, 696, 671, 661 cm–1. HRMS (EI):
calcd. for C30H28N2O5S2 560.1440; found 560.1438.
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65, 4553; f) H. W. Lam, P. A. Cooke, G. Pattenden, W. M. Ban-
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Trans. 1 1999, 847; g) K. Morimoto, K. Tsuji, T. Iio, N. Miyata,
A. Uchida, R. Osawa, H. Kitsutaka, A. Takahashi, Carcino-
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5156.
N-(6-Bromo-1-tosyl-1,2-dihydroquinolin-4-yl)-4-methyl-N-phenyl-
benzenesulfonamide (5h): White solid, m.p. 188–193 °C. Rf = 0.3
(EtOAc/hexane, 1:5). H NMR (400 MHz, CDCl3): δ = 7.60 (d, J
= 8.7 Hz, 1 H), 7.55 (s, 1 H), 7.42 (d, J = 8.0 Hz, 2 H), 7.36 (d, J
= 8.5 Hz, 1 H), 7.30 (d, J = 8.0 Hz, 2 H), 7.26–7.22 (m, 3 H), 7.18
(t, J = 7.7 Hz, 2 H), 6.94 (d, J = 8.0 Hz, 4 H), 5.79 (t, J = 4.2 Hz,
1 H), 4.59 (s, 2 H), 2.42 (s, 3 H), 2.27 (s, 3 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 144.2, 143.6, 138.9, 136.5, 136.4, 136.0,
135.0, 131.9, 129.64, 129.6, 129.1, 127.8, 127.6, 127.5, 127.45,
1
127.4, 126.9, 125.0, 119.9, 45.0, 21.7, 21.6 ppm. IR (solid): ν =
˜
3061, 1596, 1470, 1348, 1198, 1185, 1164, 1084, 1064, 949, 693,
659 cm–1. HRMS (EI): calcd. for C29H25BrN2O4S2 608.0439; found
608.0439.
N-(6-Cyano-1-tosyl-1,2-dihydroquinolin-4-yl)-4-methyl-N-phenyl-
benzenesulfonamide (5i): White solid, m.p. 135–138 °C. Rf = 0.3
1
(EtOAc/hexane, 1:3). H NMR (400 MHz, CDCl3): δ = 7.83 (d, J
= 8.5 Hz, 1 H), 7.69 (d, J = 1.9 Hz, 1 H), 7.51 (dd, J = 8.5, 1.9 Hz,
1 H), 7.43 (d, J = 8.3 Hz, 2 H), 7.35 (d, J = 8.3 Hz, 2 H), 7.25–
7.19 (m, 5 H), 7.00 (t, J = 8.0 Hz, 4 H), 5.88 (t, J = 4.5 Hz, 1 H),
4.64 (s, 2 H), 2.44 (s, 3 H), 2.30 (s, 3 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 144.5, 144.2, 140.0, 138.7, 136.3, 136.1, 135.6, 132.5,
129.8, 129.7, 129.2, 128.2, 128.1, 127.8, 127.77, 127.3, 126.8, 125.8,
125.6, 118.2, 109.6, 45.0, 21.7, 21.6 ppm. IR (solid): ν = 2926, 2229,
˜
[4] a) C. J. Weiss, T. J. Marks, J. Am. Chem. Soc. 2010, 132, 10533;
b) A. Corma, C. Gonzalez-Arellano, M. Iglesias, F. Sanchez,
Appl. Catal. A 2010, 375, 49; c) J. Yang, A. Sabarre, L. R. Fra-
1727, 1597, 1489, 1349, 1162, 1089, 1065, 696, 663, 629 cm–1
HRMS (EI): calcd. for C30H25N3O4S2 555.1286; found 555.1289.
.
Eur. J. Org. Chem. 2013, 533–540
© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
539

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Received: September 24, 2012
Published Online: November 30, 2012
540
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Eur. J. Org. Chem. 2013, 533–540