Palladium-catalyzed iodine-mediated electrophilic annulation of 2-(1-alkynyl)biphenyls with disulfides

Article abstract of DOI:10.1021/jo302634n

A palladium-catalyzed, iodine-mediated electrophilic annulation between 2-(1-alkynyl)biphenyl and disulfide has been developed. With the combination of PdCl₂ and I₂, a variety of 2-(1-alkynyl)biphenyls underwent electrophilic annulations with various disulfides successfully to afford the corresponding 9-sulfenyl phenanthrenes in moderate to excellent yields.

Full text of DOI:10.1021/jo302634n

Note
pubs.acs.org/joc
Palladium-Catalyzed Iodine-Mediated Electrophilic Annulation of
2‑(1-Alkynyl)biphenyls with Disulfides
Bo-Lun Hu,† Sha-Sha Pi,† Peng-Cheng Qian,*,† Jin-Heng Li,‡ and Xing-Guo Zhang*,†
†College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou 325035, China
‡State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University,
Changsha 410082, China
S
* Supporting Information
ABSTRACT: A palladium-catalyzed, iodine-mediated electro-
philic annulation between 2-(1-alkynyl)biphenyl and disulfide
has been developed. With the combination of PdCl2 and I2, a
variety of 2-(1-alkynyl)biphenyls underwent electrophilic
annulations with various disulfides successfully to afford the
corresponding 9-sulfenyl phenanthrenes in moderate to
excellent yields.
henanthrenes are an important class of polycyclic aromatic
palladium-catalyzed electrophilic annulation of 2-(1-alkynyl)-
Pcompounds and widely represented in many natural biphenyls with disulfides in the presence of iodine (eq 2).
products1 and biologically active molecules due to their diverse
We began our study by examining the reaction between 2-
biological activities such as anticancer,2 anti-HIV,3 and
(phenylethynyl)biphenyl 1a and 1,2-diphenyldisulfane 2a to
obtain the optimal reaction conditions. As shown in Table 1,
antimicrobial activity.4 Moreover, phenanthrenes also have a
several iodine sources, including iodine, ICl, NIS, and
PhI(OAc)2, were investigated first (entries 1−4). As expected,
all iodides could promote the electrophilic annulations but
provide the desired product 3 only in moderate yields (44−
54%, entries 1−4). Further investigation found that a 32% yield
was obtained using Larock’s I2/NaHCO3 system (entry 5).9b
After a series of trials, we found that palladium catalysts could
facilitate the reaction (entries 6−9). We observed that PdCl2
was more effective than Pd(OAc)2, Pd(PPh3)2Cl2, and
Pd(PPh3)4. The reaction yield increased sharply to 95% when
substrate 1a was treated with 1,2-diphenyldisulfane, 2 equiv of
I2, and 10 mol % of PdCl2 in THF at 80 °C (entry 6). It is
worth noting that PdCl2 could not catalyze the annulation
reaction in the absence of I2, which suggested that iodine played
a key role in this transformation (entry 10). Subsequently, the
effect of solvents was examined (entries 11−14). The results
showed that various solvents, including toluene, DMSO,
CH3NO2, and MeCN, were less effective than THF. Lower
yield was found when the loading of iodine was reduced to 1
equiv (entry 15) or when the loading of PdCl2 was reduced to 5
mol % (entry 16). The obvious decrease of reaction yield was
observed using 0.5 equiv of disulfide in this reaction, although
0.5 equiv of disulfides was enough for the electrophilic
annulations in our reported works10 (entry 17). The reaction
yield decreased to 19% when benzenethiol was used as
electrophile instead of 1,2-diphenyldisulfane (entry 18).
wide range of applications in materials science owing to their
optical and electronic properties.5 Consequently, extensive
efforts have been focused on the development of methods for
the construction of the phenanthrene ring.6 The carbocycliza-
tion of alkynylated biaryl derivatives is a frequently utilized
strategy because of the atom-economical advantage.7 For
example, Jana et al.8 developed an iron-catalyzed intramolecular
alkyne carbonyl metathesis of 2′-alkynylbiphenyl-2-carb-
aldehydes for the preparation of functionalized phenanthrenes.
Larock and co-workers also reported the electrophilic
cyclization of 2-(arylethynyl)biphenyls with ICl, NBS, or
arylsulfenyl chloride for the synthesis of phenanthrene
derivatives (Scheme 1, eq 1).9 In our former study, we
reported some transition-metal-catalyzed electrophilic cycliza-
tion of arylethynyl derivatives using disulfides as electrophilic
reagent.10 As a continual interest in the synthetic utility of
disulfides, we herein wish to report a simple and efficient
protocol for the synthesis of 9-sulfenylphenanthrenes by
Scheme 1
With the optimal reaction conditions in hand, we explored
the substrate scope of 2-(1-alkynyl)biphenyls and disulfides for
Received: December 6, 2012
Published: January 10, 2013
© 2013 American Chemical Society
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Note
a
15−19). Methyl-substituted substrates 1h, 1i, and 1k were
treated with disulfide 2a under standard conditions to afford
the corresponding products in 58−64% yields (entries 15, 16,
and 18). Substrates 1j and 1l bearing a chloro or fluoro group
on the biphenyl ring were also successfully converted to the
desired products in 31 and 81% yields, respectively (entries 17
and 19).
