Facile synthesis of sulfenyl-substituted isocoumarins, heterocycle-fused pyrones and 3-(inden-1-ylidene)isobenzofuranones by FeCl3-promoted regioselective annulation of o-(1-alkynyl)benzoates and o-(1-alkynyl) heterocyclic carboxylates with dis

Article abstract of DOI:10.1016/j.tet.2011.12.003

Reported herein is the FeCl₃-promoted intermolecular sulfoesterification of o-(1-alkynyl)benzoates with disulfides, which provides a convenient and efficient method for synthesis of 4-sulfenylisocoumarins. Various functional groups such as meth

Full text of DOI:10.1016/j.tet.2011.12.003

Tetrahedron 68 (2012) 1552e1559
Contents lists available at SciVerse ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Facile synthesis of sulfenyl-substituted isocoumarins, heterocycle-fused pyrones
and 3-(inden-1-ylidene)isobenzofuranones by FeCl3-promoted regioselective
annulation of o-(1-alkynyl)benzoates and o-(1-alkynyl)heterocyclic carboxylates
with disulfides
,b,
Zhen Li a, Jianquan Hong a, Linhong Weng a, Xigeng Zhou a
*
a Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Handan Road 220, Shanghai 200433,
People’s Republic of China
b State Key Laboratory of Organometallic Chemistry, Shanghai 200032, People’s Republic of China
a r t i c l e i n f o
a b s t r a c t
Article history:
Reported herein is the FeCl3-promoted intermolecular sulfoesterification of o-(1-alkynyl)benzoates with
disulfides, which provides a convenient and efficient method for synthesis of 4-sulfenylisocoumarins.
Various functional groups such as methoxy, halides, ester, cyano and silicon groups in the substrates are
tolerated, and heterocycle-fused chalcogenylpyrones are also successfully achieved directly from the
corresponding heterocyclic precursors under the same reaction conditions. In addition, starting from
diynylbenzoate, this reaction sequence can be combined with a bicyclization step leading to the tetra-
cyclic (E)-3-(2-phenyl-3-phenylchalcogenylinden-1-ylidene)isobenzofuranone frameworks with high
regiospecificity and exclusive trans stereoselectivity.
Received 15 September 2011
Received in revised form 21 November 2011
Accepted 2 December 2011
Available online 8 December 2011
Keywords:
o-(1-Alkynyl)benzoates
Disulfides
Sulfoesterification
Bicyclization
Ó 2011 Elsevier Ltd. All rights reserved.
Iron(III) chloride
1. Introduction
Isocoumarins represents an important class of naturally occur-
ring lactones that exhibit a diverse range of biological activities
Carboneheteroatom bond-forming reactions involving alkynes
are important synthetic transformations in organic chemistry,1 and
the direct addition of heteroatom electrophiles to alkynes is
a challenging and desirable process.2 Metal-mediated electrophilic
annulation of alkynes offers an efficient route to chemical bond
formation by converting readily accessible alkynes into desirable,
poly-substituted carbo- and heterocyclic products in a single step.3
Despite significant recent advances in this area, cyclization of al-
kynes with unactivated disulfides, the most stable and inexpensive
class of sulfur-containing electrophiles, remains little explored.
Recently, several prominent examples have demonstrated that the
sulfoetherification and sulfoamination of alkynes with diorganyl
disulfides are efficient routes to synthesize 3-sulfenylbenzo[b]fu-
rans4 and 3-sulfenylindoles5 from the readily available
2-alkynylanisoles and 2-alkynylanilines. Similarly, electrophilic
annulation of 2-alkynylthioether with diorganyl disulfides could be
of great value in the synthesis of functionalized thiophenes.6
including antimicrobial,7 antifungal,8 immunomodulatory,9 cyto-
toxic,10 antiinflammatory,11 antiangiogenic,12 and differentiation
activity against leukemic cells.13 Their biological activities have
resulted in them often being used as building blocks in pharma-
ceutical compounds. For example, the angiogenesesis inhibitor
NM-3 that contain an isocoumarin moiety, is presently undergoing
clinical trials.14 Isocoumarins are also useful intermediates for
synthesis of various carbo- and heterocyclic, as well as ring-
opening compounds.15 In addition, isocoumarin complexes have
recently developed as an efficient catalyst for glycosylation re-
action.16 During the last decades, development of new
isocoumarin-based structures and new methods for their con-
struction has attracted significant and substantial interest.17 Among
these, the electrophilic cyclization of aryl acetylenes possessing
a carboxylate or an equivalent group at adjacent position has
emerged as one of the most attractive process for the construction
of the isocoumarin ring.18 Despite the synthetic utility of these
transformations, most of these processes require the use of the
large amount of bases, mineral acids, unavailable and instable
electrophiles or expensive transition metal catalysts. Meanwhile,
there are few available methods to prepare 4-sulfenylisocoumarins.
* Corresponding author. Tel./fax: þ86 21 65641740; e-mail address: xgzhou@
fudan.edu.cn (X. Zhou).
0040-4020/$ e see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2011.12.003

Z. Li et al. / Tetrahedron 68 (2012) 1552e1559
1553
Larock and co-workers18b reported recently an intermolecular
sulfoesterification of alkynes employing relatively expensive,
highly corrosive, and toxic sulfenyl chloride as electrophile, but
a mixture of five-membered-ring and six-membered-ring lactones
is often produced.
Fe(OTf)3 as a replacement was ineffective, although small amounts
of 3aa were occasionally observed (entries 9e12). The further in-
vestigation results indicated that no desired product could be
formed in the absence of catalyst (Table 1, entry 13).
Having established an optimal protocol, we next investigated
the generality and the scope of this transformation via variation of
both o-(1-alkynyl)benzoates 1 and disulfides 2. As illustrated in
Table 2, a series of disulfides 2be2f were investigated by coupling
reaction with methyl 2-(phenylethynyl)benzoate 1a in the pres-
ence of 1 equiv of FeCl3. In general, the electronic effect of sub-
stituents on disulfides has significant impact on the yield. For
example, reaction of 1a with disulfides 2b and 2c with an electron-
donating methyl or methoxy group gave the good results (entries 2
and 3), while disulfides bearing electron-withdrawing groups such
as chloro and bromo atoms, gave the corresponding products in
moderate yields (entries 4 and 5). Aliphatic disulfide, like 1,2-
dibutyldisulfide 2f, worked smoothly under the optimal reaction
conditions, affording 3af in 82% yield (entry 6). Subsequently,
utility of substituted o-(1-alkynyl)benzoates 1 was examined. To
our delight, various electron-rich, electron-neutral, and electron-
deficient substituents were well tolerated, and the standard re-
action conditions were compatible to substrates with both aryl and
alkyl groups at another terminus of 1-ethynyl-2-benzoate. In
general, the substituents at another end of alkynes have some ef-
fect on the reaction. For instance, introduction of an electro-
deficient aryl group led to the increase of yields (entries 7e11).
However, ortho-OMe group displayed a lower reactivity, probably
due to its chelating coordination (entry 12, 62% yield). Noticeably,
the position of the methyl group in the benzene ring also plays
a key role. For example, the alkyne with the methyl at the ortho-
position (1h) gave the expected product in a higher yield than the
para-position isomer (1i) (entries 13 and 14). Substrate 1j, fur-
The development of tandem reactions based on readily available
starting materials using inexpensive catalysts for the efficient
construction of bioactive small molecules is an important goal of
organic synthesis from the viewpoints of operational simplicity,
economy, and assembly efficiency.19 During the last years we have
been interested in the development of suitable methodologies for
the expeditious synthesis of biologically relevant carbo- and het-
erocyclic compounds via sustainable and environmentally benign
iron catalyst.20 Herein, we are willing to present a convenient
method for regioselective synthesis of 4-sulfenylisocoumarins and
heterocycle-fused sulfenylpyrones via FeCl3-promoted annulation
of o-(1-alkynyl)benzoates and o-(1-alkynyl)heterocyclic carboxyl-
ates with disulfides. Moreover, bicyclization of diynylbenzoate with
dichalcogenides provides a concise synthesis of (E)-3-(2-phenyl-3-
phenylchalcogenylinden-1-ylidene)isobenzofuranones via coupled
intermolecular carbochalcogenylation/subsequent intramolecular
carboesterification sequences.
