One-pot three-component reactions of methyl ketones, phenols and a nucleophile: An expedient way to synthesize densely substituted benzofurans

Article abstract of DOI:10.1016/j.tet.2015.08.058

Three-component reactions of phenylglyoxal monohydrate, phenols, and indoles were developed with the aid of acid-catalyst, which produced various densely substituted benzofurans with good to excellent yields. On the basis of this observation, a one-pot, step-wise reaction was developed by using methyl ketones instead of using phenylglyoxal component in I₂/DMSO system. At last, three-component reaction offered a useful way to synthesize densely substituted benzofurans starting from simple and easily available substrates. The indole component can be replaced by some other nucleophiles, such as 1,2,4-trimethoxybenzene and thiophenol.

Full text of DOI:10.1016/j.tet.2015.08.058

Accepted Manuscript
One-pot three-component reactions of methyl ketones, phenols and a nucleophile: an
expedient way to synthesize densely substituted benzofurans
Cheng Cheng, Changhui Liu, Yanlong Gu
PII:
S0040-4020(15)30012-0
10.1016/j.tet.2015.08.058
TET 27080
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 5 July 2015
Revised Date: 14 August 2015
Accepted Date: 22 August 2015
Please cite this article as: Cheng C, Liu C, Gu Y, One-pot three-component reactions of methyl
ketones, phenols and a nucleophile: an expedient way to synthesize densely substituted benzofurans,
Tetrahedron (2015), doi: 10.1016/j.tet.2015.08.058.
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ACCEPTED MANUSCRIPT
For Table of Contents Use Only
One-pot three-component reactions of methyl ketones, phenols and a
nucleophile: an expedient way to synthesize densely substituted
benzofurans
Cheng Cheng, Changhui Liu and YanlongGu*
Graphic Abstract
OH
O
O
one-pot step-wise
sequential reaction
Nu
O
O
+
+
R
I2/DMSO
O
O
NuH
R
2
9 examples, 28~73% yields
OMe
O
R
CHO
NuH =
SH
MeO
OMe
N
H
intermediate
1

ACCEPTED MANUSCRIPT
One-pot three-component reactions of methyl ketones, phenols and a
nucleophile: an expedient way to synthesize densely substituted
benzofurans
a
a
a,b
Cheng Cheng , ChanghuiLiu and YanlongGu*
a
Key Laboratory for Large-Format Battery Materials and System, Ministry of Education,
School of Chemistry and Chemical Engineering, Huazhong University of Science and
Technology, 430074, Wuhan, China. Phone: (0)86-(0)27-87 54 37 32, Fax: (0)86-(0)27-87 54
4
5 32, E-mail: klgyl@hust.edu.cn
b
State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of
Chemical Physics, Lanzhou, 730000 (P.R. China)
Abstract: Three-component reactions of phenylglyoxal monohydrate, phenols and indoles
were developed with the aid of acid-catalyst, which produced various densely substituted
benzofurans with good to excellent yields. On the basis of this observation, a one-pot,
step-wise reaction was developed by using methyl ketones instead of using phenylglyoxal
component in I /DMSO system. At last, three-component reaction offered a useful way to
2
synthesize densely substituted benzofurans starting from simple and easily available
substrates. The indole component can be replaced by some other nucleophiles, such as
1
,2,4-trimethoxybenzene and thiophenol.
Keywords: Multi-component reactions, benzofurans, methyl ketone, phenylglyoxal
2

ACCEPTED MANUSCRIPT
1
. Introduction
A current trend in green organic chemistry is the development of highly integrated domino
processes with the aid of either a multi-functional catalyst system or a bi-functional reagent
1
that has well-designed structure. By using these concepts, simplified synthetic operational
units, together with reduced waste production as less workup procedures are applied can be
2
obtained. Another advantage of these strategies are that, the use of expensive and unstable
reagents may be avoided by establishing in situ generation methods, which enables a controlled
3
formation of these chemicals for the intended synthesis.
4
5
6
Recently, bifunctional aldo-X reagents, such as aldo-OH, aldo-acid, aldo-halide and
7
aldo-alkyne, have been widely used as building blocks in organic synthesis as these reagents
possess multiple reactive sides, enabling further cyclization. Alkylglyoxals are unique
variation of aldo-ketone reagents, which have been frequently employed in many organic
8
9
10
transformations. With these reagents, many heterocycles, such as furan, pyrrole, and
1
1
imidazole could be constructed by a single step reaction. Although many alkylglyoxals are
commercially available, these reagents are generally very expensive. A well-known method for
the synthesis of arylglyoxals starts from methyl ketones, which involves the use of
1
2
stoichiometric amount of high toxic selenium oxide (SeO ) as oxidant. Alcohols, styrenes
2
and phenylacetylenes have also been used as starting materials for the synthesis of arylglyoxals,
1
3
however their efficiencies are not satisfactory. In addition, because of the difficulty in
isolation, these reagents are normally available as their monohydrates. However, it is still
difficult to reach a high degree of purity and therefore, commercially available alkylglyoxals
are characterized by many degrees of purity ranging from 80% to 95%. Quite recently, a series
of interesting transformations that built-in the following two reactions (i) in situ generation of
3
arylglyoxal through a sp C-H oxidation and (ii) a downstream trapping of this reagent with
nucleophile through an electrophilic reaction, into one-pot cascade reactions have been
1
4
reported. Wu’s group first demonstrated the possibility of establishing this kind of cascade
reactions using I /DMSO system and contributed more than 10 research articles in this
2
1
5
region.
3

ACCEPTED MANUSCRIPT
Aldo-X bifuntional reagents have been frequently used as building blocks in developing
1
6
multi-component reactions (MCRs), which are a promising, hot field of chemistry since
they allow complicated molecules to be created by using one reaction in a fast and an
1
7
efficient manner.
In continuation of our research on developing MCRs of aldo-X
1
8
reagents, we envisioned that, incorporating the in situ generation of arylglyoxal from aryl
methyl ketones together with a downstream trapping of this reagent with two different
nucleophiles may allow us to develop some new MCRs. Out of this consideration, we started
a research program on this topic for a moment ago. Herein we disclose the successful
outcome of this attempt in which a hitherto-unreported one-pot, step-wise three-component
reaction of methyl ketone, phenol and indole were developed in I /DMSO system. With this
2
reaction, various densely substituted benzofurans, some of which may be valuable scaffolds
for biological screening, could be synthesized in a simple way.
2
. Results and discussion
To establish a three-component reaction based on our idea, a couple of nucleophiles that
can trap selectively the in situ generated arylglyoxal should be judiciously selected. These
nucleophiles should also be chemically stable toward I /DMSO system; otherwise, side
2
reaction may occur and consequently affect the outcome of the expected reaction
detrimentally. Therefore, our study commenced from a three-component condensation of
phenyl glyoxalmonohydrate (1a), 2-methylindole (2a), sesamol (3a) and the expected product
was 7-(2-methylindol-3-yl)-6-phenylfuro[2,3-f]-1,3-benzodioxole (4a) (Scheme 1). It should
be noted that this type of three-component condensation has not been reported yet to the best
of our knowledge. Some commonly used acids, such as toluenesulfonic acid (PTSA),
trifluoromethanesulfonic acid (TfOH) and FeCl , were proved to be effective catalysts for this
3
reaction, and the yields ranging from 86 % to 92 % were obtained. Molecular iodine can also
be used, however the yield reached only 79 % under the identical conditions. Despite the
yield is not very high, this result is very important as the addition of an external acid catalyst
may be avoided when updating the present MCR by means of replacing phenylglyoxal
component with acetophenone in conjunction with I /DMSO system. Initial event of the
2
4