To elucidate the mechanism, a control reaction of 2-
(phenylethynyl)biphenyl 1a, I2, and PdCl2 was carried out
under the standard conditions in the absence of disulfide
(Scheme 2). However, the expected product 23 could not be
detected, and almost 90% of reactant 1a was recovered. The
results revealed that the electrophilic annulation of 2-(1-
alkynyl)biphenyls with disulfides did not proceed through an
iodocyclization process.
On the basis of the present results and other mechanisms
reported in the literature,8,9 a possible mechanism was
proposed as outlined in Scheme 3. Iodine could promote the
electrophilic annulations without PdCl2 (entry 1 in Table 1),
and iodocyclization product could not be detected (Scheme 2).
These results imply that the reaction of disulfide 2 with iodine
in situ may yield active RSI. In the absence of PdCl2 (Path 1),8
the electrophilic addition of RSI to the triple bond of substrate
1 affords intermediate A. The intramolecular electrophilic
attack on the neighboring benzene ring provides intermediate
B, and subsequent deprotonation yields the desired products
3−22. In the presence of PdCl2 (Path 2), RSI could undergo
ligand exchange with PdCl2 to afford RSPdX and subsequently
inserts into alkyne 1 to produce a vinylpalladium(II) complex
C. The electrophilic aromatic palladation through a C−H
activation step provides seven-membered palladacycle D.11 The
following reductive elimination produces the desired products
3−22 and Pd(0) species, which could be reoxidized to Pd(II)
by I2 or RSI. Study of the detailed mechanism is in progress.
In summary, we have developed a practical palladium-
catalyzed iodine-mediated electrophilic annulation method for
the synthesis of 9-sulfenylphenanthrenes using commercially
available disulfides as electrophiles. In the presence of PdCl2
and I2, a variety of 2-(1-alkynyl)biphenyls underwent the
electrophilic annulations successfully with various disulfides to
afford the corresponding 9-sulfenylphenanthrenes in moderate
to excellent yields. This methodology might provide a new
strategy for constructing polycyclic aromatic hydrocarbons and
also for the synthesis of sulfenyl phenanthrenes.
Table 1. Screening Conditions
entry
[I] (equiv)
I2 (2)
[Pd] (mol %)
solvent
yield (%)
1
2
3
4
THF
54
53
44
51
32
95
62
69
65
0
ICl (2)
NIS (2)
PhI(OAc)2 (2)
I2 (2)
THF
THF
THF
b
5
THF
6
7
I2 (2)
PdCl2 (10)
THF
I2 (2)
Pd(OAc)2 (10)
Pd(PPh3)2Cl2 (10)
Pd(PPh3)4 (10)
PdCl2 (10)
THF
8
I2 (2)
THF
9
I2 (2)
THF
10
11
12
13
14
15
16
THF
I2 (2)
I2 (2)
I2 (2)
I2 (2)
I2 (1)
I2 (2)
I2 (2)
I2 (2)
PdCl2 (10)
toluene
DMSO
CH3NO2
MeCN
THF
39
trace
42
54
28
68
50
19
PdCl2 (10)
PdCl2 (10)
PdCl2 (10)
PdCl2 (10)
PdCl2 (5)
THF
c
17
d
PdCl2 (10)
THF
18
PdCl2 (10)
THF
a
Reaction conditions: 1a (0.2 mmol), 2a (0.2 mmol), [I] source, and
Pd catalyst in solvent (2 mL) under N2 atmosphere at 80 °C for 24 h.
3 equiv of NaHCO3 was added. 0.1 mmol of 2a was used. 0.2 mmol
b
c
d
of PhSH was used instead of PhSSPh.
the electrophilic annulations (Table 2). First, the reaction
between 2-(phenylethynyl)biphenyl 1a and various disulfides
2b−2i was investigated under the standard conditions. The
results disclosed that a variety of aryl disulfides and aliphatic
alkyl disulfides are suitable substrates, and the electrophilic
annulations provide the corresponding products in moderate to
good yields (entries 1−8). In general, electron-rich phenyl
disulfide afforded a higher yield than electron-deficient phenyl
disulfide. For example, substrates 2b and 2f, bearing a p-tolyl or
4-nitrophenyl group, reacted with substrate 1a to give the
corresponding products in 92 and 61% yields, respectively
(entries 1 and 5). The transformation of substrate 1a with 1,2-
dimethyldisulfane 2g or 1,2-dibenzyldisulfane 2h also pro-
ceeded successfully to provide product in good yields (entries 6
and 7), but a lower yield was observed when 1,2-dicyclohexyl-
disulfane 2i was used as coupling partner (entry 8).
