Palladium-catalyzed C-H acylation of arenes using thioethers as directing groups

Article abstract of DOI:10.1002/ejoc.201400096

A highly efficient protocol for regioselective synthesis of diaryl ketones by palladium-catalyzed direct acylation of arenes using thioethers as directing groups is reported. The possible pathway of direct acylation between thioethers and α-oxocarboxylic acids is discussed. The direct acylation of thioethers via Pd-catalyzed C-H bond activation was described. Copyright

Full text of DOI:10.1002/ejoc.201400096

FULL PAPER
DOI: 10.1002/ejoc.201400096
Palladium-Catalyzed C–H Acylation of Arenes Using Thioethers as Directing
Groups
Bo Xu,[a] Wei Liu,[a] and Chunxiang Kuang*[a,b]
Keywords: Synthetic methods / Homogeneous catalysis / Palladium / Acylation / C–H bond activation / Arenes /
Regioselectivity
A highly efficient protocol for regioselective synthesis of di-
aryl ketones by palladium-catalyzed direct acylation of ar-
enes using thioethers as directing groups is reported. The
possible pathway of direct acylation between thioethers and
α-oxocarboxylic acids is discussed.
Introduction
Diaryl ketones are fundamental building blocks of natu-
ral products, pharmaceuticals, and organic functional mate-
rials (Figure 1).[1] For example, NQDI-1[2] shows strong
specific inhibitory activity toward apoptosis signal-regulat-
ing kinase 1 (ASK1); daunorubicin,[3] another example of
a diaryl ketone, was initially isolated from streptomyces peu-
cetius. Daunorubicin is most commonly used to treat spe-
cific types of leukaemias. These ketones are usually synthe-
sized by Friedel–Crafts acylation[4] and oxidation by
alcohols[5] or by transforming carboxylic acid derivatives to
their corresponding ketones.[6] In most cases, these reac-
tions are only poorly compatible with assorted functional
groups.[4] Some reactions yield products mostly as isomeric
mixtures or products that need further functionalization.[4]
To overcome these limitations, various methods have been
developed.[4,7–10] Among these, the metal-catalyzed ligand-
directed ortho-acylation of sp2 C–H bonds represents an
ideal approach to access ketones because it avoids preacti-
vation of starting materials and thus has attracted great at-
tention.
Figure 1. Bioactive diaryl ketone molecules.
scribed a palladium-catalyzed acylation of 2-phenylpyridine
using benzylic and aliphatic alcohols as acylation rea-
gents.[13a] In 2010, Yu and co-workers reported a palladium-
catalyzed acylation reaction using oximes as directing
groups.[21] In 2011, Wang described an ortho-acylation reac-
tion using acetanilides with aldehydes as the reaction
agents.[12c] In 2011, Kim and co-workers reported a rho-
dium-catalyzed oxidative acylation of benzamides with al-
dehydes.[12g] In 2012, Wang and co-workers developed an
acylation reaction of 2-arylpyridines with α-diketones by
palladium-catalyzed C–H bond activation and C–C bond
cleavage.[14] In 2013, Ge and co-workers reported a palla-
dium-catalyzed decarboxylative cross-coupling of benzoic
acids with α-oxocarboxylic acids.[15c] In 2013, Wu and co-
workers described an efficient protocol for palladium-cata-
lyzed ortho-acylation of 2-aryl pyridines using benzylamine
as acyl surrogate.[19] In 2013, Lu and co-workers reported
palladium-catalyzed cascade oxidation/sp2 C–H bond acyl-
ation of azoarenes with aryl methanes.[20a] The above-men-
tioned metal-catalyzed acylation reactions exhibited good
functional group tolerance and moderate to good yields.
However, all these reactions use only N- or O-donor atoms,
such as in pyridyl,[12a,12b,19] oxime,[21,15e,15f] and carboxyl[15c]
systems, as the directing group (Scheme 1). The generality
of substrate scope for such systems is still limited.
Various diaryl ketones have been synthesized using car-
bon monoxide,[11] aldehydes,[12] alcohols,[13] α-diketones,[14]
α-oxocarboxylic acids,[15] acyl chlorides,[16] carboxylic
acids,[17] carboxylic anhydrides,[18] benzylamine,[19] and tol-
uene[20] as acylation partners. For example, in 2009, Cheng
reported a palladium-catalyzed acylation of 2-phenylpyr-
idine with benzaldehyde.[12a] In 2011, Li and co-workers de-
[a] Department of Chemistry, Tongji University,
Siping Road 1239, Shanghai 200092, China
E-mail: kuangcx@tongji.edu.cn.
http://chemweb.tongji.edu.cn/Teachers/Details/
a1a31ffb-88aa-4733-8fa5-8db01611b440
[b] Key Laboratory of Yangtze River Water Environment, Ministry
of Education,
Siping Road 1239, Shanghai 200092, China
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.201400096.