ACCEPTED MANUSCRIPT
reaction in Scheme 1 might be a selective assembly of 1a with two nucleophiles, sesamol and
2
-methylindole, that generates a 1/1/1 condensation product, intermediate (I), which can be
converted then into 4a through an intra-molecular dehydration. Because 1a is very expensive
substrate, 2,2-diethoxyacetophenone that is much cheaper than 1a was also used in this type
of condensation reaction. However, the yield of 4a decreased to 72 % under the identical
conditions.
Scheme 1: Acid-catalyzed three-component reaction of 1a, 2a and 3a.
We probed then the scope of the reaction with respect to both of the indole, the
alkylglyoxal and the phenol components. As evidenced by the results in Figure1, indoles
with different substituents smoothly reacted with 1a and 3a, producing the expected
benzofurans in moderate to good yields. Both electron-rich and electron-poor indoles readily
participated in this reaction. The presence of a phenyl group in C-2 position of indole favored
the progress of the reaction as 4b and 4c were obtained in more than 90% yields. But the
yields obtained with ester- or nitro-functionalized indoles are rather poor (29-38 %) (4g and
4
h). We then examined a set of alkylglyoxals spanning a convenient spectrum of lipophilicity
and reactivity with 2a and 3a as the counter reagents. The reactions proceeded very well with
those containing 2-thienyl and 2-benzofuranyl groups, and the yields of 4j and 4k reached 91 %
and 77%, respectively. Cyclopropyl group in the glyoxal component was also delivered
uneventfully into the final product 4n, and 75 % yield was obtained in this case. Efforts to
use an aqueous solution of pyruvic aldehyde fell always into failure. Fortunately, the
expected product 4m could be synthesized alternatively by using methylglyoxal 1,1-dimethyl
5

ACCEPTED MANUSCRIPT
acetal as substrate although the yield reached only 43 %. The scope of the reaction with
respect to phenol component was next investigated. As Figure1 illustrates, sesamol can be
replaced by resorcine and phloroglucinol without significantly affecting the reaction yields.
But, simple phenol unwillingly participated in this condensation and the corresponding
product 4q was obtained only in 10 % yield under the same conditions.
Figure 1: Substrate scope of three-component reaction of phenylglyoxal, indole and phenols
catalyzed by PTSA.
In seeking further improvements in the reaction, we then investigated the possibility of
replacing the phenylglyoxal component with acetophenone (5a) in I /DMSO system. As
2
shown in Scheme2, when equal amount of reagent was used, after 10 hours of reaction in the
presence of one equivalent of molecular iodine in DMSO, the expected product 4a was
formed only in 24 % of yield. Attempts were made to raise the yield by altering the reaction
parameters, such as temperature, reaction time, the ratio of substrate and dosage of I , all
2
6

ACCEPTED MANUSCRIPT
were ineffective. We also tried to add some metal-based Lewis acids, such as CuCl , FeCl3
2
and Sc(OTf) , into the reaction system but, no significant yield improvement was observed
3
(see ESI, Table S1). An electrophilic alkylation of phenylglyoxal with 2a was proved to be a
stubborn side reaction, which consumed most of the generated phenylglyoxal intermediate,
diminishing thus the possibility of forming the desired product 4a. To solve this problem, we
then turned to developing a one-pot step-wise reaction. To our delight, we found that the
yield could be improved significantly when this reaction was performed in a one-pot stepwise
mode. In this protocol, initially, an equimolar mixture of acetophenone and molecular iodine
o
was allowed to react in DMSO for 6 hours at 60 C, enable to completion of forming
phenylglyoxal 1a. Subsequently, 2-methylindole 2a and sesamol 3a were added along with
2
3
0 mol% of PTSA to the reaction solution. Then the reaction mixture was heated at 80 °C for
h (Scheme 3). This sequential reaction afforded the desired product 4a in 67% yield.
Considering the following facts: (i) alkylglyoxals are generally very expensive, and most of
them are not commercially available; and (ii) literature’s methods for their preparations are
either associated with the use of toxic reagents or plagued by low yields, the present one-pot
step-wise protocol for the synthesis of densely substituted benzofurans is very promising as it
starts from simple methyl ketones, which are readily available and not expensive. It is worth
noting that the reaction can also be effectively scaled up with the similar efficiency. For
example, the reaction of acetophenone (5a, 20 mmol) with 2-methylindole (2a, 10 mmol) and
sesamol (3a, 10 mmol) gave the corresponding benzofuran 4a in 63 % yield (2.31 g).
Scheme 2: One-pot three-component reaction of 5a, 2a and 3a in I /DMSO system.
2
7

ACCEPTED MANUSCRIPT
Scheme3: One-pot step-wise three-component reaction of 5a, 2a and 3a (the first step: 5a,
o
1
0
.0 mmol, DMSO, 1 ml, 6 hours, 60 C; the second step: 2a, 0.5 mmol, 3a, 0.5 mmol, PTAS,
o
a
.1 mmol, 80 C, 3 hours. Yield was calculated with respect to 2a. : the reaction scale is 10
mmol).
Then we investigated the substrate scope of the one-pot sequential reaction and various
methyl ketones were submitted to condensation reactions with sesamol and 2-methylindole in
I2/DMSO system. As evidenced by the results in Figure 2, acetophenones with different
substituents smoothly reacted with 2a and 3a. In all the cases, the corresponding benzofurans
were obtained in moderate yields, whatever the nature of the substituent present on the
acetophenone (electron-donating or electron-withdrawing). Acid-labile functionalities, such
as benzyloxy and methylthio groups are survived under the reaction conditions (4z and 4ai).
The presence of substituent group in ortho position of the phenyl ring resulted in a slight
decrease in yield due perhaps to the effect of stereo hindrance (4aa).
5
-Acetyl-2,3-dihydrobenzofuran that is susceptible toward both acid and oxidant can also be
used in this reaction (4aj). Aryl methyl ketones with heterocyclic groups, such as thienyl and
benzofuranyl are also viable substrates in this reaction although low yields were obtained in
some cases (4af and 4aj). A ketone containing amino group, 4-dimethylaminoacetophenone
can also be converted uneventfully to the corresponding substituted benzofuran without
damage of the amino functionality (4ae). However, attempts to use 2-acetylfuran and
acetylferrocene led only to the formation of messy mixtures. By the same token,
1
-phenyl-1,2-propanedione cannot be used in this reaction either. Only the unreacted starting
materials were recovered when 3-acetylcoumarin was used as substrate. It is gratifying that
this one-pot sequential reaction was also found to be amenable for using aliphatic ketones,
such as 3-methyl-2-butanone and methyl tert-butyl ketone. Although the yields are not good,
8

ACCEPTED MANUSCRIPT
these results are quite promising as I /DMSO system was known to be less effective for the
2
1
5
oxidation of aliphatic ketones. To further extend the scope of the reaction, other indoles and
phenols were also subjected to the condensation reaction under the conditions of Scheme 2.
2
-Phenylindole and simple indole readily participated in the reaction meanwhile resorcine
and phloroglucinol dihydrate could be smoothly converted into the desired products in
I2/DMSO system. These results further extended to the product diversity of the one-pot
step-wise sequential reaction.
H
H
H
H
N
N
N
N
O
O
O
O
O
O
O
O
R
O
SMe
O
O
O
O
O
O
O
4y 67%
4
l 61%
4z 60%
4
4
4
4
4
4
4
4
r R = Me, 49%
s R = OMe, 56%
H
H
H
N
t
N
t R = Bu , 58 %
N
u R = n-amyl, 48 %
v R = F, 47 %
w R = Cl, 50 %
i R = Br, 46 %
x R = I, 43 %
O
O
O
O
O
C H
6
5
O
O
O
O
F
4
aa 39%
4ab 58%
4ac 45%
H
N
H
H
H
N
N
N
O
O
O
O
O
O
O
O
N
O
O
O
S
O
O
4
ad 42%
4ae 37%
4af 28%
4j 36%
H
N
H
N
H
N
H
N
O
O
O
O
O
OBn
O
O
O
O
O
O
O
O
4ag 32%
4ah 36%
4ai 69%
4aj 70%
H
N
H
H
H
N
N
N
OH
O
O
O
O
O
O
O
O
HO
HO
4
b 73 %
4o 51 %
4p 53 %
4
c 35 %
Figure 2: Scope for the one-pot step-wise three-component reaction.
The above mentioned reactions stem upon the uses of arylglyoxals as intermediates, but the
isolation and purification steps were avoided. Considering also the fact that, arylglyoxals
were generally synthesized by using toxic SeO as oxidant, the present MCRs displayed
2
9