Subsequently, various 2-(1-alkynyl)biphenyls 1b−1g, which
bear different substituents at the terminal alkyne moiety, were
evaluated (entries 9−14). The results showed that different
functional groups, including p-tolyl, o-tolyl, p-ClC6H4, m-
CF3C6H4, thiophen-2-yl, and n-hexyl, were tolerated well under
standard conditions. For example, substrates 1b and 1c bearing
a p-tolyl or a bulky o-tolyl group afforded the corresponding
products in 93 and 90% yield, respectively (entries 9 and 10).
Moderate yields were observed when substrates 1d and 1e
bearing an electron-deficient phenyl group were used as
substrate (entries 11 and 12). Gratifyingly, substrate 1f bearing
a heteroaryl group furnished the desired product in a moderate
yield (60%, entry 13). Substrate 1g bearing an aliphatic alkyl
group also underwent the reaction smoothly to afford the target
product in quantitative yield (entry 14). Finally, the
substituents on the biphenyl moiety were examined (entries
EXPERIMENTAL SECTION
■
General Information. Chemicals were either purchased or
purified by standard techniques. 1H NMR and 13C NMR spectra
were measured on a 500 MHz spectrometer (1H at 500 MHz, 13C at
125 MHz), using CDCl3 as the solvent with tetramethylsilane (TMS)
as an internal standard at room temperature. Chemical shifts are given
in δ relative to TMS, and the coupling constants J are given in hertz.
19F NMR spectra were recorded on a 500 MHz spectrometer (19F at
470 MHz) and are reported relative to CFCl3 as the internal standard.
High-resolution mass spectra were recorded on an ESI-Q-TOF mass
spectrometer. All reactions under nitrogen atmosphere were
conducted using standard Schlenk techniques. Column chromatog-
raphy was performed using EM silica gel 60 (300−400 mesh).
General Procedure for the Synthesis of 9-Sulfenyl Phenan-
threnes. To a flame-dried Schlenk tube with a magnetic stirring bar
were charged 2-(1-alkynyl)biphenyls 1 (0.2 mmol), disulfide (0.2
mmol), PdCl2 (3.5 mg, 0.02 mmol), I2 (101.6 mg, 0.4 mmol), and
THF (anhydrous solvent, 2 mL) under N2 atmosphere. The reaction
mixture was stirred at 80 °C for 24 h. After the reaction equilibrium,
the mixture was poured into ethyl acetate, which was washed with
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Note
a
Table 2. Electrophilic Annulation of 2-(1-Alkynyl)biphenyls with Disulfides
a
Reaction conditions: 1 (0.2 mmol), 2 (0.2 mmol), I2 (2 equiv), and PdCl2 (10 mol %) in THF (2 mL) under N2 atmosphere at 80 °C for 24 h.
Scheme 2. Control Experiment
Scheme 3. Possible Mechanism
saturated NaS2O3 (2 × 10 mL) and then brine (1 × 10 mL). After the
aqueous layer was extracted with ethyl acetate, the combined organic
layers were dried over anhydrous Na2SO4 and evaporated under
vacuum. The residue was purified by flash column chromatography
(hexane/ethyl acetate) to afford the desired products 3−22.
Phenyl(10-phenylphenanthren-9-yl)sulfane (3): yellow solid (69.0
mg, 95% yield), mp 122−124 °C; IR (KBr, cm−1) 3054, 2917, 1594,
1
1565, 1547, 746; H NMR (300 MHz, CDCl3) δ 8.78 (d, J = 8.4 Hz,
2H), 8.61 (d, J = 8.4 Hz, 1H), 7.65−7.71 (m, 2H), 7.55−7.60 (m,
1H), 7.47−7.48 (m, 2H), 7.40−7.44 (m, 3H), 7.23−7.26 (m, 2H),
6.91−7.06 (m, 3H), 6.89−6.91 (m, 2H); 13C NMR (125 MHz,
CDCl3) δ 146.8, 140.2, 139.0, 132.2, 132.1, 131.1, 130.9, 129.5, 128.7,
128.6, 128.0, 127.9, 127.6, 127.6, 127.3, 127.2, 127.0, 126.7, 126.4,
124.6, 122.7, 122.6; LRMS (EI, 70 eV) m/z (%) 362 (M+, 100), 284
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Note
(34), 252 (39); HRMS (ESI) calcd for C26H19S+ ([M + H]+)
363.1202, found 363.1205.