2. Results and discussion
We initiated our research on the model reaction of o-(1-alkynyl)
benzoate 1a with 1,2-diphenyldisulfide 2a under different reaction
conditions (Table 1). It was found that only 3-phenyl-1H-iso-
coumarin was obtained in 91% yield upon treatment of a mixture of
1a and 2a (0.5 equiv) with 10 mol % FeCl3 in 1,2-dichloroethane
(DCE) at 80 ꢀC (entry 1). Interestingly, treatment of a 1:1 mixture
of 1a and 2a with 100 mol % FeCl3 under the same conditions led to
the formation of 3aa in 73% yield (entry 2). Elevating or decreasing
the reaction temperature was adverse to the reaction (entries 3 and
4). Inferior results were observed when the reaction was performed
in other solvents such as dichloromethane (DCM), CH3NO2, or tol-
uene (entries 5e7), whereas the strong coordinating solvents, such
as THF, tend to shut down the reacting system (entry 8). Utilization
of other Fe sources such as FeCl3$6H2O, FeBr2, Fe(NO3)3$9H2O or
nished a
b-naphthyl, proceeded smoothly and delivered the
product 3ja in good yield (entry 15) as well. Alkyne bearing
a cyclohexyl unit (1k), smoothly underwent the reaction, giving
3ka in satisfactory yield (entry 16). We were pleased to observe
that 1l containing a TMS group at one alkyne terminus was also
a suitable substrate, which provided the desired product in 74%
yield (entry 17). Gratifyingly, terminal alkyne 1m was also suc-
cessful in this transformation and provided the corresponding
product in moderate yield (entry 18). It was noted that fluoro and
chloro substituents on the benzoate moiety of 1n and 1o were
efficient in this transformation (entries 19 and 20).
Table 1
Screening conditions for annulation reaction of 1a with 2aa
Given the fact that thiophene-fused a-pyrones display a very
promising antitumor activity,21 we made an extension of this re-
action to synthesis of heterocycle-fused chalcogenylpyrones. The
expeditious synthetic procedures for o-(1-alkynyl)heterocyclic
carboxylate substrates were outlined in Supplementary data. Then,
the scope of the protocol with respect to o-(1-alkynyl)heterocyclic
carboxylates 1pe1r was investigated (Scheme 1). It was found that
o-(1-alkynyl)thiophene-3-carboxylates 1p and 1q were suitable
reactants, and desirable products 3pa, 3pg and 3qg were generated
in good to quantitative yields. Additionally, reaction of o-
(1-alkynyl)indole-2-carboxylate 1r with disulfide 2a proceeded
smoothly as well, giving the expected product 3ra in 72% yield. The
structure of compound 3ra was confirmed by X-ray diffraction
analysis (Fig. 1).
Encouraged by the above results, we further synthesized diy-
nylbenzoate 1s22 and envisioned that combination of 1s with 2
could subject to some tandem transformation in the current ex-
perimental conditions. Interestingly, treatment of 1s with 2 did
not give the expected 11-phenyl-12-(phenylchalcogenyl)-6H-
dibenzo[c,h]chromen-6-one, instead, tetracyclic (E)-3-(2-phenyl-
Entry [Fe]
Disulfide (equiv) Solvent Temp (ꢀC) Yieldc (%)
1b
2
3
4
5
6
7
8
9
10
11
12
13
FeCl3 (0.1)
0.5
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
DCE
DCE
DCE
DCE
DCM
80
80
100
45
0
FeCl3 (1.0))
FeCl3 (1.0)
FeCl3 (1.0)
FeCl3 (1.0)
FeCl3 (1.0)
FeCl3 (1.0)
FeCl3 (1.0)
FeCl3$6H2O(1.0)
FeBr2 (1.0)
73
71
58
46
35
44
0
38
17
Trace
Trace
0
45
Toluene 80
CH3NO2 80
THF
DCE
DCE
DCE
DCE
DCE
80
80
80
80
80
80
Fe(NO3)3$9H2O(1.0) 1.0
Fe(OTf)3
None
1.0
1.0
a
Reaction conditions: 1a (0.2 mmol), 2a (based on 1a), Fe salt (based on 1a) in
3-(phenylchalcogenyl)inden-1-ylidene)isobenzofuranones
(3)
solvent (2.0 mL) under N2 atmosphere for 24 h.
b
were obtained in moderate yields (Scheme 2). The formation of 3
represents the first example of one-step construction of
3-Phenyl-1H-isocoumarin was obtained in 91% yield.
Isolated yield based on 1a.
c

1554
Z. Li et al. / Tetrahedron 68 (2012) 1552e1559
Table 2 (continued)
Table 2
Scope of FeCl3-promoted sulfoesterification of o-(1-alkynyl)benzoates 1 with di-
Entry
Substrate 1
Substrate 2
Product 3
Yieldb (%)
chalcogenide 2a
12
2b
62
Entry
1
Substrate 1
Substrate 2
2a: C6H5S
Product 3
Yieldb (%)
13
14
15
2a
2b
2a
90
56
75
73
2
3
4
5
6
7
8
9
1a
1a
1a
1a
1a
2b: p-MeeC6H4S
2c: p-MeOeC6H4S
2d: p-CleC6H4S
2e: p-BreC6H4S
2f: n-BuS
79
77
57
60
82
77
75
86
16
17
18
19
2a
2b
2a
2a
2a
70
74
58
81
63
2b
20
2a
a
Reaction conditions: o-(1-alkynyl)benzoates
1 (0.2 mmol), disulfides 2
(0.2 mmol), FeCl3 (0.2 mmol), in DCE (2.0 mL) at 80 ꢀC under N2 atmosphere for
20e24 h.
b
Yield of isolated products after chromatographic purification.
2a
chalcogenyl-substituted indene ring. The structure of compound
3sa was determined by X-ray crystallography (Fig. 2).
A plausible mechanism for the FeCl3-promoted chalcogenoes-
terification of o-(1-alkynyl)benzoates with disulfides is illustrated in
Scheme 3. Initially, FeCl3 reacts with 2 to form an RSþ cation (I) and
a [FeCl3(SR)]ꢁ anion (II) as observed previously.23 The electrophilic
addition of I to alkyne results in the formation of a three-membered
cyclic sulfenonium cation III,4,5,24 which is subsequently attacked by
the oxygen of the ester functionality to form the intermediate (IV).
Finally, abstraction of the methyl group by [FeCl3(SR)]ꢁ gives the 6-
endo cyclization product 4-sulfenylisocoumarins 3, in companying
10
11
2a
2a
92
91

Z. Li et al. / Tetrahedron 68 (2012) 1552e1559
1555
Scheme 1. FeCl3-promoted chalcogenoesterification of o-(1-alkynyl)heterocyclic car-
boxylates with dichalcogenides.
Fig. 2. ORTEP plot of the X-ray crystal structure of 3sa.
Fig. 1. ORTEP plot of the X-ray crystal structure of 3ra.
with the release of MeCl.22,25 For the diynylbenzoate substrate (1s)
the different regioselectivity might be attributed to both the
stronger nucleophilicity of the alkynyl on the electron-withdrawing
group-free aryl ring and the close proximity of the related carbon
atoms.
Scheme 3. The possible mechanism for the formation of 3.