In 2012, Zhang and co-workers reported on thioether-
directed ortho-C–H arylation[22] and alkenylation[23] reac-
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Thioethers as Directing Groups in Pd-Catalyzed Arene Acylations
Scheme 1. Strategies for the synthesis of diaryl ketones.
tions. Inspired by this study, we report here the first exam- Table 1. Optimization of reaction conditions.[a]
ples of palladium (Pd)-catalyzed acylation reactions using
S-donor thioethers as the directing groups.
Results and Discussion
Initially, we focused on the acylation of (benzyl)(p-tolyl)-
sulfane with benzaldehyde; the reaction was conducted with
5 mol-% Pd(OAc)2 as catalyst and tert-butyl hydroperoxide
(TBHP, 3 equiv., 70% solution in water).[24] However, no
desired product was detected. When we used α-oxocarb-
oxylic acids as acylation partners, the reaction smoothly af-
forded desired diaryl ketone in the presence of Pd(OAc)2
Entry
Catalyst
5 mol-%
Oxidant
2.0 equiv.
Solvent
Yield
[%][b]
(10 mol-%) and Ag2CO3 (2 equiv.) at 120 °C in DMF.[15]
The desired product was isolated in 61% yield (Table 1, En-
try 1). Other oxidants, including Ag2O, K2S2O8 and 1,4-
benzoquinone, showed relatively lower efficiency (Table 1,
Entries 2, 4, and 5) whereas AgOAc was completely inactive
(Table 1, Entry 3). Among the oxidants examined, Ag2CO3
provided the highest yield (Table 1, Entry 6). The effects of
several solvents were investigated. The reaction was most
productive with N,N-dimethylacetamide (DMA) as solvent
(Table 1, Entry 6). Other solvents, such as xylene, led to
relatively lower yields (Table 1, Entry 9). A comparable re-
action efficiency was presented by toluene (Table 1, Entry
8). The reaction did not occur in 1,4-dioxane (Table 1, En-
try 7). Lowering the temperature to 100 °C decreased the
yield to 36% (Table 1, Entry 10).
1
2
3
4
5
6
7
8
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Ag2CO3
Ag2O
AgOAc
K2S2O8
BQ
Ag2CO3
Ag2CO3
Ag2CO3
Ag2CO3
Ag2CO3
DMF
DMF
DMF
DMF
DMF
DMA
61
25
trace
46
36
73
1,4-dioxane trace
toluene
xylene
DMA
50
42
36
9
10[c]
[a] Reaction conditions: (benzyl)(p-tolyl)sulfane (0.2 mmol), α-ox-
ocarboxylic acid (0.6 mmol), Pd catalyst (0.01 mmol), oxidant
(0.4 mmol), solvent (2 mL), 120 °C, 24 h. [b] Isolated yields. [c] The
reaction was conducted at 100 °C.
Upon establishing the optimized reaction conditions, the drawing groups in 3ka and 3la that presumably prevents
scope of thioethers was determined (Table 2). Generally, electrophilic attack of the PdII center onto the phenyl ring.
thioethers containing electron-donating and electron-with- Substitutions at the ortho-position of the benzyl group in
drawing groups were both tolerated under the reaction con- the thioether appeared to have no effect on the reaction
ditions and provided corresponding diaryl ketones in mod- (3ga). The regioselectivity of acylation with meta-substi-
erate to good yields (3aa–3ja). However, attempts to acylate tuted substrates may be attributable to steric effects; only
highly electron-deficient (4-nitrobenzyl)(p-tolyl)sulfane 3ka the less hindered ortho position of thioether was acylated
and (4-cyanbenzyl)(p-tolyl)sulfane 3la failed. We suspect (3da–3ea). The use of arenes bearing two electron-with-
that this failure may be due to the strong electron-with- drawing groups also provided good yields (3ca and 3cb).
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B. Xu, W. Liu, C. Kuang
FULL PAPER
Table 2. Substrate scope.[a]
[a] Reaction conditions: thioether arene 1 (0.2 mmol), α-oxocarboxylic acid 2 (0.6 mmol), Pd(OAc)2 (0.01 mmol), Ag2CO3 (0.4 mmol),
DMA (2 mL), 120 °C, 24 h. [b] Isolated yields.
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Thioethers as Directing Groups in Pd-Catalyzed Arene Acylations
Scheme 2. Plausible mechanism for thioether acylation.
Scheme 3. Removal and transformation of thioethers.
Diacylation products were not detected under our reaction
conditions (3aa–3bb, 3fa, and 3jb–3ja).
