Generation of 6H-benzo[f]cyclopenta[d][1,2]thiazepine 5,5-dioxides via a palladium-catalyzed reaction of 2-(2-alkynyl)benzenesulfonamide

Article abstract of DOI:10.1039/c2dt32452k

An efficient approach for the assembly of 6H-benzo[f]cyclopenta[d][1,2] thiazepine 5,5-dioxides via a palladium-catalyzed tandem reaction of 2-(2-alkynyl)benzenesulfonamide with 2-alkynylvinyl bromide is reported. This transformation proceeds smoothly through a double carbopalladation with high efficiency. The Royal Society of Chemistry 2013.

Full text of DOI:10.1039/c2dt32452k

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Generation of 6H-benzo[f]cyclopenta[d][1,2]thiazepine
5,5-dioxides via a palladium-catalyzed reaction of
2-(2-alkynyl)benzenesulfonamide†
Cite this: Dalton Trans., 2013, 42, 4410
Huanhuan Wang,a Yong Luo,a Xiufeng Hou*a and Jie Wu*a,b
Received 15th October 2012,
Accepted 30th November 2012
An efficient approach for the assembly of 6H-benzo[f]cyclopenta[d][1,2]thiazepine 5,5-dioxides via a
palladium-catalyzed tandem reaction of 2-(2-alkynyl)benzenesulfonamide with 2-alkynylvinyl bromide is
DOI: 10.1039/c2dt32452k
reported. This transformation proceeds smoothly through
a double carbopalladation with high
www.rsc.org/dalton
efficiency.
2-alkynylvinyl bromide 2 was used as the coupling partner
(Scheme 1). The presence of the alkynyl moiety in 2-alkynyl-
1. Introduction
Using small molecule modulators for the systematic pertur- vinyl bromide 2 would allow an alternative pathway in the reac-
bation of gene products has been a hot research area in the tion with 2-(2-alkynyl)benzenesulfonamide 1.
interdisciplinary research field of chemical biology as well as
As a privileged scaffold, the core of benzo[f][1,2]thiazepine
in the pharmaceutical industry.1 Therefore, libraries of novel dioxide has attracted much attention. For instance, Tianeptine
drug-like small molecules with maximized molecular diversity (trade-names: Stablon, Coaxil, Tatinol) is a drug used for treat-
are of high demand.2 In the past decade, the strategy of diver- ing major depressive episodes.6 Compounds such as the
sity-oriented synthesis developed by Schreiber has been widely human immunodeficiency virus protease inhibitor,7a calcium
used for the construction of natural product-like compounds sensing receptor agonists,7b and the farnesyltransferase inhibi-
in the studies of chemical genetics.3 For example, Park and co- tor7c which contain the benzo[f][1,2]thiazepine dioxide skele-
workers reported the diversity-oriented synthesis of some ton show remarkable biological activities. As part of a program
molecular frameworks with a privileged substructure, which for synthesising natural product-like compounds for different
displayed enhanced selectivity and specificity towards multiple biological applications, we are interested in benzo[f][1,2]thiazepine
biological assay systems as small molecule modulators for dioxide derivatives. Although methods exist for the synthesis
specific biological targets.4 Among the methods developed, of benzo[f][1,2]thiazepine dioxide derivatives,7a,b,8 the
tandem reactions have been utilized as an efficient approach methods usually suffer from harsh reaction conditions, multi-
for the introduction of molecular complexity.5
We are interested in the synthesis of nitrogen-containing
heterocycles via tandem reactions. We have recognized that
2-(2-alkynyl)benzenesulfonamide 1 would be a useful building
block for reaction development. Usually, 2-(2-alkynyl)benzene-
sulfonamide 1 reacts with an aryl/alkenyl halide in the pres-
ence of Pd(0) to afford compound I (6-endo cyclization, path a)
or II (5-exo cyclization, path b). However, we envisioned that a
core of benzo[f][1,2]thiazepine dioxide would be formed if
aDepartment of Chemistry, Fudan University, 220 Handan Road, Shanghai 200433,
China. E-mail: jie_wu@fudan.edu.cn; Fax: +86 21 6564 1740; Tel: +86 21 6510
2412
bState Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic
Chemistry, Chinese Academy of Sciences, 354 Fenglin Road, Shanghai 200032, China
†Electronic supplementary information (ESI) available: Experimental procedure,
characterization data, 1H and 13C NMR spectra of compounds 3, and a CIF file
of compound 3a. CCDC 892027. For ESI and crystallographic data in CIF or
Scheme 1 Palladium-catalyzed reaction of 2-(2-alkynyl)benzenesulfonamide 1
other electronic format see DOI: 10.1039/c2dt32452k
with an aryl/alkenyl halide.