3. Conclusion
In summary, we have described a facile synthetic approach to 4-
sulfenylisocoumarins by the FeCl3-promoted electrophilic cycliza-
tion of o-(1-alkynyl)benzoates and disulfides. A wide variety of o-
(1-alkynyl)benzoates undergo this cyclization from moderate to
excellent yields. This procedure allows simultaneous construction
of the isocoumarin ring system and the installation of a sulfenyl
functionality at the 4-position of the isocoumarin ring, which is
a useful complement to the current synthetic approaches to 4-
sulfenylisocoumarin. The present procedure is also an efficient
approach to thieno- and indol-fused chalcogenylpyrones that are
Scheme 2. FeCl3-promoted dicyclization reaction of diynylbenzoate 1s with dichal-
cogenides 2.

1556
Z. Li et al. / Tetrahedron 68 (2012) 1552e1559
potential pharmacological interest. Furthermore, bicyclization
products, (E)-3-(2-phenyl-3-(phenylchalcogenyl)inden-1-ylidene)
isobenzofuranones, could be achieved via a domino reaction se-
quence of diynylbenzoate with dichalcogenides.
for C22H16O2S (MþþH): 345.0949, found: 311.0918; IR (KBr):
1744 cmꢁ1
.
4.2.3. 4-((4-Methoxyphenyl)thio)-3-phenyl-1H-isochromen-1-one
(3ac). Pale yellow solid; melting point 114.0e115.8 ꢀC; 1H NMR
4. Experimental section
4.1. General methods
(400 MHz, CDCl3):
d
¼8.35 (d, J¼7.8 Hz, 1H), 8.03 (d, J¼8.1 Hz, 1H),
7.76 (d, J¼7.7 Hz, 2H), 7.71 (t, J¼7.3 Hz, 1H), 7.53 (t, J¼7.4 Hz, 1H),
7.39e7.47 (m, 3H), 7.05 (d, J¼8.7 Hz, 2H), 6.77 (d, J¼8.7 Hz, 2H); 13C
NMR (100 MHz, CDCl3):
d
¼161.5, 159.6, 158.3, 138.1, 135.2, 132.9,
All reactions were carried out under nitrogen atmosphere using
the standard Schlenk techniques. Commercial reagents and sol-
vents were used as received. Substrates 118b,22,26 and 227 were
prepared according to literatures reported. Solvents were refluxed
and distilled under nitrogen from calcium hydride. Melting points
were obtained on an SGW X4 hot-plate digital microscope melting
point apparatus and were uncorrected. 1H NMR spectra were
recorded on a JEOL ECA-400 NMR spectrometer. Chemical shifts (in
130.2, 129.7, 129.6, 128.6, 128.4, 127.9, 126.8, 126.1, 120.9, 115.0,
107.9, 55.351; HRMS (ESI): calcd for C22H16O3S (MþþH): 361.0898,
found: 361.0856; IR (KBr): 1741 cmꢁ1
.
4.2.4. 4-((4-Chlorophenyl)thio)-3-phenyl-1H-isochromen-1-one
(3ad). White solid; melting point 135.6e137.7 ꢀC; 1H NMR
(400 MHz, CDCl3):
d
¼8.37 (d, J¼7.8 Hz, 1H), 7.91 (d, J¼8.1 Hz, 1H),
7.72 (t, J¼7.6 Hz, 3H), 7.55 (t, J¼7.6 Hz, 1H), 7.39e7.47 (m, 3H), 7.21
ppm) were referenced to tetramethylsilane (
d
¼0 ppm) in CDCl3 as
(d, J¼8.6 Hz, 2H), 7.04 (d, J¼8.5 Hz, 2H); 13C NMR (100 MHz, CDCl3):
an internal standard. 13C NMR spectra were obtained by the same
NMR spectrometers and were calibrated with CDCl3
d
¼161.2, 160.4, 137.6, 135.5, 135.1, 132.6, 131.7, 130.5, 129.9, 129.5,
129.3, 128.9, 128.0, 127.2, 125.8, 120.9, 106.1; HRMS (ESI): calcd
(
d
¼77.00 ppm). High-resolution mass spectra (HRMS) were recor-
for C21H13ClO2S (MþþH): 365.0403, found: 365.0388; IR (KBr):
ded using ESI ionization sources. IR spectra were obtained on
a Nicolet FT-IR 360 spectrometer (KBr disc). X-ray diffraction data
for 3ra and 3sa (CCDC 830005, 832347) were collected on a SMART
1740 cmꢁ1
.
4.2.5. 4-((4-Bromophenyl)thio)-3-phenyl-1H-isochromen-1-one
APEX CCD diffractometer (graphite-monochromated Mo K
a
radia-
(3ae). White solid; melting point 154.3e156.5 ꢀC; 1H NMR
ꢀ
tion,
fe
u
-scan technique,
l
¼0.71073 A). The intensity data were
(400 MHz, CDCl3):
d
¼8.37 (d, J¼7.8 Hz, 1H), 7.90 (d, J¼8.1 Hz, 1H),
integrated by means of the SAINT program. SADABS was used to
perform area-detector scaling and absorption corrections. The
structures were solved by direct methods and were refined against
F2 using all reflections with the aid of the SHELXTL package. All
non-hydrogen atoms were found from the difference Fourier syn-
theses and refined anisotropically. The H atoms were included in
calculated positions with isotropic thermal parameters related to
those of the supporting carbon atoms but were not included in the
refinement. All calculations were performed using the Bruker
Smart program.
7.69e7.74 (m, 3H), 7.56 (t, J¼7.5 Hz, 1H), 7.39e7.47 (m, 3H), 7.33
(d, J¼8.4 Hz, 2H), 6.98 (d, J¼8.4 Hz, 2H); 13C NMR (100 MHz, CDCl3):
d
¼161.2, 160.5, 137.5, 135.8, 135.5, 132.6, 132.3, 130.5, 129.9, 129.3,
128.9, 128.0, 127.4, 125.811, 120.8, 119.4, 105.9; HRMS (ESI):
calcd for C21H13BrO2S (MþþH): 408.9898, found: 408.9878; IR
(KBr): 1738 cmꢁ1
.
4.2.6. 4-(Butylthio)-3-phenyl-1H-isochromen-1-one (3af). Pale yel-
low solid; melting point 51.1e52.7 ꢀC; 1H NMR (400 MHz, CDCl3):
d
¼8.35 (d, J¼7.9 Hz,1H), 8.26 (d, J¼7.8 Hz,1H), 7.84 (t, J¼8.2 Hz,1H),
7.79 (d, J¼6.7 Hz, 2H), 7.56 (t, J¼7.0 Hz, 1H), 7.44e7.48 (m, 3H), 2.51
(t, J¼7.1 Hz, 2H), 1.25e1.35 (m, 2H), 1.09e1.20 (m, 2H), 0.71
4.2. General procedure for sulfoesterification of o-(1-alkynyl)
benzoates 1 with disulfides 2
(t, J¼7.3 Hz, 3H); 13C NMR (100 MHz, CDCl3):
¼161.7, 158.5, 138.6,
d
135.1, 133.2, 130.6, 130.1, 129.8, 128.4, 127.8, 125.8, 120.8, 109.6, 35.3,
A mixture of o-(1-alkynyl)benzoates 1 (0.2 mmol), disulfides 2
(0.2 mmol), FeCl3(0.2 mmol), and anhydrous DCE (2 mL) was stir-
red in a Schlenk tube at 80 ꢀC (oil bath temperature) under N2 at-
mosphere until complete consumption of starting material as
monitored by TLC (usually 20e24 h), the mixture was diluted by
dichloromethane (10 mL), washed with saturated brine (3ꢂ10 mL),
and dried over Na2SO4, Evaporation of the solvent followed by
purification on silica gel (eluting with PE/EA¼100:1 to 30:1) pro-
vides the pure product 3.
30.9, 21.5, 13.5; HRMS (ESI): calcd for C19H18O2S (MþþH): 311.1106,
found: 311.1094; IR (KBr): 1720 cmꢁ1
.