Conclusions
In summary, an efficient approach for the direct ortho-
acylation of thioethers was developed based on a Pd-cata-
lyzed C–H activation process. The reaction provides a very
convenient and atom-economic method for the synthesis of
aromatic ketones directly from α-oxocarboxylic acids.
In our experiments, the electron-rich thioether arenes
have greater reactivity than those that are electron-
difficient. On the basis of previous literature[25] and experi-
mental results obtained here, we favor the reaction mecha-
nism based on electrophilic palladation to describe the ob-
served outcomes. A plausible mechanism is proposed and
shown in Scheme 2. First, coordination of the S atom of A
to PdII and the subsequent cyclopalladation is envisioned
to provide five-membered palladacycle B. Complex B then
Experimental Section
General: Unless stated otherwise, all reactions were performed un-
reacts with 2, which is formed by the silver-mediated decar- der air atmosphere. All solvents were used without further purifica-
tion. 1H NMR spectra were obtained at 400 MHz and recorded
relative to the tetramethylsilane signal (δ = 0 ppm) or residual pro-
tio-solvent. 13C NMR spectra were obtained at 100 MHz, and
chemical shifts were recorded relative to the solvent resonance
(CDCl3, 77.0 ppm). Data for 1H NMR are recorded as follows:
chemical shift (δ, ppm), multiplicity [s = singlet, d = doublet, t =
triplet, q = quartet, m = multiplet or unresolved, br. s = broad
singlet, coupling constant(s) in Hz, integration]. Data for 13C NMR
are reported in terms of chemical shift (δ, ppm). High-resolution
mass spectra (HRMS) were recorded with a Bruker microTOF-QII
spectrometer with ESI mode unless otherwise stated.
boxylation of 1, to generate PdII intermediate C. Finally,
reductive elimination produces desired product D and re-
generates the PdII catalyst to facilitate the catalytic cycle.
Acylated product D can be reduced to remove the phen-
ylthio group or oxidized to obtain the corresponding sulf-
oxide or sulfane to facilitate further reaction (Scheme 3).
Additionally, we tried to use sulfoxides and sulfones as the
directing group in the same way that had proven successful
with thioethers. Sulfoxides and sulfones, however, failed to
provide any of the desired acylation products.
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B. Xu, W. Liu, C. Kuang
FULL PAPER
General Procedure for the Synthesis of Thioethers: A 100 mL flask
was charged with benzyl bromides (10.0 mmol) and thiophenols
(10.0 mmol) in MeCN (15 mL). Triethylamine (15.0 mmol) was
then added dropwise at room temperature with constant stirring.
The mixture was kept for 2 h. When the reaction was determined
to be complete (on the basis of TLC analysis), the mixture was
diluted with DCM (15 mL) and filtered through a pad of celite.
The filtrate was then concentrated by evaporation under reduced
pressure. The residue was purified by flash chromatography (elute:
petroleum ether) on silica gel to yield the desired product.
by TLC). The reaction mixture was filtered through a pad of celite,
and the solvent then evaporated under reduced pressure. The resi-
due was purified by preparative TLC (ethyl acetate/petroleum ether
= 1:10, v/v) to afford desired product 6aa (47.1 mg, 80%) as a
colourless oil. 1H NMR[26] (400 MHz, CDCl3): δ = 7.80 (d, J =
7.3 Hz, 2 H), 7.59 (t, J = 7.4 Hz, 1 H), 7.46 (t, J = 7.6 Hz, 2 H),
7.39 (dd, J = 10.7, 4.3 Hz, 1 H), 7.30 (t, J = 8.2 Hz, 2 H), 7.24 (d,
J = 7.5 Hz, 1 H), 2.33 (s, 3 H) ppm.
(Phenyl){2-[(p-tolylthio)methyl]phenyl}methanone (3aa): Pale yellow
1
oil (46.5 mg, 73%). H NMR (400 MHz, CDCl3): δ = 7.75 (d, J =
7.3 Hz, 2 H), 7.58 (t, J = 7.3 Hz, 1 H), 7.44 (t, J = 7.6 Hz, 2 H),
7.37 (d, J = 3.1 Hz, 2 H), 7.29 (s, 2 H), 7.10 (d, J = 8.0 Hz, 2 H),
6.96 (d, J = 7.8 Hz, 2 H), 4.25 (s, 2 H), 2.25 (s, 3 H) ppm. 13C
NMR (101 MHz, CDCl3): δ = 197.93, 138.26, 137.96, 137.72,
136.75, 133.91, 133.01, 131.93, 131.22, 130.82, 130.34, 129.53,
General Procedure for the Acylation: A mixture of sulfur ethers 1
(0.2 mmol), α-oxocarboxylic acids 2 (0.3 mmol), Pd(OAc)2 (2.8 mg,
5 mol-%) and Ag2CO3 (110.3 mg, 0.4 mmol) in DMA (2 mL) was
stirred at 120 °C for 12 h in a closed vial. After cooling to ambient
temperature the mixture was diluted with DCM (15 mL) and fil-
tered through a pad of celite. The filtrate was then washed with
brine three times and dried over sodium sulfate. Particulates were
removed and the solvent then evaporated under reduced pressure;
the remaining residue was purified by preparative TLC to obtain
desired products 3.