4410 | Dalton Trans., 2013, 42, 4410–4415
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Table 1 Initial studies for the palladium-catalyzed reaction of N-methyl-2-(2-
phenylethynyl)benzenesulfonamide 1a with 2-alkynylvinyl bromide 2aa
Entry
Ligand
Base
Solvent
Yieldb (%)
1
2
3
4
5
6
7
8
PCy3
PCy3
PCy3
PCy3
PCy3
PCy3
PCy3
PCy3
NaOMe
Cs2CO3
t-BuONa
K3PO4
Na2CO3
KOAc
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
DMF
Trace
Trace
Trace
Trace
Trace
Trace
Trace
Trace
48
46
54
60
62
85
30
57
73
77
55
70
Trace
64
Scheme 2 A proposed route for the palladium-catalyzed reaction of 2-(2-
alkynyl)benzenesulfonamide 1 with 2-alkynylvinyl bromide 2.
NaOAc
CsOAc
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
9
PCy3
steps, and scope limitations. Thus, it is highly desirable to
develop a novel route for the efficient assembly of benzo[f][1,2]-
thiazepine dioxide derivatives.
10
11
12
13
14
15
16
17
18
19
20
21
22
Xantphos
X-phos
PPh3
DPPF
DPPP
S-Phos
DPPM
DPPE
DPPB
BINAP
DPEphos
DPPP
DPPP
Recently, a highly selective palladium-catalyzed intramole-
cular or intermolecular double carbopalladation for the forma-
tion of molecular complexity has been developed.9 Encouraged
by this result, we hypothesized that benzo[f][1,2]thiazepine
dioxide derivatives could be generated through a palladium-
catalyzed reaction of 2-(2-alkynyl)benzenesulfonamide 1 with
2-alkynylvinyl bromide 2. The proposed synthetic route is
present in Scheme 2. We envisioned that an oxidative addition
of Pd(0) to 2-alkynylvinyl bromide 2 would occur first to gen-
erate a Pd(II) species A, which might undergo coordination to
the triple bond of 2-(2-alkynyl)benzenesulfonamide 1 to afford
intermediate B. Further intramolecular insertion of a triple
bond would happen to produce intermediate C, which would
then provide the expected benzo[f][1,2]thiazepine dioxide 3 via
a C–N coupling. During the reaction process, three bonds
would be formed. Additionally, complexity and diversity could
be incorporated with high efficiency. We believed that the
hypothesis presented in Scheme 2 was feasible although theo-
retically there are several possible competitive pathways, such
as direct C–N coupling and direct cyclization of 2-(2-alkynyl)-
Toluene
a Reaction conditions: N-methyl-2-(2-phenylethynyl)benzenesulfonamide
1a (0.3 mmol), 2-alkynylvinyl bromide 2a (1.2 equiv., 0.36 mmol),
palladium catalyst (5 mol%, 0.015 mmol), ligand (5 or 10 mol%), base
(2.0 equiv., 0.6 mmol), 100 °C. b Isolated yield based on N-methyl-2-
(2-phenylethynyl)benzenesulfonamide 1a.
benzenesulfonamide
(Scheme 1).