4.2.7. 3-(4-Chlorophenyl)-4-(p-tolylthio)-1H-isochromen-1-one
(3bb). White solid; melting point 134.8e136.4 ꢀC; 1H NMR
(400 MHz, CDCl3):
d
¼8.34 (d, J¼7.9 Hz, 1H), 7.97 (d, J¼8.1 Hz, 1H),
7.67e7.70 (m, 3H), 7.53 (t, J¼7.7 Hz, 1H), 7.35 (d, J¼8.6 Hz, 2H),
6.99e7.05 (m, 4H), 2.26 (s, 3H); 13C NMR (100 MHz, CDCl3):
d
¼161.2, 158.7, 137.8, 136.4, 135.9, 135.4, 132.6, 131.2, 130.8, 130.2,
129.8, 128.9, 128.2, 126.1, 126.1, 120.8, 107.2, 20.9; HRMS (ESI): calcd
4.2.1. 3-Phenyl-4-(phenylthio)-1H-isochromen-1-one (3aa). White
solid; melting point 139.8e142.2 ꢀC; 1H NMR (400 MHz, CDCl3):
for C22H15ClO2S (MþþH): 379.0559, found: 379.0534; IR (KBr):
1739 cmꢁ1
.
d
¼8.37 (d, J¼7.7 Hz,1H), 7.97 (d, J¼8.1 Hz,1H), 7.74 (d, J¼8.2 Hz, 2H),
7.69 (t, J¼7.7 Hz,1H), 7.54 (t, J¼7.6 Hz,1H), 7.38e7.44 (m, 3H), 7.23 (t,
4.2.8. Ethyl 4-(1-oxo-4-(phenylthio)-1H-isochromen-3-yl)benzoate
J¼7.4 Hz, 2H), 7.11e7.15 (m, 3H); 13C NMR (100 MHz, CDCl3):
(3ca). White crystalline; Melting point 128.3e130.6 ꢀC; 1H NMR
d
¼161.3, 160.1, 137.9, 136.5, 135.3, 132.7, 130.3, 129.7, 129.3, 129.2,
(400 MHz, CDCl3):
d
¼8.37 (d, J¼7.8 Hz, 1H), 8.07 (d, J¼8.4 Hz, 2H),
128.7, 127.9, 126.0, 125.9, 125.6, 120.8, 106.4; HRMS (ESI): calcd for
7.98 (d, J¼8.0 Hz, 1H), 7.81 (d, J¼8.4 Hz, 2H), 7.72 (t, J¼7.2 Hz, 1H),
7.56 (t, J¼7.6 Hz, 1H), 7.20e7.25 (m, 2H), 7.09e7.15 (m, 3H), 4.38
(q, J¼7.1 Hz, 2H), 1.39 (t, J¼7.1 Hz, 3H); 13C NMR (100 MHz, CDCl3):
C21H14O2S (MþþH): 331.0793, found: 331.0778; IR (KBr): 1748 cmꢁ1
.
4.2.2. 3-Phenyl-4-(p-tolylthio)-1H-isochromen-1-one (3ab). White
solid; melting point 173.3e174.8 ꢀC; 1H NMR (400 MHz, CDCl3):
d
¼165.7, 160.9, 158.9, 137.5, 136.6, 136.1, 135.3, 131.7, 129.8, 129.3,
129.0, 129.0, 126.0, 125.9, 125.8, 120.8, 107.5, 61.1, 14.2; HRMS (ESI):
d
¼8.35 (d, J¼7.8 Hz, 1H), 7.97 (d, J¼8.1 Hz, 1H), 7.74 (d, J¼8.0 Hz,
calcd for C24H18O4S (MþþH): 403.1004, found: 403.0984; IR (KBr):
2H), 7.68 (t, J¼8.1 Hz, 1H), 7.52 (t, J¼7.5 Hz, 1H), 7.37e7.43 (m, 3H),
1741 cmꢁ1
.
6.95e7.04 (m, 4H), 2.26 (s, 3H); 13C NMR (100 MHz, CDCl3):
d
¼161.4, 159.9, 138.0, 135.7, 135.3, 132.9, 132.8, 130.3, 130.1, 129.7,
4.2.9. 4-(1-Oxo-4-(phenylthio)-1H-isochromen-3-yl)benzonitrile
129.4, 128.7, 127.9, 126.1, 126.1, 120.9, 106.9, 20.9; HRMS (ESI): calcd
(3da). Yellow solid; melting point 144.0e146.2 ꢀC; 1H NMR

Z. Li et al. / Tetrahedron 68 (2012) 1552e1559
1557
(400 MHz, CDCl3):
d
¼8.37 (d, J¼7.8 Hz, 1H), 7.99 (d, J¼8.0 Hz, 1H),
125.8, 120.9, 106.8; HRMS (ESI): calcd for C25H16O2S (MþþH):
7.86 (d, J¼7.9 Hz, 2H), 7.73 (t, J¼7.6 Hz, 1H), 7.67 (d, J¼7.7 Hz, 2H),
381.0949, found: 381.0936; IR (KBr): 1741 cmꢁ1
.
7.58 (t, J¼7.6 Hz, 1H), 7.24 (t, J¼7.5 Hz, 2H), 7.15 (t, J¼7.0 Hz, 1H), 7.11
(d J¼7.9 Hz, 2H); 13C NMR (100 MHz, CDCl3):
d¼160.7, 157.7, 137.4,
4.2.16. 3-Cyclohexyl-4-(phenylthio)-1H-isochromen-1-one (3ka). -
White solid; melting point 119.6e121.8 ꢀC; 1H NMR (400 MHz,
136.9, 135.8, 135.6, 131.7, 130.1, 130.0, 129.6, 129.5, 126.3, 126.2,
126.0, 121.0, 118.2, 113.8, 108.4; HRMS (ESI): calcd for C22H13NO2S
CDCl3):
d
¼8.29 (d, J¼7.9 Hz, 1H), 7.87 (d, J¼8.1 Hz, 1H), 7.65
(MþþH): 356.0745, found: 356.0718; IR (KBr): 1751 cmꢁ1
.
(t, J¼7.2 Hz, 1H), 7.46 (t, J¼7.5 Hz, 1H), 7.22 (t, J¼7.3 Hz, 2H),
7.10e7.14 (m, 3H), 3.49e3.57 (m, 1H), 1.79e1.83 (m, 2H), 1.71e1.75
4.2.10. 3-(3-Fluorophenyl)-4-(phenylthio)-1H-isochromen-1-one
(m, 4H), 1.21e1.39 (m, 4H); 13C NMR (100 MHz, CDCl3):
d
¼167.8,
(3ea). White crystalline; melting point 112.8e114.9 ꢀC; 1H NMR
161.7,137.9, 136.3, 135.1,129.6, 129.1, 127.9, 126.0, 125.6, 125.4, 104.5,
(400 MHz, CDCl3):
d
¼8.36 (d, J¼7.8 Hz, 1H), 7.98 (d, J¼8.1 Hz, 1H),
41.0, 30.0, 25.8, 25.4; HRMS (ESI): calcd for C21H20O2S (MþþH):
7.71 (t, J¼7.7 Hz, 1H), 7.55 (t, J¼8.1 Hz, 2H), 7.46 (d, J¼9.6 Hz, 1H),
337.1262, found: 337.1235; IR (KBr): 1735 cmꢁ1
.