129.37, 128.26, 126.33, 37.10, 21.02 ppm. IR (KBr, neat): ν = 2922,
˜
1616, 1608, 1487, 1085, 804 cm–1. HRMS: m/z = calcd. for
C21H18OS: 318.1078, found 318.1075.
(p-Tolyl){2-[(p-tolylthio)methyl]phenyl}methanone (3ab): Pale yellow
1
oil (49.9 mg, 75%). H NMR (400 MHz, CDCl3): δ = 7.66 (d, J =
8.1 Hz, 2 H), 7.36 (d, J = 3.1 Hz, 2 H), 7.27 (s, 2 H), 7.24 (d, J =
7.9 Hz, 2 H), 7.10 (d, J = 8.0 Hz, 2 H), 6.96 (d, J = 8.0 Hz, 2 H),
4.23 (s, 2 H), 2.43 (s, 3 H), 2.25 (s, 3 H) ppm. 13C NMR (101 MHz,
CDCl3): δ = 197.62, 143.96, 138.57, 137.70, 136.69, 135.14, 132.01,
131.15, 130.72, 130.52, 130.14, 129.51, 129.17, 129.00, 126.30,
Oxidation of (Phenyl){2-[(p-tolylthio)methyl]phenyl}methanone
(3aa) to (Phenyl){2-[(p-tolylsulfinyl)methyl]phenyl}methanone (4aa):
A solution of (phenyl){2-[(p-tolylthio)methyl]phenyl}methanone
(100 mg, 0.3 mmol) in CH2Cl2 (2 mL)was stirred at 0 °C as m-
CPBA (54.3 mg, 0.3 mmol) was added. After stirring for 20 min,
the aqueous saturated solution of Na2SO3 (10 mL) was added. The
organic phase was separated, washed with aqueous saturated solu-
tion of NaHCO3 (2ϫ 10 mL), dried (Na2SO4) and concentrated
under reduced pressure. The residue was purified by preparative
TLC (ethyl acetate/petroleum ether = 1:8, v/v) affording desired
37.07, 21.72, 21.02 ppm. IR (KBr, neat): ν = 2918, 1616, 1605,
˜
1490, 1081, 799 cm–1. HRMS: m/z
=
calcd. for C22H20OS:
332.1235, found 332.1233.
(Phenyl){2-[(p-tolylthio)methyl]-4-fluorophenyl}methanone
(3ba):
1
Yellow oil (49.1 mg, 73%). H NMR (400 MHz, CDCl3): δ = 7.74
(d, J = 7.6 Hz, 2 H), 7.60 (t, J = 7.3 Hz, 1 H), 7.45 (t, J = 7.5 Hz,
2 H), 7.32 (dd, J = 8.4, 5.3 Hz, 1 H), 7.08 (d, J = 7.8 Hz, 3 H),
6.99 (dd, J = 15.8, 5.0 Hz, 3 H), 4.18 (s, 2 H), 2.25 (s, 3 H) ppm.
1
product 4aa (62.2 mg, 62%) as a yellow oil. H NMR (400 MHz,
CDCl3): δ = 7.72 (d, J = 7.2 Hz, 2 H), 7.59 (t, J = 7.4 Hz, 1 H),
7.44 (dd, J = 14.6, 7.1 Hz, 4 H), 7.38 (d, J = 8.1 Hz, 3 H), 7.33 (d,
J = 7.6 Hz, 1 H), 7.19 (d, J = 7.9 Hz, 2 H), 4.55 (d, J = 12.7 Hz, 13C NMR (101 MHz, CDCl3): δ = 196.45, 160.74 (J = 247 Hz),
1 H), 4.16 (d, J = 12.7 Hz, 1 H), 2.34 (s, 3 H) ppm. 13C NMR 139.9 (J = 6 Hz), 137.01, 136.98, 133.71 (J = 3 Hz), 133.41, 132.54
(101 MHz, CDCl3): δ = 197.64, 141.39, 140.22, 138.08, 137.78,
133.00, 131.08, 130.79, 130.67, 130.44, 129.74, 128.28, 127.42,
124.24, 61.18, 21.43 ppm. HRMS: m/z = calcd. for C21H18O2S:
334.1028, found 334.1031.