1
under the palladium catalysis
2. Results and discussion
Initially, a model reaction of 2-(2-alkynyl)benzenesulfonamide
1a with 2-alkynylvinyl bromide 2a in the presence of Pd(OAc)2
(5 mol%) was studied (Table 1). A trace amount of product was
detected when the reaction took place in the presence of PCy3
(10 mol%) and NaOMe in 1,4-dioxane at 100 °C (Table 1,
Fig. 1 X-ray ORTEP illustration of 6H-benzo[f]cyclopenta[d][1,2]thiazepine 5,5-
dioxide 3a (30% probability ellipsoids).
entry 1). A similar outcome was seen when the base was identified by X-ray diffraction analysis (Fig. 1, also see the
changed to Cs2CO3, t-BuONa, K3PO4, Na2CO3, KOAc, NaOAc, ESI†). No desired product was formed in the absence of a
or CsOAc (Table 1, entries 2–8). The expected benzo[f][1,2]- phosphine ligand (data not shown in Table 1). Further
thiazepine dioxide 3a was obtained and isolated in 48% yield screening of other ligands revealed that the reaction worked
when potassium carbonate was added as the base (Table 1, efficiently in the presence of DPPP, which produced the corres-
entry 9). The structure of compound 3a was unambiguously ponding product 3a in 85% yield (Table 1, entries 10–20).
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The reaction was not successful in DMF (Table 1, entry 21). A
64% yield was obtained when the reaction was performed in
3. Conclusion
toluene (Table 1, entry 22). The reaction was slower at a lower In conclusion, we have described an efficient approach for
temperature (data not shown in Table 1). the preparation of 6H-benzo[f]cyclopenta[d][1,2]thiazepine 5,5-
Table 2 summarizes the results for the palladium-catalyzed dioxides via a palladium-catalyzed tandem reaction of 2-(2-
reaction of 2-(2-alkynyl)benzenesulfonamides 1 with 2-alkynyl- alkynyl)benzenesulfonamide with 2-alkynylvinyl bromide. The
vinyl bromides 2 under the optimized conditions (5 mol% of reaction proceeds efficiently with the formation of three bonds
Pd(OAc)2, 5 mol% of DPPP, 2.0 equiv. of K2CO3, 1,4-dioxane, in a one-pot procedure. A double carbopalladation is believed
100 °C). The double carbopalladation was found to be highly to be the key step during the reaction process. The construc-
efficient, and a range of 6H-benzo[f]cyclopenta[d][1,2]thi- tion of a library of novel drug-like small molecules with maxi-
azepine 5,5-dioxides 3 was obtained in good to excellent yields. mized molecular diversity is ongoing in our laboratory.
Different functional groups were compatible under the stan-
dard conditions. 2-(2-Alkynyl)benzenesulfonamides 1 with
various substituents (electron-donating and electron-withdraw-
4. Experimental section
ing groups) on the aromatic ring were all good partners in the
transformation. Reactions involving 2-(2-alkynyl)benzenesulfon-
amides 1 with aryl or alkyl groups attached on the triple
bond all worked well to produce the desired products 3. For
some cases, the quantitative yields were obtained. Additionally,
2-alkynylvinyl bromides 2 were workable during the reaction
process.
General procedure of the synthesis of 6H-benzo[f]cyclopenta[d]-
[1,2]thiazepine 5,5-dioxides 3 via a palladium-catalyzed reac-
tion of 2-(2-alkynyl)benzenesulfonamide 1 with 2-alkynylvinyl
bromide 2: 2-(2-alkynyl)benzenesulfonamide 1 (0.30 mmol)
was added to a mixture of Pd(OAc)2 (5 mol%), DPPP (5 mol%),
K2CO3 (0.60 mmol), and 2-alkynylvinyl bromide 2 (0.36 mmol)
in 1,4-dioxane (2.0 mL). The mixture was stirred at 100 °C.
After completion of the reaction as indicated by TLC
(∼12 hours), the mixture was cooled and diluted using EtOAc
(10 mL), washed with saturated brine (2 × 10 mL), and dried
using anhydrous Na2SO4. Evaporation of the solvent followed
by purification on silica gel provided the product 3.