Benzyl(10-phenylphenanthren-9-yl)sulfane (10): white solid (63.0
mg, 84% yield), mp 186−188 °C; IR (KBr, cm−1) 2921, 1362, 1220,
1
783, 727; H NMR (300 MHz, CDCl3) δ 8.88−8.91 (m, 1H), 8.73−
(10-Phenylphenanthren-9-yl)(p-tolyl)sulfane (4): yellow solid
(69.5 mg, 92% yield), mp 133−135 °C; IR (KBr, cm−1) 2963, 1566,
8.76 (m, 2H), 7.71−7.74 (m, 2H), 7.62−7.65 (m, 1H), 7.35−7.45 (m,
5H), 7.09−7.13 (m, 3H), 6.95−6.98 (m, 2H), 6.79−6.82 (m, 2H),
3.82 (s, 2H); 13C NMR (125 MHz, CDCl3) δ 146.2, 140.3, 137.7,
132.2, 132.1, 130.7, 130.6, 130.1, 129.2, 128.9, 128.5, 128.2, 127.8,
127.7, 127.4, 127.2, 127.0, 126.8, 126.8, 126.6, 123.0, 122.4, 40.8;
LRMS (EI, 70 eV) m/z (%) 376 (M+, 100), 284 (30), 252 (36);
HRMS (ESI) calcd for C27H21S+ ([M + H]+) 377.1358, found
377.1357.
Cyclohexyl(10-phenylphenanthren-9-yl)sulfane (11): white solid
(33.0 mg, 45% yield), mp 131−133 °C; IR (KBr, cm−1) 2917, 2850,
1713, 1364, 1223 784; 1H NMR (300 MHz, CDCl3) δ 8.87−8.90 (m,
1H), 8.67−8.73 (m, 2H), 7.67−7.70 (m, 2H), 7.60−7.64 (m, 1H),
7.46−7.49 (m, 3H), 7.41−7.42 (m, 2H), 7.28−7.31 (m, 2H), 2.78−
2.85 (m, 1H), 1.83−1.88 (m, 4H), 1.60−1.69 (m, 6H); 13C NMR
(125 MHz, CDCl3) δ 145.5, 140.6, 133.2, 132.2, 130.7, 130.6, 130.5,
129.9, 128.4, 128.3, 127.8, 127.1, 126.9, 126.7, 126.6 (2C), 122.8,
122.4, 48.6, 33.5, 26.0, 25.7; LRMS (EI, 70 eV) m/z (%) 368 (M+,
100), 286 (100), 252 (26); HRMS (ESI) calcd for C26H25S+ ([M +
H]+) 369.1671, found 369.1674.
Phenyl(10-p-tolylphenanthren-9-yl)sulfane (12): yellow solid
(70.1 mg, 93% yield), mp 109−111 °C; IR (KBr, cm−1) 2913, 1570,
1541, 1412, 1279, 935; 1H NMR (300 MHz, CDCl3) δ 8.73−8.76 (m,
2H), 8.59 (d, J = 8.0 Hz, 1H), 7.62−7.69 (m, 2H), 7.43−7.54 (m,
3H), 7.20−7.23 (m, 2H), 7.13−7.15 (m, 2H), 7.03−7.06 (m, 2H),
6.90−6.99 (m, 3H), 2.42 (s, 3H); 13C NMR (125 MHz, CDCl3) δ
146.9, 139.1, 137.2, 136.9, 132.4, 132.1, 131.1, 130.9, 129.4, 128.8,
128.7, 128.6, 128.1, 127.6, 127.5, 127.1, 127.0, 126.7, 126.3, 124.6,
122.7, 122.5, 21.4; LRMS (EI, 70 eV) m/z (%) 376 (M+, 100), 284
(34), 252 (26); HRMS (ESI) calcd for C27H21S+ ([M + H]+)
377.1359, found 377.1357.
1
1528, 741; H NMR (300 MHz, CDCl3) δ 8.72−8.76 (m, 2H), 8.61
(d, J = 8.0 Hz, 1H), 7.62−7.69 (m, 2H), 7.52−7.58 (m, 1H), 7.45−
7.47 (m, 2H), 7.40−7.42 (m, 3H), 7.24−7.27 (m, 2H), 6.79−6.88 (m,
4H), 2.18 (s, 3H); 13C NMR (125 MHz, CDCl3) δ 146.6, 140.2,
135.3, 134.4, 132.8, 132.2, 132.0, 131.0, 130.9, 129.8, 129.5, 129.4,
128.7, 128.1, 128.0, 127.5, 127.3, 127.0, 126.7, 126.4, 122.7, 122.5,
20.8; LRMS (EI, 70 eV) m/z (%) 376 (M+, 100), 343 (14), 284 (31),
252 (23); HRMS (ESI) calcd for C27H21S+ ([M + H]+) 377.1358,
found 377.1358.