(J = 8 Hz), 131.43, 130.30, 129.61, 128.43, 117.15 (J = 21 Hz),
116.20 (J = 23 Hz), 36.48, 21.04 ppm. IR (KBr, neat): ν = 2924,
˜
1678, 1615, 1592, 1473, 1112, 811 cm–1. HRMS: m/z = calcd. for
C21H17FOS: 336.0984, found 336.0981.
(p-Tolyl){2-[(p-tolylthio)methyl]-4-fluorophenyl}methanone
(3bb):
Oxidation of (Phenyl){2-[(p-tolylthio)methyl]phenyl}methanone
(3aa) to (Phenyl)[2-(tosylmethyl)phenyl]methanone (5aa): A solution
of (phenyl){2-[(p-tolylthio)methyl]phenyl}methanone (100 mg,
0.3 mmol) in CH2Cl2 (2 mL) was stirred at 0 °C as m-CPBA
(114 mg, 0.62 mmol) was added. After stirring for 1 h, the aqueous
saturated solution of Na2SO3 (10 mL) was added. The organic
phase was separated, washed with aqueous saturated solution of
NaHCO3 (2ϫ 10 mL), dried (Na2SO4) and concentrated under re-
duced pressure. The residue was purified by preparative TLC (ethyl
acetate/petroleum ether = 1:8, v/v) affording desired product 5aa
1
Yellow oil (50.5 mg, 72%). H NMR (400 MHz, CDCl3): δ = 7.68
(d, J = 8.1 Hz, 2 H), 7.33 (dd, J = 8.5, 5.3 Hz, 1 H), 7.27 (d, J =
7.9 Hz, 2 H), 7.10 (d, J = 8.0 Hz, 2 H), 7.06 (dd, J = 8.4, 2.7 Hz,
1 H), 7.00 (dd, J = 11.1, 5.2 Hz, 3 H), 4.19 (s, 2 H), 2.46 (s, 3 H),
2.28 (s, 3 H) ppm. 13C NMR (101 MHz, CDCl3): δ = 196.12, 160.76
(J = 247 Hz), 144.45, 140.23 (J = 6 Hz), 136.95, 134.43, 133.46 (J
= 4 Hz), 132.43 (J = 8 Hz), 131.57, 131.37, 130.48, 129.59, 129.16,
116.93 (J = 21 Hz), 116.03 (J = 22 Hz), 36.46, 21.76, 21.03 ppm.
IR (KBr, neat): ν = 2922, 1683, 1615, 1594, 1482, 1085, 802 cm–1.
˜
1
HRMS: m/z = calcd. for C22H19FOS: 350.1141, found 350.1144.
(86.2 mg, 82%) as a yellow oil. H NMR (400 MHz, CDCl3): δ =
7.64 (d, J = 7.2 Hz, 2 H), 7.58–7.49 (m, 5 H), 7.44–7.34 (m, 4 H),
7.13 (d, J = 8.0 Hz, 2 H), 4.84 (s, 2 H), 2.30 (s, 3 H) ppm. 13C
NMR (101 MHz, CDCl3): δ = 197.30, 144.61, 139.13, 137.29,
135.63, 133.61, 132.93, 131.00, 130.72, 130.57, 129.69, 128.35,
128.09, 127.83, 127.81, 57.99, 21.61 ppm. HRMS: m/z = calcd. for
C21H18O3S: 350.0977, found 350.0974.
(Phenyl){2-[(p-tolylthio)methyl]-4,5-dichlorophenyl}methanone
(3ca): Pale yellow oil (52.7 mg, 68 %). 1H NMR (400 MHz,
CDCl3): δ = 7.71 (d, J = 7.5 Hz, 2 H), 7.62 (t, J = 7.4 Hz, 1 H),
7.46 (t, J = 7.7 Hz, 2 H), 7.42 (s, 1 H), 7.36 (s, 1 H), 7.08 (d, J =
8.1 Hz, 2 H), 6.98 (d, J = 8.0 Hz, 2 H), 4.14 (s, 2 H), 2.26 (s, 3
H) ppm. 13C NMR (101 MHz, CDCl3): δ = 195.50, 138.46, 137.73,
137.45, 136.81, 134.47, 133.59, 132.55, 131.72, 130.88, 130.79,
Reduction of (Phenyl){2-[(p-tolylthio)methyl]phenyl}methanone (3aa)
130.55, 130.24, 129.75, 128.54, 36.42, 21.05 ppm. IR (KBr, neat): ν
˜
to (2-Methylphenyl)phenylmethanone (6aa):
(phenyl){2-[(p-tolylthio)methyl]phenyl}methanone
A
solution of
(100 mg,
= 2925, 1615, 1597, 1484, 1079, 801 cm–1. HRMS: m/z = calcd. for
C21H1615Cl2OS: 386.0299, found 386.0298.