ACCEPTED MANUSCRIPT
salient advantages in terms of avoiding the use of toxic reagents and minimizing the
generation of wastes. All these features gave us impulsion to explore the possibility of using
other nucleophiles to replace the indole component in these MCRs. We found that, in
I2/DMSO system, 1,2,4-trimethoxybenzene and thiophenol reacted in the same way with 3a
and 5a to afford the corresponding benzofuran products 7a and 9a with 71 % and 42% of
yields respectively (Scheme 4). These results demonstrated that the strategy of screening
three-component reactions with I /DMSO system by using aryl methyl ketones as starting
2
material for generating arylglyoxal intermediate is indeed viable for creating MCRs.
Scheme 4: Three-component reaction of 3a, 5a and 6a or 8a in I /DMSO system.
2
3
. Conclusions
In conclusion, a three-component reaction of alkylglyoxals, phenols and indoles were
developed by using Brønsted acid as catalyst, which produced densely substituted
benzofurans in moderate to excellent yields. Because alkylglyoxals are generally expensive
and their synthesis is plagued not only by low yield but also by the use of toxic reagent, an
alternative one-pot, step-wise three-component reaction was also developed in I /DMSO
2
system by using methyl ketone instead of the alkylglyoxal component. Indole,
1
,2,4-trimethoxybenzene and thiophenol were all able to act as counterpart nucleophile in
conjunction with phenols, such as sesamol, phloroglucinol dihydrate and resorcine. The
unique ability of I /DMSO system is the key to make the reaction possible as it works as dual
2
oxidant and acid catalyst in the reaction. This approach may be useful for establishing a wide
1
0

ACCEPTED MANUSCRIPT
range of library of densely substituted benzofurans with variation of the combination of
nucleophiles.
4
. Experimental Section
.1. General
4
Melting points were determined by microscopic melting point meter and were uncorrected.
IR spectra were recorded on a FT-IR Bruker (EQUINOX 55) using KBr pellets or neat liquid
1
13
technology. H and C NMR spectra were recorded on a Bruker AV-400. Chemical shifts are
expressed in ppm relative to Me Si in solvent. All chemicals used were of reagent grade and
4
were used as received without further purification. All reactions were conducted in a 10 mL
of V-type flask equipped with triangle magnetic stirring.
4
.2. One-pot three-component reaction of phenylglyoxal monohydrate, 2-methylindole
and sesamol
In a typical reaction, phenylglyoxal monohydrate (0.2 mmol) was mixed with 2-methylindol
(0.2 mmol), sesamol (0.2 mmol) and PTSA (0.04 mmol, 20 mol%) in nitromethane (1.0 mL),
o
The mixture was then stirred at 80 C for 3 hours. After the completion of the reaction, the
mixture was cooled to room temperature, and the product was obtained by isolation with
preparative TLC (eluting solution: petroleum ether / dichloromethane = 1 / 2 (v/v)). Tests for
substrate scope were performed according to an analogous procedure.
4
.3. One-pot three-component reaction of acetophenone, sesamol and 2-methylindole
In a typical reaction, a mixture of acetophenone (0.3 mmol), 2-methylindol (0.2 mmol),
sesamol (0.3mmol), I (0.3mmol) and PTSA (0.04mmol, 20 mol%) in DMSO (1.0 mL) was
2
o
stirred at 80 C for 6 hours. After the disappearance of the reactants (monitored by TLC)
water was added (10mL) to the reaction mixture, then extracted with EtOAc (3 × 10 mL).
The acquired organic phase was combined and dried with anhydrous Na SO . The volatile
2
4
components were removed under reduced pressure. The product was obtained by isolation
with preparative TLC (eluting solution: petroleum ether / dichloromethane = 1 / 2 (v/v)).
4
2
.4. One-pot step-wise three-component reaction of acetophenone, sesamol and
-methylindole
1
1

ACCEPTED MANUSCRIPT
In a typical reaction, acetophenone (0.4 mmol) and I (0.4 mmol) was stirred in DMSO (1 mL)
2
o
at 60 C for 6 hours. After the mixture was cooled to room temperature and subsequently,
2
-methylindol (0.2 mmol), sesamol (0.2 mmol) were added to the reaction solution along
o
with PTSA (0.04mmol, 20 mol%). The mixture was then stirred at 80 C for 3 hours. At the
end of the reaction, water (10mL) was added and then extracted with EtOAc (3 × 10 mL).
The acquired organic phase was combined and dried with anhydrous Na SO . The volatile
2
4
components were removed under reduced pressure. The product was obtained by isolation
with preparative TLC (eluting solution: petroleum ether / dichloromethane = 1 / 2 (v/v)).
Tests for substrate scope and the reaction of using other nucleophiles were all performed
according to an analogous procedure. When a 10 mmol scale reaction was conducted, the
product was isolated by silica column chromatography.
4
.5. Spectroscopic data of new compounds:
4
.5.1. 2-Methyl-3-(6-phenyl-[1,3]dioxolo[4,5-f]benzofuran-7-yl)-1H-indole (4a). Yellow
o
1
o
1
solid; mp: 172–175 C; H NMR (400 MHz, CDCl , 25 C, TMS): H NMR (400 MHz,
3
o
CDCl 25 C, TMS) δ 8.00 (s, 1H), 7.65–7.60 (m, 2H), 7.29 (d,J = 5.6 Hz, 1H), 7.19–7.12 (m,
3,
5
H), 7.06 (s, 1H), 7.02 (t, J = 7.5 Hz, 1H), 6.66 (s, 1H), 5.87 (d, J = 1.2 Hz, 2H), 2.07 (s, 3H).
1
3
o
C NMR (100 MHz, CDCl , 25 C) δ 150.9, 149.3, 146.5, 144.6, 135.9, 133.2, 131.6, 128.5,
3
1
28.4, 128.2, 128.0, 127.4, 125.5, 124.8, 121.6, 119.9, 119.7, 110.8, 110.5, 104.5, 101.3, 99.5,
-1
9
3.5, 12.5; IR: γ = 3403, 2913, 1728, 1461, 1308, 1147, 1037, 946, 846, 745, 695 cm ;
+
HRMS (ESI): m/z: calcd for C H NNaO : 390.1106 [M+Na] ; found: 390.1110.
2
4
17
3
4
.5.2. 2-Phenyl-3-(6-phenyl-[1,3]dioxolo[4,5-f]benzofuran-7-yl)-1H-indole (4b).Yellow
1
o
liquid; H NMR (400 MHz, CDCl , 25 C, TMS) δ 8.56 (s, 1H), 7.62 (d, J = 7.0 Hz, 2H),
3
7
.43 (d, J = 8.0 Hz, 2H), 7.24 (d, J = 8.0 Hz, 1H), 7.19–7.08 (m, 8H), 7.03 (s, 1H), 7.00 (t, J
1
3
o
=
7.6 Hz, 1H), 6.44 (s, 1H), 5.82 ppm (s, 2H); C NMR (100 MHz, CDCl , 25 C) δ 151.4,
3
1
1
3
49.5, 146.5, 144.6, 136.4, 135.4, 132.4, 131.3, 128.9, 128.8, 128.4, 127.8, 127.5, 126.9,
25.5, 124.4, 122.9, 120.4, 120.4, 111.1, 110.8, 104.6, 101.2, 99.3, 93.4 ppm; IR: γ = 3414,
-1
060, 2981, 2898, 1722, 1460, 1307, 1153, 1038, 922, 745, 694 cm ; HRMS (ESI): m/z:
+
calcd for C H NNaO : 452.1263 [M+Na] ; found: 452.1261.
2
9
19
3
1
2