(4-Chlorophenyl)(10-phenylphenanthren-9-yl)sulfane (5): yellow
solid (59.1 mg, 75% yield), mp 135−136 °C; IR (KBr, cm−1) 2923,
1669, 1566, 1544, 1277, 938, 826; 1H NMR (300 MHz, CDCl3) δ 8.76
(d, J = 8.2 Hz, 2H), 8.56 (d, J = 8.2 Hz, 1H), 7.67−7.70 (m, 2H),
7.55−7.60 (m, 1H), 7.46−7.48 (m, 2H), 7.41−7.43 (m, 3H), 7.21−
7.23 (m, 2H), 7.00−7.03 (m, 2H), 6.79−6.81 (m, 2H); 13C NMR
(125 MHz, CDCl3) δ 147.0, 140.0, 137.5, 132.2, 131.8, 131.2, 131.0,
130.5, 129.4, 128.8(2C), 128.0, 127.8 (2C), 127.7, 127.6, 127.5, 127.2,
126.8, 126.7, 122.9, 122.6; LRMS (EI, 70 eV) m/z (%) 396 (M+, 100),
328 (23), 284 (48), 252 (60); HRMS (ESI) calcd for C26H18ClS+ ([M
+ H]+) 397.0812, found 397.0808.
(4-Fluorophenyl)(10-phenylphenanthren-9-yl)sulfane (6): yellow
solid (58.6 mg, 77% yield), mp 43−44 °C; IR (KBr, cm−1) 1717, 1684,
1541, 1507, 1097; 1H NMR (300 MHz, CDCl3) δ 8.76 (d, J = 8.4 Hz,
2H), 8.62 (d, J = 8.4 Hz, 1H), 7.65−7.71 (m, 2H), 7.56−7.62 (m,
1H), 7.46−7.47 (m, 2H), 7.41−7.43 (m, 3H), 7.20−7.23 (m, 2H),
6.83−6.88 (m, 2H), 6.73−6.79 (m, 2H); 13C NMR (125 MHz,
CDCl3) δ 160.8 (d, JC−F = 243.0 Hz), 146.7, 140.1, 133.9 (2C), 132.2,
132.0, 131.1, 131.0, 129.6, 128.7, 128.4, 128.3, 128.0, 127.9, 127.7,
127.6, 127.4, 127.1, 126.8, 122.7 (d, JC−F = 31.9 Hz), 115.7 (d, JC−F
=
Phenyl(10-o-tolylphenanthren-9-yl)sulfane (13): yellow solid
22.9 Hz); 19F NMR (470 MHz) δ −117.90; LRMS (EI, 70 eV) m/z
(%) 380 (M+, 88), 328 (54), 284 (64), 252 (100); HRMS (ESI) calcd
for C26H18FS+ ([M + H]+) 381.1108, found 381.1112.
(68.0 mg, 90% yield), mp 51−53 °C; IR (KBr, cm−1) 2913, 1610,
1
1567, 1541, 1445, 1137; H NMR (300 MHz, CDCl3) δ 8.79 (d, J =
8.2 Hz, 2H), 8.59 (d, J = 8.2 Hz, 1H), 7.66−7.72 (m, 2H), 7.55−7.60
(m, 1H), 7.44−7.49 (m, 1H), 7.32−7.37 (m, 3H), 7.17−7.23 (m, 1H),
6.91−7.07 (m, 4H), 6.88−6.91 (m, 2H), 1.92 (s, 3H); 13C NMR (125
MHz, CDCl3) δ 146.1, 139.6, 138.5, 136.6, 132.1, 131.7, 131.1, 130.9,
129.7, 129.3, 128.6 (2C), 128.1, 128.0, 127.7 (2C), 127.5, 127.2, 127.0,
126.6, 125.5, 124.7, 122.8, 122.7, 19.9; LRMS (EI, 70 eV) m/z (%)
376 (M+, 100), 284 (29), 252 (22); HRMS (ESI) calcd for C27H21S+
([M + H]+) 377.1359, found 377.1359.
(3-Fluorophenyl)(10-phenylphenanthren-9-yl)sulfane (7): yellow
solid (54.4 mg, 72% yield), mp 88−90 °C; IR (KBr, cm−1) 1688, 1524,
1493, 1005; 1H NMR (300 MHz, CDCl3) δ 8.78 (d, J = 8.2 Hz, 2H),
8.57 (d, J = 8.1 Hz, 1H), 7.67−7.72 (m, 2H), 7.56−7.61 (m, 1H),
7.47−7.49 (m, 2H), 7.41−7.43 (m, 3H), 7.23−7.25 (m, 2H), 6.98−
7.05 (m, 1H), 6.67−6.70 (m, 2H), 6.55−6.58 (m, 1H); 13C NMR
(125 MHz, CDCl3) δ 162.9 (d, JC−F = 245.0 Hz), 147.2, 141.4 (d, JC−F
= 7.8 Hz), 140.0, 132.2, 131.9, 131.3, 131.0, 129.9 (d, JC−F = 8.5 Hz),
129.4, 128.8, 128.0, 127.9, 127.8, 127.7, 127.5, 127.2, 126.8, 126.4,
122.9, 122.6, 122.0 (d, JC−F = 2.5 Hz), 113.2 (d, JC−F = 23.8 Hz), 111.7
(d, JC−F = 21.3 Hz); LRMS (EI, 70 eV) m/z (%) 380 (M+, 100), 328
(24), 284 (43), 252 (62); HRMS (ESI) calcd for C26H18FS+ ([M +
H]+) 381.1108, found 381.1103.