0.3 mmol) in methanol (2 mL) was added 0.6 mL of hydrazine hy-
drate. The Raney-Nickel was added partly at room temperature
until only a small amount of the substrate remained (as monitored
(p-Tolyl){2-[(p-tolylthio)methyl]-4,5-dichlorophenyl}methanone
(3cb): Pale yellow oil (56.2 mg, 70 %). 1H NMR (400 MHz,
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Thioethers as Directing Groups in Pd-Catalyzed Arene Acylations
CDCl3): δ = 7.64 (d, J = 8.1 Hz, 2 H), 7.43 (s, 1 H), 7.37 (s, 1 H),
7.27–7.29 (d, 2 H), 7.11 (d, J = 8.1 Hz, 2 H), 7.00 (d, J = 7.9 Hz,
7.74 (d, J = 7.4 Hz, 2 H), 7.56 (t, J = 7.4 Hz, 1 H), 7.41 (t, J =
7.7 Hz, 2 H), 7.29 (d, J = 7.5 Hz, 1 H), 7.18 (t, J = 7.6 Hz, 1 H),
2 H), 4.15 (s, 2 H), 2.47 (s, 3 H), 2.28 (s, 3 H) ppm. 13C NMR 7.11 (t, J = 7.5 Hz, 3 H), 6.94 (d, J = 7.9 Hz, 2 H), 4.29 (s, 2 H),
(101 MHz, CDCl3): δ = 195.14, 144.69, 138.24, 138.04, 137.39,
134.28, 134.23, 132.45, 131.66, 130.87, 130.73, 130.49, 130.42, = 198.32, 139.30, 138.60, 137.69, 136.82, 135.07, 132.98, 132.59,
130.14, 129.88, 129.73, 129.27, 36.40, 21.78, 21.05 ppm. IR (KBr, 132.42, 131.35, 130.50, 129.56, 128.14, 126.95, 126.18, 33.77, 21.04,
2.44 (s, 3 H), 2.22 (s, 3 H) ppm. 13C NMR (101 MHz, CDCl3): δ
neat): ν = 2919, 1615, 1607, 1490, 1077, 803 cm–1. HRMS: m/z 19.73 ppm. IR (KBr, neat): ν = 2922, 1616, 1608, 1487, 1085,
˜
˜
calcd. for C22H1815Cl2OS: 400.0455, found 400.0457.
804 cm–1. HRMS: m/z calcd. for C22H20OS: 332.1235, found
332.1233.
(Phenyl){2-[(p-tolylthio)methyl]-4-methylphenyl}methanone (3da):
Pale yellow oil (52.5 mg, 79%). H NMR (400 MHz, CDCl3): δ =
1
(Phenyl){2-[(p-tolylthio)methyl]-4-methoxyphenyl}methanone (3ha):
Pale yellow oil (52.2 mg, 75%). H NMR (400 MHz, CDCl3): δ =
1
7.74 (d, J = 7.2 Hz, 2 H), 7.56 (t, J = 7.4 Hz, 1 H), 7.43 (t, J =
7.7 Hz, 2 H), 7.22–7.17 (m, 2 H), 7.12 (d, J = 8.1 Hz, 2 H), 7.06
(d, J = 7.8 Hz, 1 H), 6.97 (d, J = 7.9 Hz, 2 H), 4.26 (s, 2 H), 2.35
(s, 3 H), 2.25 (s, 3 H) ppm. 13C NMR (101 MHz, CDCl3): δ =
197.92, 140.86, 138.10, 138.09, 136.67, 135.33, 132.78, 132.15,
131.69, 131.19, 130.30, 129.95, 129.50, 128.18, 126.94, 37.10, 21.38,
7.71 (d, J = 7.3 Hz, 2 H), 7.56 (t, J = 7.4 Hz, 1 H), 7.43 (t, J =
7.6 Hz, 2 H), 7.29 (d, J = 8.5 Hz, 1 H), 7.15 (d, J = 8.0 Hz, 2 H),
6.98 (d, J = 7.9 Hz, 2 H), 6.87 (d, J = 2.4 Hz, 1 H), 6.74 (dd, J =
8.5, 2.4 Hz, 1 H), 4.32 (s, 2 H), 3.79 (s, 3 H), 2.25 (s, 3 H) ppm.