ACCEPTED MANUSCRIPT
4
.5.3. 1-Ethyl-2-phenyl-3-(6-phenyl-[1,3]dioxolo[4,5-f]benzofuran-7-yl)-1H-indole (4c).
1
o
Yellow liquid; H NMR (400 MHz, CDCl , 25 C, TMS) δ 7.49–7.45 (m, 3H), 7.37 (d, J =
3
7
2
1
1
1
.9 Hz, 1H), 7.18–7.06 (m, 10H), 6.95 (s, 1H), 6.57 (s, 1H), 5.83 (s, 2H), 4.18 (q, J = 7.2 Hz,
13
o
H), 1.32 ppm (t, J = 7.1 Hz, 3H); C NMR (101 MHz, CDCl , 25 C) δ 151.6, 149.2, 146.2,
3
44.4, 138.9, 136.9, 131.8, 131.5, 130.1, 128.4, 128.3, 128.2, 127.9, 127.3, 125.8, 125.0,
22.2, 120.5, 120.1, 110.9, 110.1, 105.3, 101.2, 99.3, 93.3, 39.1, 15.6 ppm; IR: γ = 2977,
-1
930, 2897, 1737, 1461, 1308, 1241, 1162, 1091, 1041, 945, 743, 697 cm ; HRMS (ESI):
+
m/z: calcd for C H NNaO : 480.1576 [M+Na] ; found: 480.1572.
3
1
23
3
4
1
.5.4. 3-(6-Phenyl-[1,3]dioxolo[4,5-f]benzofuran-7-yl)-1H-indole (4d). Brown solid; mp:
o
1
o
86–189 C; H NMR (400Mz, DMSO, 25 C) δ 11.53 (s, 1H), 7.66 (d, J = 2.4 Hz, 1H), 7.57
(d, J = 7.0 Hz, 2H), 7.51 (d, J = 8.2 Hz, 1H), 7.35 (s, 1H), 7.28–7.22 (m, 3H), 7.13 (t, J = 7.5
13
Hz, 1H), 7.02 (d, J = 7.9 Hz, 1H), 6.89 (t, J = 7.4 Hz, 1H), 6.82 (s, 1H), 6.05 ppm (s, 2H); C
o
NMR (100Mz, DMSO, 25 C) δ 149.7, 149.1, 146.8, 144.9, 137.0, 131.3, 128.9, 128.1, 126.0,
1
3
25.9, 125.5, 124.4, 122.0, 119.9, 119.6, 112.5, 111.8, 105.5, 101.8, 99.1, 94.0 ppm; IR: γ =
-1
422, 2918, 1460, 1305, 1162, 1097, 1032, 801, 745, 694 cm ; HRMS (ESI): m/z: calcd for
+
C H NNaO :376.0950 [M+Na] ; found: 376.09501.
23
15
3
4
.5.5. 1-Ethyl-2-methyl-3-(6-phenyl-[1,3]dioxolo[4,5-f]benzofuran-7-yl)-1H-indole (4e).
1
o
Yellow liquid; H NMR (400 MHz, CDCl , 25 C, TMS) δ 7.63–7.61 (m, 2H), 7.38 (d, J =
3
8
.2 Hz, 1H), 7.34 (d, J = 7.9 Hz, 1H), 7.22–7.16 (m, 4H), 7.07 (s, 1H), 7.04 (dd, J = 10.0, 4.9
Hz, 1H), 6.67 (s, 1H), 5.92 (d, J = 3.0 Hz, 2H), 4.19 (q, J = 7.3 Hz, 2H), 2.15 (s, 3H), 1.38
13
o
ppm (t, J = 7.2 Hz, 3H); C NMR (100 MHz, CDCl , 25 C) δ 150.8, 149.3, 146.4, 144.5,
3
1
1
36.2, 134.1, 131.7, 128.4, 127.5, 127.3, 125.5, 124.9, 121.1, 119.8, 119.5, 111.2, 109.0,
03.8, 101.3, 99.6, 93.4, 38.2, 15.5, 11.1 ppm; IR: γ = 2976, 2921, 1735, 1462, 1307, 1159,
-1
1
131, 1035, 945, 742, 695 cm ; HRMS (ESI): m/z: calcd for C H NNaO : 418.1419
26 21 3
+
[
M+Na] ; found: 418.1412.
1
3

ACCEPTED MANUSCRIPT
4
.5.6. 2,5-Dimethyl-3-(6-phenyl-[1,3]dioxolo[4,5-f]benzofuran-7-yl)-1H-indole (4f). Yellow
1
o
liquid; H NMR (400 MHz, CDCl , 25 C, TMS) δ 7.94 (s, 1H), 7.63 (d, J = 7.2 Hz, 2H),
3
7
5
1
1
2
.24–7.15 (m, 4H), 7.10 (s, 1H), 7.07 (s, 1H), 7.00 (d, J = 8.1 Hz, 1H), 6.67 (s, 1H),
13
o
.95–5.93 (m, 2H), 2.34 (s, 3H), 2.10 ppm (s, 3H); C NMR (100 MHz, CDCl , 25 C) δ
3
50.9, 149.3, 146.4, 144.5, 134.1, 133.2, 131.6, 129.2, 128.6, 128.4, 127.9, 127.4, 125.5,
24.8, 123.1, 119.3, 110.8, 110.1, 104.0, 101.3, 99.5, 93.4, 21.5, 12.5 ppm; IR: γ = 3397,
-1
917, 1733, 1462, 1307, 1159, 1037, 943, 799, 765, 694 cm ; HRMS (ESI): m/z: calcd for
+
C H NNaO : 404.1263 [M+Na] ; found: 404.1260.
25
19
3
4
.5.7. Ethyl 3-(6-phenyl-[1,3]dioxolo[4,5-f]benzofuran-7-yl)-1H-indole-2-carboxylate (4g).
o
1
o
Yellow solid; mp: 209–212 C; H NMR (400 MHz, CDCl , 25 C, TMS) δ 9.41 (s, 1H), 7.56
3
(d, J = 6.8 Hz, 2H), 7.49 (d, J = 8.5 Hz, 1H), 7.36 (d, J = 8.1 Hz, 2H), 7.18(q, J = 8.0 Hz 3H),
7
.08 (s, 1H), 7.05 (d, J = 8.2 Hz, 1H), 6.57 (s, 1H), 5.95 (s, 2H), 4.09 (ddd, J = 14.1, 7.1, 3.4
1
3
o
Hz, 2H), 0.90 ppm (d, J = 7.1 Hz, 3H); C NMR (100 MHz, CDCl , 25 C) δ 162.2, 151.4,
3
1
1
1
49.2, 146.4, 144.6, 136.5, 131.4, 128.8, 128.5, 127.7, 126.1, 125.6, 125.6, 124.7, 122.3,
21.1, 113.6, 112.1, 109.9, 109.5, 101.4, 99.3, 93.4, 61.1, 13.8 ppm; IR: γ = 3328, 2919, 1727,
-1
694, 1462, 1309, 1248, 1161, 1036, 945, 747, 694 cm ; HRMS (ESI): m/z: calcd for
+
C H KNO : 464.0900 [M+K] ; found: 464.0892.
26
19
5
4
.5.8. 6-Nitro-3-(6-phenyl-[1,3]dioxolo[4,5-f]benzofuran-7-yl)-1H-indole (4h). Orange solid;
o
1
o
mp: 198–201 C; H NMR (400Mz, DMSO, 25 C) δ 12.30 (s, 1H), 8.44 (d, J = 2.0 Hz, 1H),
8
.12 (d, J = 2.4 Hz, 1H), 7.77 (dd, J = 8.8, 2.1 Hz, 1H), 7.51 (dd, J = 8.0, 1.3 Hz, 2H), 7.37 (s,
13
1
H), 7.30–7.25 (m, 3H), 7.13 (d, J = 8.8 Hz, 1H), 6.82 (s, 1H), 6.06 ppm (s, 2H); C NMR
o
(
100Mz, DMSO, 25 C) δ 162.8, 149.2, 147.0, 145.1, 142.7, 135.4, 132.5, 130.9, 130.8,
1
2
29.1, 128.5, 126.0, 124.0, 120.0, 114.8, 110.3, 109.3, 106.9, 101.9, 98.9, 94.0 ppm; IR: γ =
-1
917, 1507, 1461, 1335, 1311, 1163, 1033, 821, 696 cm ; HRMS (ESI): m/z: calcd for
+
C H N NaO : 435.0957 [M+Na] ; found: 435.0955.
24
16
2
5
4
.5.9. 3-(6-(4-Bromophenyl)-[1,3]dioxolo[4,5-f]benzofuran-7-yl)-2-methyl-1H-indole (4i).
1
4