(10-(4-Chlorophenyl)phenanthren-9-yl)(phenyl)sulfane (14): yel-
low solid (48.1 mg, 56% yield), mp 131−133 °C; IR (KBr, cm−1)
1
3005, 1698, 1653, 1528; H NMR (300 MHz, CDCl3) δ 8.76−8.79
(m, 2H), 8.62 (d, J = 8.3 Hz, 1H), 7.67−7.71 (m, 2H), 7.57−7.60 (m,
1H), 7.44−7.50 (m, 2H), 7.37−7.38 (m, 2H), 7.15−7.16 (m, 2H),
7.05−7.08 (m, 2H), 6.98−7.01 (m, 1H), 6.86−6.88 (m, 2H); 13C
NMR (125 MHz, CDCl3) δ 145.5, 138.7, 138.5, 133.4, 132.0 (2C),
131.1, 130.9, 129.5, 128.7, 128.4, 128.2, 128.0, 127.8, 127.7, 127.5,
127.3, 126.9, 126.3, 124.8, 122.8, 122.7; LRMS (EI, 70 eV) m/z (%)
396 (M+, 100), 284 (31), 252 (22); HRMS (ESI) calcd for
C26H18ClS+ ([M + H]+) 397.0812, found 397.0811.
(4-Nitrophenyl)(10-phenylphenanthren-9-yl)sulfane (8):9b white
solid (50.0 mg, 61% yield), mp 185−187 °C; IR (KBr, cm−1) 2916,
1704, 1496, 1359, 1036, 744; 1H NMR (300 MHz, CDCl3) δ 8.80 (d, J
= 8.2 Hz, 2H), 8.44 (d, J = 8.2 Hz, 1H), 7.91 (d, J = 8.7 Hz, 2H),
7.69−7.75 (m, 2H), 7.57−7.62 (m, 1H), 7.47−7.51 (m, 2H), 7.41−
7.43 (m, 3H), 7.19−7.23 (m, 2H), 6.95 (d, J = 8.8 Hz, 2H); 13C NMR
(125 MHz, CDCl3) δ 148.9, 147.7, 144.7, 139.6, 132.0, 131.3, 131.2,
131.0, 129.1, 128.9, 128.3, 128.1, 128.0, 127.8, 127.5, 127.1, 127.0,
125.5, 124.6, 123.8, 123.1, 122.7; LRMS (EI, 70 eV) m/z (%) 407
(M+, 23), 322 (35), 252 (100), 207 (44).
Phenyl(10-(3-(trifluoromethyl)phenyl)phenanthren-9-yl)sulfane
(15): yellow solid (36.4 mg, 42% yield), mp 116−118 °C; IR (KBr,
1
cm−1) 2884, 1664, 1528, 1184; H NMR (300 MHz, CDCl3) δ 8.81
(d, J = 8.4 Hz, 2H), 8.71 (d, J = 8.4 Hz, 1H), 7.71−7.76 (m, 4H),
7.39−7.64 (m, 6H), 7.04−7.07 (m, 2H), 6.84−6.86 (m, 2H); 13C
NMR (125 MHz, CDCl3) δ 145.0, 140.7, 138.5, 133.0, 132.2, 131.8,
131.1, 130.9, 130.3 (q, JC−F = 32 Hz), 129.5, 128.8, 128.4, 128.1, 128.0,
Methyl(10-phenylphenanthren-9-yl)sulfane (9): white solid (49.4
mg, 82% yield), mp 137−139 °C; IR (KBr, cm−1) 1364, 1223, 772,
1
733; H NMR (300 MHz, CDCl3) δ 8.85−8.88 (m, 1H), 8.70−8.77
127.9, 127.8, 127.5, 126.6, 126.5 125.1, 124.2 (2C), 124.1 (q, JC−F
=
270.6 Hz), 122.8 (2C); 19F NMR (470 MHz) δ −62.49; LRMS (EI,
70 eV) m/z (%) 430 (M+, 16), 322 (100), 252 (84), 207 (56); HRMS
(ESI) calcd for C27H18F3S+ ([M + H]+) 431.1076, found 431.1069.
2-(10-(Phenylthio)phenanthren-9-yl)thiophene (16): yellow solid
(43.6 mg, 60% yield), mp 150−152 °C; IR (KBr, cm−1) 2913, 1573,
(m, 2H), 7.69−7.73 (m, 2H), 7.59−7.64 (m, 1H), 7.50−7.53 (m, 3H),
7.41−7.43 (m, 2H), 7.31−7.33 (m, 2H), 2.17 (s, 3H); 13C NMR (125
MHz, CDCl3) δ 145.2, 140.8, 132.1, 132.0, 131.6, 130.8, 130.5, 129.9,
128.4, 128.0, 127.7, 127.4, 127.2, 127.1, 126.8, 126.6, 123.0, 122.4,
20.0; LRMS (EI, 70 eV) m/z (%) 300 (M+, 100), 285 (86), 284 (67),
252 (39); HRMS (ESI) calcd for C21H17S+ ([M + H]+) 301.1045,
found 301.1051.