Table 2 Synthesis of 6H-benzo[f]cyclopenta[d][1,2]thiazepine 5,5-di-
oxides 3 via a palladium-catalyzed reaction of 2-(2-alkynyl)benzenesulfon-
amide 1 with 2-alkynylvinyl bromide 2a
6-Methyl-7,10-diphenyl-8,9-dipropyl-6H-benzo[f]cyclopenta[d]-
[1,2]thiazepine 5,5-dioxide (3a)
Dark red solid; 1H NMR (400 MHz, CDCl3) δ 0.43 (t, J = 7.3 Hz,
3H), 0.73 (t, J = 6.9 Hz, 3H), 1.13–1.26 (m, 4H), 1.43–1.56 (m,
1H), 1.87–1.92 (m, 1H), 2.16–2.24 (m, 1H), 2.29–2.36 (m, 2H),
2.68 (s, 3H), 7.02 (d, J = 7.8 Hz, 2H), 7.09 (t, J = 7.8 Hz, 1H),
7.18–7.25 (m, 4H), 7.39–7.44 (m, 3H), 7.50–7.56 (m, 2H), 7.77
(d, J = 6.4 Hz, 1H), 7.90 (d, J = 7.8 Hz, 1H); 13C NMR (100 MHz,
CDCl3) δ 14.2, 14.5, 23.5, 25.5, 28.5, 29.0, 36.9, 125.3, 126.3,
127.0, 127.6, 128.3, 128.5, 128.8, 130.0, 130.6, 131.5, 133.2,
133.7, 134.0, 136.4, 136.0, 137.8, 142.6, 146.1, 146.5; HRMS
(ESI) calcd for C31H31NO2S: 504.1968 (M + Na+), found:
504.1970.
2-Methoxy-6-methyl-7,10-diphenyl-8,9-dipropyl-6H-benzo[f]-
cyclopenta[d][1,2]thiazepine 5,5-dioxide (3b)
Dark red solid; 1H NMR (400 MHz, CDCl3) δ 0.43 (t, J = 6.9 Hz,
3H), 0.73 (t, J = 7.3 Hz, 3H), 1.14–1.27 (m, 4H), 1.48–1.53 (m,
1H), 1.91–1.96 (m, 1H), 2.20–2.26 (m, 1H), 2.30–2.36 (m, 1H),
2.70 (s, 3H), 3.25 (s, 3H), 6.50 (s, 1H), 6.71 (d, J = 8.2 Hz, 2H),
7.26–7.54 (m, 9H), 7.80 (d, J = 8.7 Hz, 2H); 13C NMR (100 MHz,
CDCl3) δ 14.3, 14.5, 23.6, 25.6, 28.5, 29.0, 36.9, 55.1, 113.6,
116.7, 126.9, 127.6, 128.2, 128.3, 128.7, 128.8, 130.1, 130.6,
132.8, 133.7, 134.1, 135.8, 136.5, 138.4, 142.3, 146.0, 147.1,
161.6; HRMS (ESI) calcd for C32H33NO3S: 534.2073 (M + Na+),
found: 534.2077.
a Isolated yield based on 2-(2-alkynyl)benzenesulfonamide 1.