ACCEPTED MANUSCRIPT
o
1
o
Brown solid; mp: 188–191 C; H NMR (400 MHz, CDCl , 25 C, TMS) δ 8.18 (s, 1H), 7.91
3
(d, J = 8.6 Hz, 0.5H), 7.79 (d, J = 8.6 Hz, 0.5H), 7.67 (d, J = 8.6 Hz, 0.5H), 7.58 (d, J = 8.5
Hz, 0.5H), 7.49 (d, J = 8.7 Hz, 2H), 7.39 (d, J = 8.1 Hz, 1H), 7.35 (s, 1H), 7.29–7.25 (m, 1H),
7
3
1
.19 (t, J = 7.6 Hz, 1H), 7.06 (s, 1H), 6.66 (s, 1H), 5.97 (d, J = 2.1 Hz, 2H), 2.19 ppm (s,
1
3
H); C NMR (100 MHz, CDCl ) δ 149.7, 149.4, 146.7, 144.7, 135.9, 133.1, 131.6, 130.5,
3
28.4, 127.9, 126.9, 125.7, 124.6, 121.7, 121.3, 120.0, 119.5, 110.6, 101.4, 99.5, 93.4, 12.6
-1
ppm; IR: γ = 3397, 2917, 1722, 1460, 1307, 1147, 1038, 947, 828, 746 cm ; HRMS (ESI):
+
m/z: calcd for C H BrNNaO : 468.0211 [M+Na] ; found: 468.0205.
2
4
16
3
4
.5.10. 3-(6-(Benzofuran-2-yl)-[1,3]dioxolo[4,5-f]benzofuran-7-yl)-2-methyl-
1
o
1
H-indole (4j). Yellow liquid; H NMR (400 MHz, CDCl , 25 C, TMS) δ 8.26 (s, 1H), 7.40
3
(d, J = 8.0 Hz, 1H), 7.33 (dd, J = 14.0, 7.7 Hz, 3H), 7.19–7.15 (m, 3H), 7.11 (d, J = 2.3 Hz,
1
H), 7.04 (dd, J = 8.6, 5.6 Hz, 1H), 6.71 (s, 1H), 6.56 (s, 1H), 5.89 (d, J = 2.7 Hz, 2H), 2.22
1
3
o
ppm (s, 3H); C NMR (100 MHz, CDCl , 25 C) δ 154.6, 150.0, 147.8, 147.3, 145.1, 143.2,
3
1
1
1
35.9, 133.9, 128.8, 128.4, 128.1, 128.0, 124.5, 123.9, 123.2, 121.7, 121.0, 120.0, 119.6,
13.5, 111.3, 110.7, 103.6, 103.3, 101.6, 99.6, 93.7, 12.7 ppm; IR: γ = 3405, 2905, 1732,
-1
618, 1617, 1461, 1302, 1259, 1170, 1147, 1038, 945, 805, 746 cm ; HRMS (ESI): m/z:
+
calcd for C H NNaO : 430.1055 [M+Na] ; found: 430.1056.
2
6
17
4
4
1
1
7
0
.5.11. 3-(6-(5-Bromothiophen-2-yl)-[1,3]dioxolo[4,5-f]benzofuran-7-yl)-2-methyl-
1
o
H-indole (4k).Yellow liquid; H NMR (400 MHz, CDCl , 25 C, TMS) δ 8.19 (d, J = 5.6 Hz,
3
H), 7.43 (s, 0.52H), 7.34 (d, J = 8.1 Hz, 0.48H), 7.19 (d, J = 7.3 Hz, 1H), 7.17–7.14 (m, 1H),
.10 (d, J = 4.7 Hz, 2H), 7.06–7.04 (m, 1H), 6.89 (q, J = 4.8 Hz, 1H), 6.63 (s, 0.42H), 6.58 (s,
1
3
.58H), 5.92 (d, J = 1.5 Hz, 2H), 2.24 (d, J = 6.4 Hz, 1.39H), 2.19 ppm (s, 1.65H); C NMR
o
(
100 MHz, CDCl , 25 C) δ 149.1, 148.0, 147.8, 146.5, 146.4, 144.8, 144.7, 136.6, 135.9,
3
1
1
1
34.7, 133.0, 127.3, 127.3, 125.3, 125.1, 124.2, 125.1, 123.2, 121.6, 120.7, 119.9, 119.5,
15.0, 113.5, 110.5, 101.4, 101.3, 99.2, 98.9, 93.5, 93.4, 12.7, 12.6 ppm; IR: γ =3411, 2898,
-1
461, 1306, 1169, 1146, 1037, 946, 908, 734, 702 cm ; HRMS (ESI): m/z: calcd for
+
C H BrNNaO S: 473.9775 [M+Na] ; found: 473.9772.
22
14
3
1
5