1
1337, 1097, 882; H NMR (300 MHz, CDCl3) δ 8.76 (d, J = 7.4 Hz,
2H), 8.60 (d, J = 7.4 Hz, 1H), 7.66−7.74 (m, 3H), 7.52−7.59 (m,
1303
dx.doi.org/10.1021/jo302634n | J. Org. Chem. 2013, 78, 1300−1305

The Journal of Organic Chemistry
Note
2H), 7.45 (d, J = 8.5 Hz, 1H), 7.07−7.15 (m, 3H), 7.02 (d, J = 6.9 Hz,
1H), 6.94−6.98 (m, 3H); 13C NMR (125 MHz, CDCl3) δ 140.4,
139.4, 138.9, 132.8, 131.8, 131.3, 130.9, 130.4, 128.7, 128.4, 128.3,
128.1, 127.8, 127.6, 127.5, 127.0, 126.7, 126.4, 125.8, 124.8, 122.8,
122.5; LRMS (EI, 70 eV) m/z (%)368 (M+, 100), 252 (54), 207 (64);
= 2.3 Hz), 139.9, 138.7, 132.6, 132.5, 130.7, 130.6, 130.5, 129.5, 128.8,
128.7, 128.0, 127.7, 127.5, 127.4, 126.8, 126.4, 124.8, 122.8, 116.4 (d,
JC−F = 23.0 Hz), 107.9 (d, JC−F = 22.4 Hz); 19F NMR (470 MHz) δ
−117.60; LRMS (EI, 70 eV) m/z (%) 380 (M+, 100), 302 (35), 270
(38); HRMS (ESI) calcd for C26H18FS+ ([M + H]+) 381.1108, found
381.1110.
+
HRMS (ESI) calcd for C24H17S2 ([M + H]+) 369.0766, found
369.0765.
(10-Hexylphenanthren-9-yl)(phenyl)sulfane (17): yellow oil (72.9
mg, 99% yield); IR (KBr, cm−1) 2919, 1598, 1557, 1541, 1421, 811;
1H NMR (300 MHz, CDCl3) δ 7.51−7.52 (m, 1H), 7.49−7.50 (m,
1H), 7.37−7.41 (m, 3H), 7.29−7.34 (m, 3H), 7.17−7.21 (m, 3H),
6.94−6.97 (m, 2H), 2.23−2.43 (m, 2H), 1.32−1.37 (m, 2H), 1.11−
1.25 (m, 6H), 0.83 (t, J = 6.6 Hz, 3H); 13C NMR (125 MHz, CDCl3)
δ 142.3, 140.9, 140.5, 140.1, 134.5, 131.1, 130.4, 130.2, 129.4, 129.3,
129.2, 128.7, 128.4, 128.0, 127.9, 127.3, 127.1, 127.0, 39.8, 31.4, 28.5,
27.2, 22.4, 14.1; LRMS (EI, 70 eV) m/z (%) 370 (M+, 88), 322 (100),
252 (34); HRMS (ESI) calcd for C26H27S+ ([M + H]+) 371.1828,
found 371.1824.
ASSOCIATED CONTENT
* Supporting Information
X-ray data of compound 3 and characterization data for all new
and known compounds. This material is available free of charge
via the Internet at http://pubs.acs.org.
■
S
AUTHOR INFORMATION
Corresponding Author
*E-mail: zxg@wzu.edu.cn, pcq@wzu.edu.cn.
■
(2-Methyl-10-phenylphenanthren-9-yl)(phenyl)sulfane (18): yel-
low solid (48.3 mg, 64% yield), mp 123−125 °C; IR (KBr, cm−1)
2920, 1605, 1529, 1514, 1339, 803, 739; 1H NMR (500 MHz, CDCl3)
δ 8.72 (d, J = 8.2 Hz, 1H), 8.66 (d, J = 8.2 Hz, 1H), 8.58 (d, J = 8.2
Hz, 1H), 7.62−7.67 (m, 1H), 7.50−7.55 (m, 2H), 7.40−7.42 (m, 3H),
7.21−7.24 (m, 3H), 6.97−7.07 (m, 3H), 6.87−6.90 (m, 2H), 2.39 (s,
3H); 13C NMR (125 MHz, CDCl3) δ 146.6, 140.3, 139.1, 136.6,
132.3, 131.7, 130.9, 129.9, 129.5, 129.4, 129.0, 128.6, 128.2, 128.0,
127.9, 127.3, 127.1, 127.0 (2C), 126.3, 124.6, 122.5, 21.6; LRMS (EI,
70 eV) m/z (%) 376 (M+, 100), 284 (32), 252 (25); HRMS (ESI)
calcd for C27H21S+ ([M + H]+) 377.1358, found 377.1358.