7.33e7.38 (m,1H), 7.23 (t, J¼7.6 Hz, 2H), 7.09e7.15 (m, 4H); 13C NMR
(100 MHz, CDCl3):
d
¼163.2, 160.9, 158.4, 137.6, 136.1, 135.4, 134.6,
4.2.17. 4-(p-Tolylthio)-3-(trimethylsilyl)-1H-isochromen-1-one
129.8,129.5, 129.3, 129.0,126.1,126.0,125.8,125.2,120.8,117.3,117.1,
(3lb). Pale yellow crystalline; melting point 108.3e109.9 ꢀC; 1H
116.6, 116.4, 107.3; HRMS (ESI): calcd for C21H13FO2S (MþþH):
NMR (400 MHz, CDCl3):
1H), 7.62 (t, J¼8.1 Hz, 1H), 7.49 (t, J¼7.7 Hz, 1H), 6.97e7.04 (m, 4H),
2.26 (s, 3H), 0.39 (s, 9H); 13C NMR (100 MHz, CDCl3):
d
¼8.30 (d, J¼7.9 Hz, 1H), 7.71 (d, J¼8.0 Hz,
349.0698, found: 349.0678; IR (KBr): 1739 cmꢁ1
.
d
¼170.5, 162.7,
4.2.11. 3-(2-Bromophenyl)-4-(phenylthio)-1H-isochromen-1-one
136.5, 135.5, 134.9, 132.7, 129.9, 129.5, 129.0, 125.8, 125.0, 121.9,
(3fa). Pale yellow solid; Melting point 91.7e93.7 ꢀC; 1H NMR
118.8, 20.9, -0.7; HRMS (ESI): calcd for C19H20O2SSi (MþþH):
(400 MHz, CDCl3):
d
¼8.36 (d, J¼7.8 Hz, 1H), 7.92 (d, J¼7.9 Hz, 1H),
341.1031, found: 341.1013; IR (KBr): 1732 cmꢁ1
.
7.67 (t, J¼8.0 Hz, 1H), 7.59 (d, J¼7.3 Hz, 1H), 7.53 (t, J¼7.6 Hz, 1H),
7.36 (d, J¼6.9 Hz, 1H), 7.24e7.29 (m, 2H), 7.15 (t, J¼7.2 Hz, 2H),
4.2.18. 4-(Phenylthio)-1H-isochromen-1-one (3ma). Pale yellow
solid; melting point 98.9e100.7 ꢀC; 1H NMR (400 MHz, CDCl3):
7.05e7.09 (m, 3H); 13C NMR (100 MHz, CDCl3):
d¼161.2, 159.0,
137.2, 135.6, 135.5, 134.5, 132.9, 131.4, 131.2, 131.1, 130.1, 129.2, 127.1,
126.9, 126.1, 123.4, 121.3, 109.7, 107.5; HRMS (ESI): calcd
for C21H13BrO2S (MþþH): 408.9898, found: 408.9871; IR (KBr):
d
¼8.33 (d, J¼7.7 Hz, 1H), 7.68e7.78 (m, 3H), 7.55 (t, J¼7.7 Hz, 1H),
7.35e7.45 (m, 1H), 7.22 (t, J¼6.3 Hz, 3H), 7.16 (t, J¼6.8 Hz, 1H); 13C
NMR (100 MHz, CDCl3):
d
¼161.4, 149.9, 136.5, 135.3, 130.2, 129.5,
1748 cmꢁ1
.
129.3, 127.1, 126.4, 125.3, 121.7, 110.9, 107.7; HRMS (ESI): calcd
for C15H10O2S (MþþH): 255.0480, found: 255.0460; IR (KBr):
4.2.12. 3-(2-Methoxyphenyl)-4-(p-tolylthio)-1H-isochromen-1-one
(3gb). Pale yellow oil; 1H NMR (400 MHz, CDCl3):
1738 cmꢁ1
.
d¼8.35
(d, J¼7.9 Hz, 1H), 7.90 (d, J¼8.1 Hz, 1H), 7.66 (t, J¼8.2 Hz, 1H), 7.51
(t, J¼7.8 Hz, 1H), 7.35e7.42 (m, 2H), 6.92e7.02 (m, 6H), 3.71 (s, 3H),
4.2.19. 6-Fluoro-3-phenyl-4-(phenylthio)-1H-isochromen-1-one
(3na). Whitesolid;meltingpoint 139.1e141.4 ꢀC;1HNMR (400 MHz,
2.23 (s, 3H); 13C NMR (100 MHz, CDCl3):
d¼162.0, 158.0, 157.4,
CDCl3):
d
¼8.36e8.39 (m,1H), 7.74 (d, J¼6.9 Hz, 2H), 7.62 (d, J¼7.6 Hz,
137.7, 135.4, 135.1, 132.7, 131.5, 130.7, 129.7, 129.7, 128.5, 126.9,
125.8, 122.6, 121.2, 120.1, 111.0, 109.7, 55.4, 20.9; HRMS (ESI): calcd
for C23H18O3S (MþþH): 375.1055, found: 375.1022; IR (KBr):
1H), 7.38e7.47 (m, 3H), 7.19e7.25 (m, 3H), 7.15 (d, J¼7.3 Hz, 1H), 7.12
(d, J¼7.4 Hz, 2H); 13C NMR (100 MHz, CDCl3):
¼168.6, 166.0, 161.5,
d
160.5, 141.5, 135.9, 133.3, 133.2, 132.5, 130.6, 129.5, 129.4, 128.0, 126.1,
117.2, 117.0, 112.4, 112.1, 106.1; HRMS (ESI): calcd for C21H13FO2S
1738 cmꢁ1
.
(MþþH): 349.0698, found: 349.0675; IR (KBr): 1740 cmꢁ1
.
4.2.13. 4-(Phenylthio)-3-(o-tolyl)-1H-isochromen-1-one (3ha). White
solid; melting point 116.3e118.8 ꢀC; 1H NMR (400 MHz, CDCl3):
4.2.20. 8-Chloro-3-phenyl-4-(phenylthio)-1H-isochromen-1-one
d
¼8.38 (d, J¼7.8 Hz, 1H), 7.95 (d, J¼8.1 Hz, 1H), 7.72 (t, J¼8.0 Hz, 1H),
(3oa). White solid; melting point 119.1e121.0 ꢀC; 1H NMR
7.56 (t, J¼7.6 Hz, 1H), 7.23e7.34 (m, 3H), 7.15e7.18 (m, 3H), 7.10 (t,
(400 MHz, CDCl3):
d
¼7.95e7.97 (m, 1H), 7.73 (d, J¼6.9 Hz, 2H), 7.56
J¼6.7 Hz, 1H), 7.04 (d, J¼7.4 Hz, 2H), 2.29 (s, 3H); 13C NMR (100 MHz,
(d, J¼5.0 Hz, 2H), 7.44 (d, J¼7.0 Hz, 1H), 7.39 (t, J¼7.5 Hz, 2H), 7.23
CDCl3):
d¼161.6, 160.9, 137.6, 137.1, 136.1, 135.4, 132.8, 130.3, 130.0,
(d, J¼7.8 Hz, 2H), 7.15 (d, J¼7.4 Hz, 1H), 7.09e7.12 (m, 2H); 13C NMR
130.0, 129.6, 129.1, 128.9, 126.6, 125.9, 125.8, 125.4, 121.0, 108.8, 19.8;
(100 MHz, CDCl3):
d
¼161.0, 157.7, 140.8, 137.2, 136.2, 134.8, 134.8,
HRMS (ESI): calcd for C22H16O2S (MþþH): 345.0949, found:
132.4, 131.6, 130.5, 129.3, 127.9, 125.9, 125.8, 125.0, 117.9, 105.8;
345.0924; IR (KBr): 1742 cmꢁ1
.
HRMS (ESI): calcd for C21H13ClO2S (MþþH): 365.0403, found:
365.0378; IR (KBr): 1739 cmꢁ1
.
4.2.14. 3-(p-Tolyl)-4-(p-tolylthio)-1H-isochromen-1-one
White solid; melting point 150.1e151.8 ꢀC; 1H NMR (400 MHz,
CDCl3):
(3ib). -
4.3. General experimental procedure for FeCl3-promoted
chalcogenoesterification of o-(1-alkynyl)heterocyclic
carboxylates 1 with dichalcogenides 2
d
¼8.35 (d, J¼7.9 Hz, 1H), 7.96 (d, J¼8.1 Hz, 1H), 7.64e7.69
(m, 3H), 7.51 (t, J¼7.8 Hz, 1H), 7.20 (d, J¼8.0 Hz, 2H), 7.00e7.05
(m, 4H), 2.38 (s, 3H), 2.26 (s, 3H); 13C NMR (100 MHz, CDCl3):
d
¼161.6, 160.2, 140.6, 138.2, 135.6, 135.3, 133.0, 130.1, 129.9, 129.7,
A mixture of o-(1-alkynyl)heteroates 1 (0.2 mmol), dichalcoge-
nides 2 (0.2 mmol), FeCl3(0.2 mmol), and anhydrous DCE (2 mL)
was stirred in a Schlenk tube at 80 ꢀC (oil bath temperature) under
N2 atmosphere until complete consumption of starting material as
monitored by TLC (usually 12 or 24 h), the mixture was diluted by
dichloromethane (10 mL), washed with saturated brine (3ꢂ10 mL),
and dried over Na2SO4, Evaporation of the solvent followed by
purification on silica gel (eluting with PE/EA¼75:1) provides the
pure product 3.