4412 | Dalton Trans., 2013, 42, 4410–4415
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2,6-Dimethyl-7,10-diphenyl-8,9-dipropyl-6H-benzo[f]-
cyclopenta[d][1,2]thiazepine 5,5-dioxide (3c)
10-Cyclopropyl-2,6-dimethyl-7-phenyl-8,9-dipropyl-6H-benzo[f]-
cyclopenta[d][1,2]thiazepine 5,5-dioxide (3g)
Dark red solid; 1H NMR (400 MHz, CDCl3) δ 0.42 (t, J = 7.3 Hz, Dark red solid; 1H NMR (400 MHz, CDCl3) δ −1.20 to −0.15
3H), 0.72 (t, J = 7.3 Hz, 3H), 1.11–1.27 (m, 4H), 1.47–1.52 (m, (m, 1H), 0.37 (t, J = 7.3 Hz, 3H), 0.40–0.45 (m, 1H), 0.60–0.66
1H), 1.87–1.93 (m, 1H), 1.97 (s, 3H), 2.18–2.26 (m, 1H), (m, 1H), 0.92–1.77 (m, 6H), 1.47–1.54 (m, 2H), 1.66–1.80 (m,
2.29–2.36 (m, 1H), 2.67 (s, 3H), 6.78 (s, 1H), 6.99 (d, J = 7.8 Hz, 3H), 2.32–2.40 (m, 1H), 2.45 (s, 3H), 2.50–2.58 (m, 1H), 2.60 (s,
2H), 7.23–7.52 (m, 9H), 7.77 (d, J = 7.8 Hz, 2H); 13C NMR 3H), 7.16 (d, J = 7.8 Hz, 2H), 7.33–7.36 (m, 2H), 7.47 (d, J = 6.9
(100 MHz, CDCl3) δ 14.2, 14.5, 21.3, 23.6, 25.5, 28.5, 29.0, 36.8, Hz, 2H), 7.65–7.69 (m, 2H), 7.8 (d, J = 7.8 Hz, 2H); 13C NMR
126.2, 126.4 126.9, 127.6, 128.2, 128.4, 128.8, 130.0, 130.5, (100 MHz, CDCl3) δ 7.8, 10.1, 10.5, 14.1, 14.8, 21.7, 24.0, 25.3,
133.2, 133.6, 133.7, 133.9, 134.4, 136.5, 138.0, 142.0, 142.5, 28.5, 28.8, 36.6, 126.1, 126.4, 127.3, 128.0, 128.8, 130.0, 130.1,
145.9, 146.5; HRMS (ESI) calcd for C32H33NO2S: 518.2124 132.4, 133.0, 133.3, 133.4, 134.1, 136.8, 141.7, 144.5, 144.7,
+
(M + Na+), found: 518.2142.
146.0; HRMS (ESI) calcd for C29H33NO2S: 482.2124 (M + Na ),
found: 482.2132.
2-Chloro-6-methyl-7,10-diphenyl-8,9-dipropyl-6H-benzo[f]-
cyclopenta[d][1,2]thiazepine 5,5-dioxide (3d)
10-Butyl-6-methyl-7-phenyl-8,9-dipropyl-6H-benzo[f]-
cyclopenta[d][1,2]thiazepine 5,5-dioxide (3h)
Dark red solid; 1H NMR (400 MHz, CDCl3) δ 0.43 (t, J = 7.3 Hz,
3H), 0.74 (t, J = 7.3 Hz, 3H), 1.10–1.29 (m, 4H), 1.48–1.54 (m,
1H), 1.89–1.94 (m, 1H), 2.18–2.27 (m, 1H), 2.28–2.36 (m, 1H),
2.69 (s, 3H), 6.94 (s, 1H), 7.14 (d, J = 8.2 Hz, 2H), 7.30 (d, J =
6.4 Hz, 2H), 7.40–7.41 (m, 3H), 7.52–7.54 (m, 2H), 7.74–7.76
(m, 1H), 7.81 (d, J = 8.7 Hz, 2H); 13C NMR (100 MHz, CDCl3) δ
14.2, 14.5, 23.5, 25.5, 28.4, 29.0, 36.9, 125.6, 126.1 127.4, 127.7,
128.4, 128.7, 128.9, 129.9, 130.7, 133.1, 133.3, 133.7, 134.6,
134.8, 135.6, 136.1, 137.2, 137.8, 142.7, 146.7, 147.3; HRMS
(ESI) calcd for C31H30ClNO2S: 538.1578 (M + Na+), found:
538.1569.
1
Dark red oil; H NMR (400 MHz, CDCl3) δ 0.39 (t, J = 6.9 Hz,
3H) 0.90 (t, J = 7.3 Hz, 3H), 0.98 (t, J = 7.3 Hz, 3H), 1.05–1.12
(m, 2H), 1.36–1.42 (m, 2H), 1.49–1.58 (m, 5H), 1.76–1.82 (m,
1H), 2.30 (t, J = 7.8 Hz, 2H), 2.44–2.49 (m, 2H), 2.61 (s, 3H),
7.34–7.36 (m, 3H), 7.47–7.60 (m, 4H), 7.71 (d, J = 6.0 Hz, 1H),
7.96 (d, J = 8.4 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 13.7,
14.0, 14.7, 22.8, 24.2, 25.2, 26.9, 28.3, 28.7, 32.3, 36.4, 125.5,
126.6, 126.7, 127.9, 128.6, 129.8, 130.1, 131.2, 132.0, 133.3,
133.4, 133.7, 134.3, 136.3, 136.5, 142.8, 144.0, 146.1; HRMS
(ESI) calcd for
500.2001.