13C NMR (101 MHz, CDCl3): δ = 197.28, 161.22, 141.24, 138.59,
136.79, 132.56, 132.52, 132.00, 131.43, 130.29, 130.20, 129.56,
21.01 ppm. IR (KBr, neat): ν = 2918, 1623, 1605, 1487, 1081,
˜
804 cm–1. HRMS: m/z calcd. for C22H20OS: 332.1235, found
128.15, 116.29, 111.51, 55.34, 37.40, 21.02 ppm. IR (KBr, neat): ν
˜
= 2932, 1613, 1604, 1483, 1237, 1169, 1086, 806 cm–1. HRMS: m/z
332.1238.
calcd. for C22H20O2S: 348.1184, found 348.1187.
(p-Tolyl){2-[(p-tolylthio)methyl]-4-methylphenyl}methanone (3 db):
Pale yellow oil (56.1 mg, 81%). H NMR (400 MHz, CDCl3): δ =
1
(4-Chlorophenyl){2-[(p-tolylthio)methyl]-4-methoxyphenyl}-
methanone (3hc): Pale yellow oil (56.6 mg, 74 %). 1H NMR
(400 MHz, CDCl3): δ = 7.64 (d, J = 8.5 Hz, 2 H), 7.39 (d, J =
8.5 Hz, 2 H), 7.24 (d, J = 8.7 Hz, 1 H), 7.13 (d, J = 8.1 Hz, 2 H),
6.97 (d, J = 7.9 Hz, 2 H), 6.86 (d, J = 2.4 Hz, 1 H), 6.74 (dd, J =
8.5, 2.5 Hz, 1 H), 4.30 (s, 2 H), 3.79 (s, 3 H), 2.25 (s, 3 H) ppm.
13C NMR (101 MHz, CDCl3): δ = 195.97, 161.36, 141.42, 139.00,
136.97, 136.86, 132.27, 131.58, 131.54, 129.85, 129.58, 128.48,
7.64 (d, J = 8.1 Hz, 2 H), 7.21 (s, 2 H), 7.18 (d, J = 3.4 Hz, 2 H),
7.11 (d, J = 8.1 Hz, 2 H), 7.05 (d, J = 7.9 Hz, 1 H), 6.96 (d, J =
7.9 Hz, 2 H), 4.24 (s, 2 H), 2.42 (s, 3 H), 2.34 (s, 3 H), 2.25 (s, 3
H) ppm. 13C NMR (101 MHz, CDCl3): δ = 197.61, 143.67, 140.58,
137.82, 136.61, 135.66, 135.48, 132.23, 131.58, 131.11, 130.48,
129.70, 129.47, 128.91, 126.90, 37.07, 21.69, 21.36, 21.01 ppm. IR
(KBr, neat): ν = 2918, 1617, 1605, 1474, 1078, 812 cm–1. HRMS:
˜
116.48, 111.58, 100.00, 55.38, 37.35, 21.02 ppm. IR (KBr, neat): ν
˜
m/z calcd. for C23H22OS: 346.1391, found 346.1394.
= 2921, 1614, 1606, 1488, 1237, 1162, 1085, 812 cm–1. HRMS: m/z
(4-Chlorophenyl){2-[(p-tolylthio)methyl]-4-methylphenyl}methanone:
(3dc): Pale yellow oil (57.1 mg, 78 %). 1H NMR (400 MHz,
CDCl3): δ = 7.66 (d, J = 8.5 Hz, 2 H), 7.39 (d, J = 8.5 Hz, 2 H),
7.19–7.14 (m, 2 H), 7.10 (d, J = 8.1 Hz, 2 H), 7.06 (d, J = 7.8 Hz,
1 H), 6.96 (d, J = 7.9 Hz, 2 H), 4.24 (s, 2 H), 2.35 (s, 3 H), 2.25 (s, 3
H) ppm. 13C NMR (101 MHz, CDCl3): δ = 196.60, 141.11, 139.27,
138.27, 136.85, 136.36, 134.87, 131.86, 131.65, 131.28, 129.66,
calcd. for C22H19ClO2S: 382.0794, found 382.0796.
(p-Tolyl){2-[(p-tolylthio)methyl]-5-(1-methylethyl)phenyl}-
methanone: (3ib): Pale yellow oil (57.6 mg, 77 %) 1H NMR
(400 MHz, CDCl3): δ = 7.68 (d, J = 8.1 Hz, 2 H), 7.30 (d, J =
8.0 Hz, 1 H), 7.25–7.21 (m, 3 H), 7.15–7.10 (m, 2 H), 7.09 (s, 1 H),
6.97 (d, J = 8.0 Hz, 2 H), 4.20 (s, 2 H), 2.87 (dt, J = 13.8, 6.9 Hz,
1 H), 2.43 (s, 3 H), 2.25 (s, 3 H), 1.20 (d, J = 6.9 Hz, 6 H) ppm.
13C NMR (101 MHz, CDCl3): δ = 197.90, 147.10, 143.90, 138.50,
136.46, 135.23, 134.71, 132.46, 130.79, 130.66, 130.53, 129.48,
129.00, 128.24, 127.30, 36.75, 33.65, 23.78, 21.72, 21.01 ppm. IR
129.52, 128.50, 127.01, 37.04, 21.38, 21.01 ppm. IR (KBr, neat): ν
˜
= 2927, 1617, 1606, 1475, 1069, 812 cm–1. HRMS: m/z calcd. for
C22H1915ClOS: 366.0845, found 366.0847.