129.4, 128.6, 128.5, 126.0, 120.8, 106.3, 21.5, 20.9; HRMS (ESI): calcd
for C23H18O2S (MþþH): 359.1106, found: 359.1085; IR (KBr):
1741 cmꢁ1
.
4.2.15. 3-(Naphthalen-2-yl)-4-(phenylthio)-1H-isochromen-1-one
(3ja). Pale yellow solid; melting point 146.3e148.3 ꢀC; 1H NMR
(400 MHz, CDCl3):
d¼8.38 (d, J¼7.8 Hz, 1H), 8.25 (s, 1H), 8.50
(d, J¼8.1 Hz, 1H), 7.82 (t, J¼9.4 Hz, 4H), 7.70 (t, J¼7.7 Hz, 1H),
7.46e7.56 (m, 3H), 7.21e7.25 (m, 2H), 7.13 (t, J¼7.3 Hz, 3H); 13C NMR
(100 MHz, CDCl3):
d¼161.5, 160.2, 138.1, 136.7, 135.4, 134.0, 132.4,
4.3.1. 3-Phenyl-4-(phenylthio)-6,7,8,9-tetrahydro-1H-benzo[4,5]
thieno[3,2-c]pyran-1-one (3pa). Yellow crystalline; melting point
130.1,130.0,129.9,129.4,128.9,128.8,127.7,127.5, 126.6, 126.1,126.1,

1558
Z. Li et al. / Tetrahedron 68 (2012) 1552e1559
164.7e167.2 ꢀC; 1H NMR (400 MHz, CDCl3):
d
¼7.80 (d, J¼7.9 Hz,
1H), 8.58 (d, J¼8.4 Hz, 1H), 8.41 (d, J¼7.8 Hz, 1H), 7.55e7.65 (m, 2H),
2H), 7.36e7.43 (m, 3H), 7.21e2.25 (m, 2H), 7.12e7.17 (m, 3H),
7.48 (t, J¼7.4 Hz, 1H), 7.37e7.43 (m, 3H), 7.24 (d, J¼7.2 Hz, 1H), 7.20
(d, J¼7.9 Hz, 2H), 7.03e7.05 (m, 3H), 6.94e6.96 (m, 2H), 6.76
2.96e3.04 (m, 2H), 2.66e2.74 (m, 2H), 1.78e1.88 (m, 4H); 13C NMR
(100 MHz, CDCl3):
d
¼159.2, 157.3, 154.6, 138.3, 135.4, 135.1, 131.8,
(d, J¼8.5 Hz, 1H); 13C NMR (100 MHz, CDCl3):
¼160.8, 149.2, 143.9,
d
130.2, 129.2, 127.9, 126.7, 126.2, 121.5, 104.5, 25.3, 25.2, 22.7, 21.8;
143.2, 135.5, 135.2, 134.4, 133.9, 130.4, 129.9, 129.7, 129.6, 129.1,
128.8, 128.2, 128.1, 127.5, 127.2, 127.0, 125.8, 124.3, 123.0, 122.0,
113.5; HRMS (ESI): calcd for C29H18O2Se (MþþH): 479.0550, found:
HRMS (ESI): calcd for C23H18O2S2 (MþþH): 391.0826, found:
391.0795; IR (KBr): 1729 cmꢁ1
.
479.0511; IR (KBr): 1775 cmꢁ1
.
4.3.2. 3-Phenyl-4-(phenylselanyl)-6,7,8,9-tetrahydro-1H-benzo[4,5]
thieno[3,2-c]pyran-1-one (3pg). Yellow crystalline; melting point
Acknowledgements
164.1e166.4 ꢀC; 1H NMR (400 MHz, CDCl3):
d
¼7.72 (d, J¼7.2 Hz,
2H), 7.36e7.43 (m, 3H), 7.24e2.26 (m, 2H), 7.18e7.20 (m, 3H),
We thank the NNSF of China, 973 Program (2009CB825300), the
Research Fund for the Doctoral Program of Higher Education of
China, and Shanghai Leading Academic Discipline Project for
financial support (B108).
2.96e3.04 (m, 2H), 2.66e2.74 (m, 2H), 1.76e1.88 (m, 4H); 13C NMR
(100 MHz, CDCl3):
d
¼158.7, 157.7, 156.0, 138.1, 135.6, 132.8, 130.7,
130.0, 129.6, 129.5, 129.4, 127.8, 126.9, 121.1, 100.1, 25.5, 25.1, 22.7,
21.8; HRMS (ESI): calcd for C23H18O2SSe (MþþH): 439.0271, found:
439.0226; IR (KBr): 1726 cmꢁ1
.
Supplementary data
4.3.3. Ethyl 3-methyl-4-oxo-6-phenyl-7-(phenylselanyl)-4H-thieno
[3,2-c]pyran-2-carboxylate (3qg). Yellow crystalline; melting point
Supplementary data associated with this article can be found in
the online version, at doi:10.1016/j.tet.2011.12.003. These data in-
clude MOL files and InChIKeys of the most important compounds
described in this article.
117.2e119.8 ꢀC; 1H NMR (400 MHz, CDCl3):
d
¼7.74 (d, J¼7.6 Hz, 2H),
7.38e7.47 (m, 3H), 7.22e2.25 (m, 2H), 7.18e7.21 (m, 3H), 4.33
(q, J¼7.1 Hz, 2H), 2.90 (s, 3H), 1.35 (t, J¼7.0 Hz, 3H); 13C NMR
(100 MHz, CDCl3):
d
¼161.9, 161.5, 160.8, 157.1, 147.3, 132.1, 130.6,
References and notes
130.1, 129.7, 129.5, 129.5, 127.8, 127.6, 127.2, 121.7, 99.6, 61.3, 15.0,
14.2; HRMS (ESI): calcd for C23H18O4SSe (MþþH): 471.0169, found:
1. For selected examples: (a) Yao, P. Y.; Zhang, Y.; Hsung, R. P.; Zhao, K. Org. Lett.
2008, 10, 4275; (b) Shi, Z. Z.; Zhang, C.; Li, S.; Pan, D. L.; Ding, S. T.; Cui, Y. X.; Jiao,
N. Angew. Chem., Int. Ed. 2009, 48, 4572; (c) Li, L.; Wang, M.; Zhang, X. J.; Jiang,
Y. W.; Ma, D. W. Org. Lett. 2009, 11, 1309; (d) Wang, Z. Q.; Lei, Y.; Zhou, M. B.;
Chen, G. X.; Song, R. J.; Xie, Y. X.; Li, J. H. Org. Lett. 2011, 11, 14; (e) Gou, F. R.; Huo,
P. F.; Bi, H. P.; Guan, Z. H.; Liang, Y. M. Org. Lett. 2009, 11, 3418; (f) Zhao, L. G.; Lu,
X. Y. Angew. Chem., Int. Ed. 2002, 41, 4343.
2. (a) Godoi, B.; Schumacher, R. F.; Zeni, G. Chem. Rev. 2011, 111, 2937 and refer-
ences therein; (b) Lamannaa, G.; Menichettia, S. Adv. Synth. Catal. 2007, 349,
2188; (c) Ganta, A.; Snowden, T. S. Org. Lett. 2008, 10, 5103.