C
29H35NO2S: 500.2020 (M + K+), found:
10-(4-Fluorophenyl)-6-methyl-7-phenyl-8,9-dipropyl-6H-benzo-
[f]cyclopenta[d][1,2]thiazepine 5,5-dioxide (3i)
10-(4-Chlorophenyl)-2,6-dimethyl-7-phenyl-8,9-dipropyl-6H-
benzo[f]cyclopenta[d][1,2]thiazepine 5,5-dioxide (3e)
Dark red solid; 1H NMR (400 MHz, CDCl3) δ 0.42 (t, J = 6.9 Hz,
3H), 0.73 (t, J = 6.8 Hz, 3H), 1.12–1.25 (m, 4H), 1.47–1.54 (m,
1H), 1.86–1.90 (m, 1H), 2.03 (s, 3H), 2.20–2.24 (m, 1H),
2.28–2.34 (m, 1H), 2.68 (s, 3H), 7.00 (d, J = 7.8 Hz, 2H), 7.12 (t,
J = 7.8 Hz, 2H), 7.22 (t, J = 7.3 Hz, 2H), 7.36–7.55 (m, 5H), 7.76
Dark red solid; 1H NMR (400 MHz, CDCl3) δ 0.42 (t, J = 6.9 Hz,
3H), 0.74 (t, J = 7.3 Hz, 3H), 1.09–1.25 (m, 4H), 1.42–1.53 (m,
1H), 1.85–1.92 (m, 1H), 2.03 (s, 3H), 2.17–2.24 (m, 1H),
2.26–2.34 (m, 1H), 2.67 (s, 3H), 6.78 (s, 1H), 7.02 (d, J = 7.8 Hz,
2H), 7.25–7.39 (m, 5H), 7.49–7.54 (m, 2H),7.74–7.79 (m, 2H);
13C NMR (100 MHz, CDCl3) δ 14.2, 14.5, 21.4, 23.6, 25.5, 28.5,
29.0, 36.9, 126.4, 126.5 128.0, 128.3, 128.6, 128.9, 130.0, 130.6,
132.7, 133.4, 133.7, 133.9, 134.0, 134.3, 136.3, 136.6, 141.9,
142.2, 144.3 147.1; HRMS (ESI) calcd for C32H32ClNO2S:
552.1734 (M + Na+), found: 552.1734.
(d, J = 5.5 Hz, 1H), 7.90 (d, J = 7.8 Hz, 1H); 13C NMR (100 MHz,
2
CDCl3) δ 14.2, 14.5, 23.5, 25.5, 28.6, 29.0, 36.9, 115.5 (d, JCF
=
21.0 Hz); 125.7, 126.4 127.8, 128.3, 128.9, 130.0, 130.7, 131.5,
131.7, 133.0, 133.5, 133.6, 133.8 (d, 3JCF = 8.6 Hz), 136.3, 136.7,
1
142.2, 144.8, 146.8, 162.0 (d, JCF = 245.0 Hz); HRMS (ESI)
calcd for C31H30FNO2S: 522.1873 (M + Na+), found: 522.1874.