ACCEPTED MANUSCRIPT
4
.5.12. 3-(6-(Benzo[d][1,3]dioxol-5-yl)-[1,3]dioxolo[4,5-f]benzofuran-7-yl)-2-
o
1
o
methyl-1H-indole (4l). Brown solid; mp: 240–243 C; H NMR (400Mz, DMSO, 25 C) δ
1.34 (s, 1H), 7.40 (d, J = 8.0 Hz, 1H), 7.31 (s, 1H), 7.11–7.04 (m, 3H), 6.97 (d, J = 1.6 Hz,
H), 6.93–6.89 (m, 1H), 6.84 (d, J = 8.3 Hz, 1H), 6.58 (s, 1H), 6.03 (d, J = 1.4 Hz, 2H), 5.97
1
1
1
3
o
(
d, J = 1.2 Hz, 2H), 2.20 ppm (s, 3H);. C NMR (100Mz, DMSO, 25 C) δ 150.1, 148.7,
47.9, 147.2, 146.5, 144.8, 136.4, 134.3, 127.7, 125.4, 124.5, 121.2, 119.6, 119.5, 118.7,
11.5, 110.1, 109.1, 105.5, 102.5, 101.8, 101.6, 99.0, 94.0, 12.7 ppm; IR: γ = 3399, 2917,
1
1
1
4
-1
459, 1307, 1245, 1145, 1037, 810, 746 cm ; HRMS (ESI): m/z: calcd for C H NNaO :
2
5
17
5
+
34.1004 [M+Na] ; found: 434.1001.
4
.5.13. 2-Methyl-3-(6-methyl-[1,3]dioxolo[4,5-f]benzofuran-7-yl)-1H-indole (4m). Yellow
1
o
liquid; H NMR (400 MHz, CDCl , 25 C, TMS) δ 8.05 (s, 1H), 7.33 (t, J = 7.4 Hz, 2H), 7.16
3
(t, J = 7.7 Hz, 1H), 7.07 (dd, J = 8.9, 5.9 Hz, 1H), 6.99 (s, 1H), 6.68 (s, 1H), 5.94–5.91 (m,
1
3
o
2
1
1
H), 2.32 ppm (d, J = 1.3 Hz, 6H); C NMR (100 MHz, CDCl , 25 C) δ 151.4, 149.1, 145.2,
3
44.0, 135.6, 132.7, 128.5, 123.5, 121.5, 119.7, 119.3, 110.4, 110.1, 104.2, 101.1, 99.1, 93.3,
-1
3.2, 12.6 ppm; IR: γ = 3404, 2917, 1725, 1461, 1302, 1143, 1038, 944, 746 cm ; HRMS
+
(
ESI): m/z: calcd for C H NNaO : 328.0950 [M+Na] ; found: 328.0949.
1
9
15
3
4
.5.14. 3-(6-Cyclopropyl-[1,3]dioxolo[4,5-f]benzofuran-7-yl)-2-methyl-1H-indole (4n).
1
o
Yellow liquid; H NMR (400 MHz, CDCl , 25 C, TMS) δ 7.99 (s, 1H), 7.44 (d, J = 7.6 Hz,
3
1
5
2
H), 7.27 (s, 1H), 7.15 (t, J = 7.2 Hz, 1H), 7.07 (t, J = 7.6 Hz, 1H), 6.92 (s, 1H), 6.66 (s, 1H),
.88 (d, J = 2.4 Hz, 2H), 2.33 (s, 3H), 1.85 (ddd, J = 8.4, 5.0, 3.3 Hz, 1H), 1.07 (dd, J = 6.1,
1
3
.8 Hz, 1H), 1.00 (dd, J = 6.3, 2.7 Hz, 1H), 0.89–0.83 ppm (m, 2H); C NMR (100 MHz,
o
CDCl , 25 C) δ 155.0, 148.4, 145.1, 144.1, 135.7, 133.1, 128.7, 123.9, 121.4, 119.7, 119.5,
3
110.5, 109.3, 104.1, 101.1, 98.9, 93.4, 12.7, 9.2, 7.2, 6.9 ppm; IR: γ = 3404, 2915, 1728, 1461,
-1
1
300, 1139, 1037, 943, 850, 746 cm ; HRMS (ESI): m/z: calcd for C H NNaO : 354.1106
21
17
3
+
[
M+Na] ; found: 354.1102.
1
6

ACCEPTED MANUSCRIPT
1
4
.5.15. 3-(2-Methyl-1H-indol-3-yl)-2-phenylbenzofuran-6-ol (4o). Yellow liquid; H NMR
o
(
400 MHz, CDCl , 25 C, TMS) δ 8.11 (s, 1H), 7.65 (d, J = 7.0 Hz, 2H), 7.32 (dd, J = 11.9,
3
8
.1 Hz, 2H), 7.21 (d, J = 1.9 Hz, 1H), 7.19–7.16 (m, 3H), 7.11 (d, J = 8.4 Hz, 1H), 7.06 (d, J
1.9 Hz, 1H), 7.04–7.01 (m, 1H), 6.70 (dd, J = 8.4, 2.1 Hz, 1H), 6.04 (s, 1H), 2.12 ppm (s,
=
1
3
o
3
1
1
1
H); C NMR (100 MHz, CDCl , 25 C) δ 155.0, 154.2, 150.3, 135.8, 133.2, 131.6, 128.4,
3
28.4, 128.3, 127.9, 127.5, 125.7, 124.8, 121.5, 121.3, 119.8, 119.7, 111.8, 110.5, 110.1,
04.5, 98.2, 12.6 ppm; IR: γ = 3404, 2921, 1706, 1621, 1487, 1458, 1374, 1283, 1149, 1116,
-1
059, 961, 812, 766, 746, 694 cm ; HRMS (ESI): m/z: calcd for C H NO : 340.1338
23
18
2
+
[
M+H] ; found: 340.1331.
1
4
.5.16. 3-(2-Methyl-1H-indol-3-yl)-2-phenylbenzofuran-4,6-diol (4p). Yellow liquid; H
o
NMR (400 MHz, CDCl , 25 C, TMS) δ 8.42 (s, 1H), 7.52 (d, J = 6.7 Hz, 2H), 7.39 (d, J =
3
7
.8 Hz, 1H), 7.33 (d, J = 8.0 Hz, 1H), 7.18 (ddd, J = 9.5, 8.1, 1.5 Hz, 5H), 6.68 (d, J = 1.8 Hz,
1
3
1
H), 6.49 (s, 1H), 6.24 (d, J = 1.8 Hz, 1H), 5.48 (s, 1H), 2.14 ppm (s, 3H). C NMR (100
o
MHz, CDCl , 25 C) δ 156.0, 155.6, 151.0, 149.3, 136.0, 134.2, 131.2, 128.5, 128.4, 127.9,
3
1
27.7, 127.5, 125.3, 122.5, 120.8, 119.0, 112.5, 110.9, 107.1, 103.4, 98.3, 91.2, 12.2 ppm; IR:
-1
γ = 3495, 3400, 2923, 1705, 1634, 1494, 1458, 1262, 1139, 1074, 826, 748, 694 cm ; HRMS
+
(
ESI): m/z: calcd for C H NO : 356.1287 [M+H] ; found: 356.1280.
2
3
18
3
1
4
.5.17. 2-Methyl-3-(2-phenylbenzofuran-3-yl)-1H-indole (4q).Yellow liquid; H NMR (400
o
MHz, CDCl , 25 C, TMS) δ 8.14 (s, 1H), 7.72 (d, J = 6.8 Hz, 2H), 7.59 (d, J = 8.4 Hz, 1H),
3
7
.41 (d, J = 8.1 Hz, 1H), 7.33 (t, J = 7.6 Hz, 4H), 7.29–7.25 (m, 2H), 7.21–7.17 (m, 2H), 7.05
13
o
(
t, J = 7.5 Hz, 1H), 2.19 ppm(s, 3H) ; C NMR (100 MHz, CDCl , 25 C) δ 150.6, 141.6,
3
1
31.2, 130.0, 128.4, 127.9, 126.9, 126.9, 126.8, 126.1, 124.4, 122.6, 121.5, 121.0, 120.4,
1
20.3, 119.7, 111.1, 110.4, 12.6 ppm; IR: γ = 2920, 2851, 1730, 1462, 1260, 1159, 1096,
-1
+
1
042, 802, 742, 693 cm ;HRMS (ESI): m/z: calcd for C H NNaO: 346.1208 [M+Na] ;
23 17
found: 346.1206.
4
.5.18. 2-Methyl-3-(6-(p-tolyl)-[1,3]dioxolo[4,5-f]benzofuran-7-yl)-1H-indole (4r). Yellow
1
7