3. For selected examples: (a) Jurberg, I. D.; Odabachian, Y.; Gagosz, F. J. Am. Chem.
Soc. 2010, 132, 3543; (b) Ota, K.; Lee, S. I.; Tang, J. M.; Takachi, M.; Nakai, H.;
Morimoto, T.; Sakurai, H.; Kataoka, K.; Chatani, N. J. Am. Chem. Soc. 2009, 131,
15203; (c) Balamurugan, R. ,; Gudla, V. Org. Lett. 2009, 11, 3116; (d) Hirano, K.;
Satoh, T.; Miura, M. Org. Lett. 2011, 13, 2395; (e) Nakamura, I.; Sato, T.; Terada,
M.; Yamamoto, Y. Org. Lett. 2007, 9, 4081; (f) Cho, E. J.; Kim, M.; Lee, D. Org. Lett.
2006, 8, 5413; (g) Asao, N.; Sato, K. Org. Lett. 2006, 8, 5361.
4. (a) Du, H. A.; Zhang, X. G.; Tang, R. Y.; Li, J. H. J. Org. Chem. 2009, 74, 7844; (b)
Gay, R. M.; Manarin, F.; Schneider, C. C.; Barancelli, D. A.; Costa, M. D.; Zeni, G. J.
Org. Chem. 2010, 75, 5701.
471.0115; IR (KBr): 1750 cmꢁ1
.
4.3.4. 5-Methyl-3-phenyl-4-(phenylthio)pyrano[4,3-b]indol-1(5H)-
one (3ra). White crystalline; melting point 239.2e240.7 ꢀC; 1H
NMR (400 MHz, CDCl3):
2H), 7.43e7.50 (m, 2H), 7.36e7.42 (m, 3H), 7.17e7.23 (m, 4H),
7.06e7.14 (m, 2H), 4.26 (s, 3H); 13C NMR (100 MHz, CDCl3):
d¼8.34 (d, J¼8.3 Hz, 1H), 7.73 (d, J¼7.9 Hz,
d¼158.1,
156.4, 141.5, 137.2, 132.5, 129.8, 129.5, 129.4, 127.9, 127.9, 126.3,
125.7, 125.6, 124.1, 121.5, 121.3, 121.0, 110.3, 105.0, 31.5; HRMS (ESI):
calcd for C24H17NO2S (MþþH): 384.1058, found: 384.1017; IR (KBr):
1719 cmꢁ1
.
4.4. General experimental procedure for FeCl3-promoted
domino reaction sequence of diynylbenzoate 1s with
dichalcogenides 2
5. (a) Guo, Y. J.; Tang, R. Y.; Li, J. H.; Zhong, P.; Zhang, X. G. Adv. Synth. Catal. 2009,
351, 2615; (b) Li, Z.; Hong, L. C.; Liu, R. T.; Shen, J. Z.; Zhou, X. G. Tetrahedron Lett.
2011, 52, 1343.
A mixture of diynylbenzoate 1s (0.2 mmol), dichalcogenide 2
(0.2 mmol), FeCl3(0.2 mmol), and anhydrous DCE (2 mL) was stir-
red in a Schlenk tube at 80 ꢀC (oil bath temperature) under N2 at-
mosphere until complete consumption of starting material as
monitored by TLC (36 h), the mixture was diluted by dichloro-
methane (10 mL), washed with saturated brine (3ꢂ10 mL), and
dried over Na2SO4, Evaporation of the solvent followed by purifi-
cation on silica gel (eluting with PE/EA¼50:1) provides the pure
product 3.
6. Yue, D. W.; Larock, R. C. J. Org. Chem. 2002, 67, 1905.
7. (a) Barrero, A. F.; Oltra, J. E.; Herrador, M. M.; Cabrera, E.; Sanchez, J. F.; Quilez, J.
F.; Rojas, F. J.; Reyes, J. F. Tetrahedron 1993, 49, 141; (b) Abraham, W. R.; Arfmann,
H. A. Phytochemistry 1988, 27, 3310; (c) Matsuda, H.; Shimoda, H.; Yoshikawa,
M. Bioorg. Med. Chem. 1999, 7, 1445; (d) Yoshikawa, M.; Harada, E.; Naitoh, Y.;
Inoue, K.; Matsuda, H.; Shimoda, H.; Yamahara, J.; Murakami, N. Chem. Pharm.
Bull. 1994, 42, 2225.
8. (a) Simon, A.; Dunlop, R. W.; Ghisalberti, E. L.; Sivasithamparam, K. Soil Biol.
Biochem. 1988, 20, 263; (b) Claydon, N.; Allan, M.; Hanson, J. R.; Avent, A. G.
Trans. Br. Mycol. Soc. 1987, 88, 503; (c) Culter, H. G.; Cox, R. H.; Crumley, F. G.;
Cole, P. O. Agric. Biol. Chem. 1986, 50, 2943; (d) Nozawa, K.; Yamada, M.; Tsuda,
Y.; Kawai, K.; Nakajima, S. Chem. Pharm. Bull. 1981, 29, 2689.
9. (a) Matsuda, H.; Shimoda, H.; Yamahara, J.; Yoshikawa, M. Bioorg. Med. Chem.
Lett. 1998, 8, 215; (b) Shimoda, H.; Matsuda, H.; Yamahara, J.; Yoshikawa, M.
Biol. Pharm. Bull. 1998, 21, 809.
10. Whyte, A. C.; Gloer, J. B.; Scott, J. A.; Mallock, D. J. Nat. Prod. 1996, 59, 765.
11. Furuta, T.; Fukuyama, Y.; Asakawa, Y. Phytochemistry 1986, 25, 517.
12. Lee, J. H.; Park, Y. J.; Kim, H. S.; Hong, Y. S.; Kim, K. W.; Lee, J. J. J. Antibiot. 2001,
54, 463.
4.4.1. (E)-3-(2-Phenyl-3-(phenylthio)-1H-inden-1-ylidene)iso-
benzofuran-1(3H)-one (3sa). Red crystalline; melting point
175.0e177.5 ꢀC; 1H NMR (400 MHz, CDCl3):
d¼8.48 (d, J¼7.7 Hz,
1H), 7.91 (d, J¼7.6 Hz, 1H), 7.40e7.45 (m, 6H), 7.31 (t, J¼7.7 Hz, 1H),
7.17e7.24 (m, 5H), 7.09e7.15 (m, 3H), 5.78 (d, J¼8.2 Hz, 1H); 13C
NMR (100 MHz, CDCl3):
d
¼165.9, 147.9, 142.6, 140.2, 137.4, 136.8,
13. Umehara, K.; Matsumoto, M.; Nakamura, M.; Miyase, T.; Kuronyanagi, M.;
136.3, 135.7, 135.3, 133.8, 130.6, 130.4, 129.0, 128.9, 128.6, 128.4,
128.3, 127.0, 126.8, 126.5, 126.2, 126.1, 125.8, 125.5, 124.9, 121.4;
HRMS (ESI): calcd for C29H18O2S (MþþH): 431.1106, found:
Noguchi, H. Chem. Pharm. Bull. 2000, 48, 566.
14. (a) Oikawa, T.; Sasaki, M.; Inose, M.; Shimamura, M.; Kuboki, H.; Hirano, S. I.;
Kumagai, H.; Ishizuka, M.; Takeuchi, T. Anticancer Res. 1997, 17, 1881; (b) Sal-
loum, R. M.; Jaskowiak, N. T.; Maureci, H. J.; Seetharam, S.; Beckett, M. A.;
Koons, A. M.; Hari, D. M.; Gupta, V. K.; Reimer, C.; Kalluri, R.; Posner, M. C.;
Hellman, S.; Kufe, D. W.; Weichselbaum, R. R. Cancer Res. 2000, 60, 6958.