10-(4-Methoxyphenyl)-2,6-dimethyl-7-phenyl-8,9-dipropyl-6H-
benzo[f]cyclopenta[d][1,2]thiazepine 5,5-dioxide (3f)
6-Methyl-7-phenyl-8,9-dipropyl-10-(p-tolyl)-6H-benzo[f]-
cyclopenta[d][1,2]thiazepine 5,5-dioxide (3j)
Dark red solid; 1H NMR (400 MHz, CDCl3) δ 0.42 (t, J = 7.4 Hz, Dark red solid; 1H NMR (400 MHz, CDCl3) δ 0.43 (t, J = 7.4 Hz,
3H), 0.74 (t, J = 7.3 Hz, 3H), 1.10–1.25 (m, 4H), 1.47–1.54 (m, 3H), 0.74 (t, J = 7.3 Hz, 3H), 1.12–1.27 (m, 4H), 1.49–1.56 (m,
1H), 1.86–1.92 (m, 1H), 2.01 (s, 3H), 2.18–2.25 (m, 1H), 1H), 1.87–1.95 (m, 1H), 2.18–2.24 (m, 1H), 2.30–2.35 (m, 4H),
2.29–2.38 (m, 1H), 2.66 (s, 3H), 6.83 (s, 1H), 6.99 (d, J = 7.8 Hz, 2.67 (s, 3H), 7.05–7.12 (m, 5H), 7.20 (t, J = 7.8 Hz, 2H),
2H), 7.35–7.42 (m, 2H), 7.47–7.53 (m, 2H), 7.75–7.78 (m, 2H); 7.37–7.44 (m, 2H), 7.76–7.54 (m, 2H), 7.77 (d, J = 6.0 Hz, 1H),
13C NMR (100 MHz, CDCl3) δ 14.3, 14.6, 21.5, 23.6, 25.5, 28.6, 7.90 (d, J = 7.8 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 14.3,
29.0, 36.8, 55.3, 113.9, 126.2, 126.4 127.3, 128.2, 128.8, 130.0, 14.6, 21.4, 23.6, 25.5, 28.5, 29.0, 36.9, 125.4, 126.3 127.4, 128.2,
130.1, 130.5, 133.3, 133.6, 133.7, 133.8, 133.9, 134.3, 136.6, 128.8, 129.2, 130.0, 130.5, 131.6, 133.4, 133.7, 134.2, 134.7,
136.6, 142.0, 142.7, 145.6 146.2, 158.7; HRMS (ESI) calcd for 136.4, 136.5, 136.6, 142.8, 146.1, 146.2; HRMS (ESI) calcd for
C33H35NO3S: 548.2230 (M + Na+), found: 548.2239.
C32H33NO2S: 518.2124 (M + Na+), found: 518.2117.
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8,9-Diethyl-6-methyl-7,10-diphenyl-6H-benzo[f]cyclopenta[d]-
[1,2]thiazepine 5,5-dioxide (3k)
7-(4-Methoxyphenyl)-2,6-dimethyl-10-phenyl-8,9-dipropyl-6H-
benzo[f]cyclopenta[d][1,2]thiazepine 5,5-dioxide (3o)
Dark red solid; 1H NMR (400 MHz, CDCl3) δ 0.70 (t, J = 7.4 Hz, Dark red solid; 1H NMR (400 MHz, CDCl3) δ 0.47 (t, J = 6.8 Hz,
3H), 0.80 (t, J = 6.9 Hz, 3H), 1.60–1.65 (m, 1H), 1.95–2.00 (m, 3H), 0.73 (t, J = 7.3 Hz, 3H), 1.12–1.25 (m, 4H), 1.56–1.63 (m,
1H), 2.26–2.38 (m, 2H), 2.68 (s, 3H), 7.02 (d, J = 7.8 Hz, 2H), 1H), 1.96–2.22 (m, 4H), 2.20–2.26 (m, 1H), 2.30–2.36 (m, 1H),
7.09 (t, J = 7.3 Hz, 1H), 7.18–7.25 (m, 4H), 7.38–7.44 (m, 3H), 2.68 (s, 3H), 6.77 (s, 1H), 6.89 (d, J = 8.2 Hz, 1H), 6.98 (d, J =
7.51 (d, J = 7.3 Hz, 2H), 7.79 (d, J = 7.8 Hz, 1H), 7.90 (d, J = 7.8 7.8 Hz, 1H), 7.05 (d, J = 8.2 Hz, 1H), 7.23–7.35 (m, 6H), 7.68 (d,
Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 14.8, 16.7, 19.3, 19.6, J = 8.2 Hz, 1H), 7.77 (d, J = 7.8 Hz, 1H); 13C NMR (100 MHz,
36.9, 125.6, 126.3, 127.0, 127.6, 128.2, 128.5, 128.8, 129.9, CDCl3) δ 14.3, 14.6, 21.3, 23.7, 25.4, 28.5, 29.0, 37.0, 55.6,
130.6, 131.6, 132.9, 133.6, 133.7, 134.0, 134.9, 136.5, 137.7, 113.4, 114.6, 126.1, 126.4, 126.8, 127.5, 128.3, 128.6, 130.2,
143.8, 146.1, 146.4; HRMS (ESI) calcd for
476.1655 (M + Na+), found: 476.1655.