ACCEPTED MANUSCRIPT
1
o
liquid; H NMR (400 MHz, CDCl , 25 C, TMS) δ 8.01 (s, 1H), 7.51 (d, J = 8.2 Hz, 2H),
3
7
.32 (t, J = 8.7 Hz, 2H), 7.16 (t, J = 7.2 Hz, 2H), 7.06 (s, 1H), 7.01 (d, J = 8.3 Hz, 2H), 6.65
1
3
(
s, 1H), 5.92 (d, J = 2.0 Hz, 2H), 2.26 (s, 3H), 2.13 ppm (s, 3H). C NMR (100 MHz, CDCl ,
3
o
2
1
2
5 C) δ 151.2, 149.1, 146.2, 144.4, 137.3, 135.8, 133.1, 129.2, 128.8, 128.2, 125.4, 124.8,
21.5, 119.9, 119.7, 110.5, 109.9, 104.6, 101.3, 99.4, 93.4, 21.3, 12.6 ppm; IR: γ = 3403,
-1
919, 1727, 1460, 1309, 1146, 1038, 947, 823, 745 cm ; HRMS (ESI): m/z: calcd for
+
C H NNaO : 404.1263 [M+Na] ; found: 404.1261.
25
19
3
4
.5.19. 3-(6-(4-Methoxyphenyl)-[1,3]dioxolo[4,5-f]benzofuran-7-yl)-2-methyl-1H-
o
1
o
indole (4s). Brown solid; mp: 195–197 C; H NMR (400 MHz, CDCl , 25 C, TMS) δ 8.06
3
(s, 1H), 7.55 (d, J = 8.9 Hz, 2H), 7.33 (d, J = 7.6 Hz, 2H), 7.17 (d, J = 7.8 Hz, 1H), 7.06 (s,
1
3
1
5
8
4
H), 6.75 (d, J = 8.9 Hz, 2H), 6.65 (s, 1H), 5.93 (d, J = 2.3 Hz, 2H), 3.74 (s, 3H), 2.15 ppm (s,
1
3
o
H). C NMR (100 MHz, CDCl , 25 C) δ 159.0, 151.1, 149.0, 146.0, 144.4, 135.8, 133.0,
3
28.3, 127.0, 124.9, 124.4, 121.5, 119.9, 119.7, 113.9 , 110.4, 108.9, 104.6, 101.2, 99.3, 93.3,
5.2, 12.6 ppm; IR: γ = 3401, 2908, 1733, 1506, 1460, 1308, 1251, 1176, 1246, 1035, 946,
-1
+
36, 746 cm ; HRMS (ESI): m/z: calcd for C H NNaO : 420.1212 [M+Na] ; found:
25
19
4
20.1212.
4
.5.20. 3-(6-(4-(Tert-butyl)phenyl)-[1,3]dioxolo[4,5-f]benzofuran-7-yl)-2-methyl-1H-
o
1
o
indole (4t). Yellow solid; mp: 202–205 C; H NMR (400 MHz, CDCl , 25 C, TMS) δ 8.06
3
(s, 1H), 7.56 (d, J = 8.3 Hz, 2H), 7.34 (d, J = 8.0 Hz, 1H), 7.30 (d, J = 7.8 Hz, 1H), 7.22 (dd,
J = 8.1, 3.5 Hz, 2H), 7.14 (dd, J = 7.5, 3.4 Hz, 1H), 7.05 (d, J = 4.6 Hz, 1H), 7.03 (s, 1H),
13
6
.63 (s, 1H), 5.92 (s, 2H), 2.14 (d, J = 3.0 Hz, 3H), 1.24 ppm (d, J = 4.0 Hz, 9H); C NMR
o
(
100 MHz, CDCl , 25 C) δ 151.2, 150.4, 149.1, 146.2, 144.4, 135.8, 133.2, 128.7, 128.4,
3
1
1
25.4, 125.1, 124.9, 121.5, 119.9, 119.7, 110.4, 109.9, 104.6, 101.2, 99.3, 93.4, 34.6, 31.2,
-1
2.6 ppm; IR: γ = 3403, 2961, 1734, 1460, 1308, 1146, 1038, 947, 840, 745 cm ; HRMS
+
(
ESI): m/z: calcd for C H NNaO : 446.1732 [M+Na] ; found: 446.1730.
2
8
25
3
4
.5.21. 2-Methyl-3-(6-(4-pentylphenyl)-[1,3]dioxolo[4,5-f]benzofuran-7-yl)-1H-
1
8

ACCEPTED MANUSCRIPT
o
1
o
indole (4u). Yellow solid; mp: 168–172 C; H NMR (400 MHz, CDCl , 25 C, TMS) δ 8.07
3
(s, 1H), 7.54 (d, J = 8.3 Hz, 2H), 7.32 (dd, J = 12.9, 8.0 Hz, 2H), 7.16 (d, J = 7.9 Hz, 1H),
7
.06 (s, 1H), 7.03 (t, J = 7.7 Hz, 3H), 6.65 (s, 1H), 5.93 (d, J = 2.3 Hz, 2H), 2.14 (s, 3H), 1.55
1
3
(
dt, J = 14.8, 7.5 Hz, 3H), 1.32–1.23 (m, 6H), 0.85 ppm (t, J = 6.7 Hz, 3H); C NMR (100
o
MHz, CDCl , 25 C) δ 151.2, 149.1, 146.2, 144.4, 142.4, 135.8, 133.1, 129.0, 128.5, 128.3,
3
1
2
25.4, 124.8, 121.5, 119.8, 119.7, 110.4, 109.9, 104.6, 101.2, 99.4, 93.4, 35.7, 31.5, 30.9,
-1
2.6, 14.1, 12.6 ppm; IR: γ = 3405, 2927, 1461, 1309, 1174, 1146, 1038, 947, 845, 744 cm ;
+
HRMS (ESI): m/z: calcd for C H NNaO : 460.1889 [M+Na] ; found: 460.1885.
2
9
27
3
4
.5.22. 3-(6-(4-Fluorophenyl)-[1,3]dioxolo[4,5-f]benzofuran-7-yl)-2-methyl-1H-
o
1
o
indole(4v). Yellow solid; mp: 207–210 C; H NMR (400 MHz, CDCl , 25 C, TMS) δ 8.14 (s,
3
1
H), 7.59 (dd, J = 8.8, 5.5 Hz, 2H), 7.39 (d, J = 8.1 Hz, 1H), 7.28 (d, J = 7.6 Hz, 1H),
.21–7.15 (m, 1H), 7.07–7.03 (m, 2H), 6.92 (t, J = 8.8 Hz, 2H), 6.67 (s, 1H), 5.97 (d, J = 2.4
7
1
3
o
Hz, 2H), 2.19 ppm (s, 3H); C NMR (100 MHz, CDCl , 25 C) δ 163.2 (d, J = 246 Hz),
3
1
50.0, 149.2, 146.4, 144.5, 135.8, 133.0, 128.0, 127.3 (d, J = 8.0 Hz), 124.6, 121.7 (d, J =
7.8 Hz), 120.2, 119.9, 119.5, 118.6, 115.8 (d, J = 8 Hz), 115.4 (d, J = 21 Hz), 115.3, 110.5 (d,
1
19
o
J = 10.5 Hz), 104.2, 101.3, 99.4, 93.3, 12.5 ppm; F NMR (377 MHz, CDCl , 25 C) δ
3
-113.74 ppm; IR: γ = 3399, 2922, 1674, 1504, 1460, 1309, 1231, 1172, 1147, 1037, 947, 909,
-1
+
8
38, 814, 744 cm ; HRMS (ESI): m/z: calcd for C H FNNaO : 408.1012 [M+Na] ; found:
24 16 3
4
08.1004.
4
.5.23. 3-(6-(4-Chlorophenyl)-[1,3]dioxolo[4,5-f]benzofuran-7-yl)-2-methyl-1H-
1
o
indole (4w). Yellow liquid; H NMR (400 MHz, CDCl , 25 C, TMS) δ 8.21 (s, 1H), 7.99 (d, J
3
=
8.5 Hz, 0.5H), 7.87 (d, J = 8.5 Hz, 0.5H), 7.55 (d, J = 8.6 Hz, 2H), 7.43–7.37 (m, 1H), 7.27
(d, J = 8.0 Hz, 1H), 7.19 (t, J = 6.6 Hz, 3H), 7.06 (s, 1H), 6.66 (s, 1H), 5.97 (d, J = 2.1 Hz,
1
3
o
2
1
1
1
H), 2.19 ppm (s, 3H); C NMR (100 MHz, CDCl , 25 C) δ 149.7, 149.3, 146.6, 144.6,
3
35.8, 133.0, 133.0, 131.3, 130.0, 129.6, 129.5, 129.1, 128.6, 127.9, 126.6, 124.5, 121.7,
20.0, 119.5, 111.2, 110.5, 104.2, 101.3, 99.4, 93.3, 12.6 ppm; IR: γ = 3399, 2923, 1460,
-1
307, 1251, 1173, 1147, 1093, 1038, 1013, 947, 909, 831, 801, 736 cm ; HRMS (ESI): m/z:
1
9