(Phenyl){2-[(4-chlorophenylthio)methyl]-4-methylphenyl}methanone
(3ea): Pale yellow oil (52.2 mg, 74 %). 1H NMR (400 MHz,
CDCl3): δ = 7.74 (d, J = 7.4 Hz, 2 H), 7.60 (t, J = 7.4 Hz, 1 H),
7.46 (t, J = 7.7 Hz, 2 H), 7.26–7.21 (m, 2 H), 7.18–7.08 (m, 5 H),
4.30 (s, 2 H), 2.39 (s, 3 H) ppm. 13C NMR (101 MHz, CDCl3): δ
= 197.81, 141.06, 137.96, 137.55, 135.27, 134.37, 132.94, 132.63,
131.91, 131.64, 130.24, 130.11, 128.85, 128.26, 127.18, 36.67,
(KBr, neat): ν = 3012, 2918, 1616, 1605, 1490, 1081, 799 cm–1. H-
˜
MS: m/z calcd. for C25H26OS: 374.1704, found 374.1701.
(Phenyl){2-[(4-bromophenylthio)methyl]phenyl}methanone (3ja): Yel-
1
low oil (61.1 mg, 80%). H NMR (400 MHz, CDCl3): δ = 7.75 (d,
J = 7.4 Hz, 2 H), 7.61 (t, J = 7.3 Hz, 1 H), 7.46 (t, J = 7.7 Hz, 2
H), 7.41 (d, J = 2.9 Hz, 2 H), 7.31 (d, J = 4.3 Hz, 2 H), 7.28 (d, J
= 3.0 Hz, 2 H), 7.06 (d, J = 8.4 Hz, 2 H), 4.29 (s, 2 H) ppm. 13C
NMR (101 MHz, CDCl3): δ = 197.83, 138.20, 137.57, 137.32,
134.86, 133.20, 132.09, 131.82, 130.79, 130.52, 130.29, 129.54,
21.40 ppm. IR (KBr, neat): ν = 2924, 1612, 1610, 1492, 1079,
˜
805 cm–1. HRMS: m/z calcd. for C21H1715ClOS: 352.0689, found
352.0685.
128.36, 126.60, 120.66, 36.49 ppm. IR (KBr, neat): ν = 2927, 1615,
˜
(Phenyl){2-[(p-tolylthio)methyl]-5-chlorophenyl}methanone (3fa):
1598, 1490, 1091, 808 cm–1. HRMS: m/z calcd. for C20H15BrOS:
1
Pale yellow oil (53.6 mg, 76%). H NMR (400 MHz, CDCl3): δ =
382.0027, found 382.0023.
7.73 (d, J = 7.5 Hz, 2 H), 7.61 (t, J = 7.4 Hz, 1 H), 7.46 (t, J =
7.7 Hz, 2 H), 7.35–7.26 (m, 4 H), 7.08 (d, J = 8.0 Hz, 2 H), 6.97
(d, J = 8.0 Hz, 2 H), 4.17 (s, 2 H), 2.25 (s, 3 H) ppm. 13C NMR
(101 MHz, CDCl3): δ = 196.42, 139.74, 137.10, 136.98, 136.56,
133.44, 132.32, 132.13, 131.47, 131.30, 130.31, 130.25, 129.65,
Supporting Information (see footnote on the first page of this arti-
1
cle): Copies of H and 13C NMR spectra for all key intermediates
and final products.
128.98, 128.46, 36.58, 21.04 ppm. IR (KBr, neat): ν = 2927, 1612,
˜
Acknowledgments
1611, 1492, 1074, 803 cm–1. HRMS: m/z calcd. for C21H1715ClOS:
352.0689, found 352.0687.
Financial support was provided by the National Natural Science
Foundation of China (NSFC) (grant number 21272174) and the
Key Projects of Shanghai in Biomedicine (grant number
(Phenyl){2-[(p-tolylthio)methyl]-3-methylphenyl}methanone (3ga):
Pale yellow oil (48.5 mg, 73%). H NMR (400 MHz, CDCl3): δ =
1
Eur. J. Org. Chem. 2014, 2576–2583
© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
2581

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Received: January 20, 2014
Published Online: February 19, 2014
3208.
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