(3-Methyl-10-phenylphenanthren-9-yl)(phenyl)sulfane (19): yel-
low solid (45.4 mg, 60% yield), mp 127−129 °C; IR (KBr, cm−1)
3077, 2923, 1609, 1557, 1502, 1425, 1317, 1121; 1H NMR (500 MHz,
CDCl3) δ 8.87 (d, J = 8.5 Hz, 1H), 8.69 (d, J = 7.8 Hz, 1H), 7.62−7.65
(m, 1H), 7.55−7.58 (m, 2H), 7.39−7.41 (m, 3H), 7.36−7.37 (m, 2H),
7.21−7.23 (m, 2H), 7.05−7.08 (m, 2H), 6.97−7.08 (m, 1H), 6.90 (d, J
= 7.5 Hz, 2H), 3.18 (s, 3H); 13C NMR (125 MHz, CDCl3) δ 147.2,
140.9, 138.9, 135.0, 133.7, 133.0, 132.2, 132.1, 131.4, 129.5, 129.1,
128.6, 127.9, 127.7, 127.3, 127.2, 127.1, 126.9, 126.4, 125.8, 125.7,
124.6, 29.7; LRMS (EI, 70 eV) m/z (%) 376 (M+, 100), 284 (30), 252
(23); HRMS (ESI) calcd for C27H21S+ ([M + H]+) 377.1358, found
377.1362.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We thank the National Natural Science Foundation of China
(Nos. 21002070 and 21102104) and Zhejiang Provincial
Natural Science Foundation of China (No. Y4100307) for
financial support.
REFERENCES
■
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1
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2946, 1623, 1522, 1218; H NMR (300 MHz, CDCl3) δ 8.66−8.70
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(m, 1H), 7.56−7.61 (m, 1H), 7.29−7.37 (m, 3H), 7.18−7.21 (m, 2H),
7.00−7.10 (m, 3H), 6.84−6.87 (m, 2H); 13C NMR (125 MHz,
CDCl3) δ 144.1, 142.2, 138.8, 134.5, 132.5, 132.1, 131.7, 131.0, 130.4,,
130.3, 129.9, 128.9, 128.7, 128.6, 128.4, 127.8, 127.3, 127.2, 126.5,
124.9, 123.0, 122.3; LRMS (EI, 70 eV) m/z (%) 430 (M+, 3), 376
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(7-Methyl-10-phenylphenanthren-9-yl)(phenyl)sulfane (21): yel-
low solid (43.3 mg, 58% yield), mp 125−127 °C; IR (KBr, cm−1)
2963, 1694, 1503, 1278, 941; 1H NMR (500 MHz, CDCl3) δ 8.75 (d, J
= 8.0 Hz, 1H), 8.54 (s, 1H), 8.48 (d, J = 8.0 Hz, 1H), 7.63−7.69 (m,
1H), 7.43−7.45 (m, 2H), 7.37−7.40 (m, 4H), 7.22−7.24 (m, 2H),
7.02−7.06 (m, 2H), 6.95−6.98 (m, 1H), 6.88−6.90 (m, 2H), 2.59 (s,
3H); 13C NMR (125 MHz, CDCl3) δ 145.8, 140.3, 139.1, 136.8,
132.6, 132.4, 130.9, 130.8, 130.0, 129.6, 129.3, 128.7, 128.6, 127.9
(2C), 127.4, 127.3, 126.6, 126.3, 124.6, 122.6, 122.5, 21.9; LRMS (EI,
70 eV) m/z (%) 376 (M+, 100), 284 (33), 252 (25); HRMS (ESI)
calcd for C27H21S+ ([M + H]+) 377.1358, found 377.1359.
́
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̈
low solid (59.1 mg, 81% yield), mp 113−115 °C; IR (KBr, cm−1)
̈
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2967, 1528, 1441, 1366, 1275; H NMR (500 MHz, CDCl3) δ 8.58−
8.62 (m, 2H), 8.35 (d, J = 8.5 Hz, 1H), 7.67−7.70 (m, 1H), 7.46−7.51
(m, 2H), 7.41−7.42 (m, 3H), 7.27−7.31 (m, 1H), 7.23−7.24 (m, 2H),
7.05−7.08 (m, 2H), 6.98−7.01 (m, 1H), 6.87−6.89 (m, 2H); 13C
NMR (125 MHz, CDCl3) δ 161.8 (d, JC−F = 245.5 Hz), 146.0 (d, JC−F
(8) Bera, K.; Sarkar, S.; Jalal, S.; Jana, U. J. Org. Chem. 2012, 77, 8780.
1304
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Note
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1305
dx.doi.org/10.1021/jo302634n | J. Org. Chem. 2013, 78, 1300−1305