C
29H27NO2S: 131.5, 132.5, 133.7, 133.8, 134.3, 135.6, 138.1, 141.9, 142.0,
145.4, 146.8; HRMS (ESI) calcd for C33H35NO3S: 548.2230
(M + Na+), found: 548.2230.
6-Benzyl-7,10-diphenyl-8,9-dipropyl-6H-benzo[f]cyclopenta[d]-
[1,2]thiazepine 5,5-dioxide (3l)
Crystal data for 3a
C31H31NO2S, Mr = 481.63, monoclinic, space group P21/n,
a = 10.517(4), b = 13.401(5), c = 18.699(7) Å, β = 90.737(5)°,
Dark red solid; 1H NMR (400 MHz, CDCl3) δ 0.43 (t, J = 7.3 Hz,
3H), 0.73 (t, J = 6.8 Hz, 3H), 1.13–1.28 (m, 4H), 1.42–1.49 (m,
1H), 1.84–1.91 (m, 1H), 2.18–2.24 (m, 1H), 2.29–2.38 (m, 1H),
4.31 (d, J = 16.0 Hz, 2H), 4.82 (d, J = 16.0 Hz, 2H), 6.45 (d, J =
7.8, 2), 6.80 (t, J = 6.8 Hz, 2H), 6.86–6.91 (m, 5H), 7.22–7.26 (m,
2H), 7.32–7.33 (m, 3H), 7.50–7.55 (m, 3H), 7.77 (d, J = 6.0 Hz,
1H); 13C NMR (100 MHz, CDCl3) δ 14.3, 14.6, 23.6, 25.6, 28.5,
29.1, 53.3, 125.5, 126.9 127.2, 127.8, 127.9, 128.2, 128.3, 128.4,
128.6, 130.0, 130.4, 131.1, 133.2, 133.5, 133.7, 133.8, 133.9,
135.3, 136.0, 137.9, 139.2, 142.3, 145.7, 146.1; HRMS (ESI)
calcd for C37H35NO2S: 580.2281 (M + Na+), found: 580.2281.
V = 2635.2(18) Å3, Z = 4, Dc = 1.903 g cm−1, μ = 0.151 mm−1
,
F000 = 1024, GOF = 0.920. A total of 10 715 reflections were
collected, 4631 of which were unique (Rint = 0.0638). R1/wR2 =
0.0482/0.1377 for 323 parameters and 4631 reflections (I >
2σ(I)).
Financial support from the National Natural Science Foun-
dation of China (No. 21032007, 21172038) is gratefully
acknowledged.
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7-(4-Chlorophenyl)-6-methyl-10-phenyl-8,9-dipropyl-6H-benzo-
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Dark red solid; 1H NMR (400 MHz, CDCl3) δ 0.47 (t, J = 6.9 Hz,
3H), 0.72 (t, J = 7.3 Hz, 3H), 1.11–1.28 (m, 4H), 1.51–1.59 (m,
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cyclopenta[d][1,2]thiazepine 5,5-dioxide (3n)
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3H), 0.73 (t, J = 7.3 Hz, 3H), 1.13–1.27 (m, 4H), 1.55–1.61 (m,
1H), 1.90–1.98 (m, 1H), 2.19–2.26 (m, 1H), 2.30–2.38 (m, 1H),
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