15. For selected papers: (a) Goel, A.; Singh, F. V.; Kumar, V.; Reichert, M.; Gulder, T.
M.; Bringmann, G. J. Org. Chem. 2007, 72, 7765; (b) Goel, A.; Singh, F. V.; Dixit,
M.; Verma, D.; Raghunandan, R.; Maulik, P. R. Chem. Asian J. 2007, 2, 239; (c)
Afarinkia, K.; Bearpark, M. J.; Ndibwami, A. J. Org. Chem. 2005, 70, 1122; (d)
431.1062; IR (KBr): 1774 cmꢁ1
.
4.4.2. (E)-3-(2-Phenyl-3-(phenylselanyl)-1H-inden-1-ylidene)iso-
benzofuran-1(3H)-one (3sg). Red crystalline; melting point
192.2e194.9 ꢀC; 1H NMR (400 MHz, CDCl3):
d
¼8.70 (d, J¼8.4 Hz,

Z. Li et al. / Tetrahedron 68 (2012) 1552e1559
1559
Manivel, P.; Roopan, S. M.; Khan, F. N. J. Chil. Chem.Soc. 2008, 53, 1609; (e) Jana,
R.; Trivedi, R.; Tunge, J. A. Org. Lett. 2011, 11, 3434; (f) Qadeer, G.; Rama, N. H.;
Garduno-Ramírez, M. L. J. Fluorine Chem. 2007, 128, 641; (g) Tovar, J. D.; Swager,
T. M. J. Org. Chem. 1999, 64, 6499; (h) Rudyanto, M.; Kobayashi, K.; Honda, T.
Heterocycles 2009, 79, 753.
Maiti, S.; Biswas, S.; Jana, U. J. Org. Chem. 2010, 75, 1674; (f) Sue, D.; Kawabata,
T.; Sasamori, T.; Tokitoh, N.; Tsubaki, K. Org. Lett. 2010, 12, 256.
20. (a) Huang, W.; Shen, Q. S.; Wang, J. L.; Zhou, X. G. J. Org. Chem. 2008, 73, 1586;
(b) Huang, W.; Zheng, P. Z.; Zhang, Z. X.; Liu, R. T.; Chen, Z. X.; Zhou, X. G. J. Org.
Chem. 2008, 73, 6845; (c) Wang, J. L.; Zhang, L. X.; Jing, Y. F.; Huang, W.; Zhou,
X. G. Tetrahedron Lett. 2009, 50, 4978; (d) Bu, X. L.; Hong, J. Q.; Zhou, X. G. Adv.
Synth. Catal. 2011, 353, 2111.
21. (a) Queiroz, M. R. P.; Calhelha, R. C.; Vale, L. A.; Pinto, E.; Nascimento, M. S. Eur. J.
Med. Chem. 2009, 44, 1893; (b) Ram, V. J.; Goel, A.; Shukla, P. K.; Kapil, A. Bioorg.
Med. Chem. Lett. 1997, 7, 3101; (c) Raju, S.; Batchu, V. R.; Swamy, N. K.; Dev, R. V.;
Sreekanth, B. R.; Babu, J. M.; Vyas, K.; Kumar, P. R.; Mukkanti, K.; Annamalai, P.;
Palb, M. Tetrahedron 2006, 62, 9554.
22. Chang, W. R.; Lo, Y. H.; Lee, C. Y.; Wu, M. J. Adv. Synth. Catal. 2008, 350, 1248.
23. (a) Yu, L.; Ren, L. F.; Yi, R.; Wu, Y. L.; Chen, T.; Guo, R. J. Organomet. Chem. 2011,
696, 2228; (b) Usugi, S. I.; Yorimitsu, H.; Shinokubo, H.; Oshima, K. Org. Lett.
2004, 6, 601; (c) Beletskaya, I. P.; Sigeev, A. S.; Peregudov, A. S.; Petrovskii, P. V.;
Khrustalev, V. N. Chem. Lett. 2010, 39, 720.
24. (a) Taniguchi, N. J. Org. Chem. 2006, 71, 7874; (b) Taniguchi, N. Tetrahedron
2009, 65, 2782; (c) Hamel, P. J. Org. Chem. 2002, 67, 2854; (d) Li, Z.; Hong, J. Q.;
Zhou, X. G. Tetrahedron 2011, 67, 3680.
~
16. Zhu, Y. G.; Yu, B. Angew. Chem., Int. Ed. 2011, 50, 8329.
17. For selected papers: (a) Pal, S.; Chatare, V.; Pal, M. Curr. Org. Chem. 2011, 15, 782;
(b) Komeyama, K.; Takahashi, K.; Takaki, K. Org. Lett. 2008, 10, 5119; (c) Jean, M.;
Renault, J.; Weghe, P.; Asao, N. Tetrahedron Lett. 2010, 51, 378; (d) Liang, Y.; Xie, Y.
X.; Li, J. H. Synthesis 2007, 3, 400; (e) Marchal, E.; Uriac, P.; Legouin, B.; Toupet, L.;
Weghe, P. Tetrahedron 2007, 63, 9979; (f) Shimizu, M.; Hirano, K.; Satoh, T.; Miura,
M. J. Org. Chem. 2009, 74, 3478; (g) Mehta, S.; Larock, R. C. J. Org. Chem. 2010, 75,
1652; (h) Bras, G. L.; Hamze, A.; Messaoudi, S.; Provot, O.; Calvez, P. B. L.; Brion, J.
D.; Alami, M. Synthesis 2008, 10, 1607; (i) Woon, E. Y.; Dhami, A.; Mahon, M. F.;
Threadgill, M. D. Tetrahedron 2006, 62, 4829; (j) Bellina, F.; Ciucci, D.; Vergamini,
P.; Rossi, R. Tetrahedron 2000, 56, 2533; (k) Rossi, R.; Bellina, F.; Biagetti, M.;
Catanese, A.; Mannina, L. Tetrahedron Lett. 2000, 41, 5151; (l) Batu, G.; Stevenson,
R. J. Org. Chem. 1980, 45, 1532; (m) Liao, H. Y.; Cheng, C. H. J. Org. Chem. 1995, 60,
3711; (n) Larock, R. C.; Doty, M. J.; Han, X. J. J. Org. Chem. 1999, 64, 8770.
18. For selected papers: (a) Sashida, H.; Kawamukai, A. Synthesis 1999, 1145; (b)
Yao, T. L.; Larock, R. C. J. Org. Chem. 2003, 68, 5936; (c) Biagetti, M.; Bellina, F.;
Carpita, A.; Stabile, P.; Rossi, R. Tetrahedron 2002, 58, 5023; (d) Mitamura, T.;
Iwata, K.; Ogawa, A. Org. Lett. 2009, 11, 3422.
25. Zhou, C. X.; Dubrovsky, A. V.; Larock, R. C. J. Org. Chem. 2006, 71, 1626.
26. Crawford, L. A.; McNab, H.; Mount, A. R.; Wharton, S. I. J. Org. Chem. 2008, 73,
6642.
19. For selected papers: (a) Patil, N. T.; Yamamoto, Y. Chem. Rev. 2008, 108, 3395; (b)
Li, S.; Jia, W.; Jiao, N. Adv. Synth. Catal. 2009, 351, 569; (c) Qiu, J. W.; Zhang, X. G.;
Tang, R. Y.; Zhong, P.; Li, J. H. Adv. Synth. Catal. 2009, 351, 2319; (d) Cao, K.;
Zhang, F. M.; Tu, Y. Q.; Zhuo, X. T.; Fan, C. A. Chem.dEur. J. 2009, 15, 6332; (e)
27. (a) Kabalka, G. W.; Reddy, M. S.; Yao, M. L. Tetrahedron Lett. 2009, 50, 7340; (b)
Ali, M. H.; McDermott, M. Tetrahedron Lett. 2002, 43, 6271; (c) Singh, D.; Deo-
bald, A. M.; Camargo, L. S.; Tabarelli, G.; Rodrigues, O. D.; Braga, A. L. Org. Lett.
2010, 12, 3288.