ACCEPTED MANUSCRIPT
+
calcd for C H ClNNaO : 424.0716 [M+Na] ; found: 424.0711.
2
4
16
3
1
4
.5.24. 3-(2-(4-Iodophenyl)-1H-inden-3-yl)-2-methyl-1H-indole (4x). Yellow liquid; H NMR
o
(
400 MHz, CDCl , 25 C, TMS) δ 8.17 (s, 1H), 7.90 (d, J = 8.5 Hz, 0.5H), 7.80 (d, J = 8.5 Hz,
3
0
7
1
1
1
1
5
.5H), 7.74 (d, J = 8.5 Hz, 0.5H), 7.63 (d, J = 8.5 Hz, 0.5H), 7.54 (d, J = 8.6 Hz, 2H),
.39–7.34 (m, 1H), 7.28 (s, 1H), 7.19 (t, J = 8.0 Hz, 2H), 7.06 (d, J = 1.7 Hz, 1H), 6.66 (s,
13
o
H), 5.97 (d, J = 2.2 Hz, 2H), 2.19 ppm (s, 3H); C NMR (100 MHz, CDCl , 25 C) δ 149.8,
3
49.3, 146.7, 144.6, 138.6, 138.1, 137.5, 135.8, 129.5, 128.3, 127.9, 127.0, 126.1, 125.6,
21.7, 120.0, 119.5, 110.5, 101.3, 99.4, 93.4, 12.6 ppm; IR: γ = 3397, 2921, 1729, 1580, 1459,
-1
305, 1251, 1146, 1037, 1006, 822, 745 cm ; HRMS (ESI): m/z: calcd for C H INNaO :
2
4
16
3
+
16.0073 [M+Na] ; found: 516.0068.
4
.5.25.3-(6-(2,3-Dihydrobenzo[b][1,4]dioxin-6-yl)-[1,3]dioxolo[4,5-f]benzofuran-7-
1
o
yl)-2-methyl-1H-indole (4y). Yellow liquid; H NMR (400Mz, DMSO, 25 C) δ 11.32 (s, 1H),
7
7
1
1
.39 (d, J = 8.0 Hz, 1H), 7.32 (s, 1H), 7.09-7.04 (m, 3H), 6.98 (d, J = 1.9 Hz, 1H), 6.91 (t, J =
.4 Hz, 1H), 6.78 (d, J = 8.5 Hz, 1H), 6.55 (s, 1H), 6.03 (d, J = 1.5 Hz, 2H), 4.18 (dd, J =
1
3
o
4.2, 4.6 Hz, 4H), 2.18 ppm (s, 3H);. C NMR (100Mz, DMSO, 25 C) δ 149.53, 148.2,
46.0, 144.3, 143.2, 143.1, 135.9, 133.8, 127.3, 124.2, 124.1, 120.7, 119.0, 118.2, 117.3,
113.4, 111.0, 109.5, 102.1, 101.3, 98.4, 93.6, 64.2, 64.0, 12.3 ppm; IR: γ = 3399, 3231, 2912,
-1
1
551, 1460, 1310, 1253, 1172, 1145, 1064, 1035, 747 cm ; HRMS (ESI): m/z: calcd for
+
C H NNaO : 448.1161 [M+Na] ; found: 448.1158.
26
19
5
4
.5.26. 2-Methyl-3-(6-(4-(methylthio)phenyl)-[1,3]dioxolo[4,5-f]benzofuran-7-yl)-1H-indole
o
1
o
(
4z). Yellow solid; mp: 194–197 C; H NMR (400 MHz, CDCl , 25 C, TMS) δ 8.13 (s, 1H),
3
7
1
.53 (d, J = 8.4 Hz, 2H), 7.33 (d, J = 8.1 Hz, 1H), 7.29 (d, J = 7.9 Hz, 1H), 7.16 (t, J = 7.5 Hz,
H), 7.07–7.01 (m, 4H), 6.64 (s, 1H), 5.92 (d, J = 1.6 Hz, 2H), 2.39 (s, 3H), 2.14 ppm (s, 3H);
1
3
o
C NMR (100 MHz, CDCl , 25 C) δ 150.6, 149.2, 146.4, 144.5, 137.7, 135.9, 133.1, 128.4,
3
1
1
28.4, 128.1, 126.2, 125.8, 124.8, 121.6, 119.9, 119.6, 110.5, 110.3, 104.4, 101.3, 99.4, 93.4,
-1
5.5, 12.6 ppm; IR: γ = 3400, 2920, 1730, 1461, 1307, 1147, 1038, 947, 825, 746 cm ;
2
0

ACCEPTED MANUSCRIPT
+
HRMS (ESI): m/z: calcd for C H NNaO S: 436.0983 [M+Na] ; found: 436.0980.
2
5
19
3
4
.5.27. 3-(6-(2-Fluorophenyl)-[1,3]dioxolo[4,5-f]benzofuran-7-yl)-2-methyl-1H-indole (4aa).
1
o
Yellow liquid; H NMR (400 MHz, CDCl , 25 C, TMS) δ 8.02 (s, 1H), 7.37–7.35 (m, 2H),
3
7
6
2
1
.22–7.19 (m, 1H), 7.18–7.14 (m, 1H), 7.10 (s, 1H), 7.07-7.02 (m, 2H), 6.99–6.95 (m, 1H),
1
3
.80 (s, 1H), 5.97 (dd, J = 7.7, 1.2 Hz, 2H), 2.04 ppm (s, 3H). C NMR (100 MHz, CDCl ,
3
o
5 C) δ 159.5(d, J = 252.0 Hz), 150.1, 146.5, 144.5, 135.6, 132.8, 130.1 (d, J = 3.0 Hz),
29.7 (d, J = 8.1 Hz), 128.3 (d, J = 9.8 Hz), 127.9, 124.0 (d, J = 3.6 Hz), 123.5, 121.4, 119.8,
119.4, 116.3 (d, J = 21.8 Hz), 113.5, 110.4, 104.2, 101.3, 99.7, 93.5, 77.4, 77.1, 76.8, 12.3
-1 19
ppm; IR: γ = 3399, 2919, 1731, 1460, 1309, 1146, 1037, 946, 757 cm . F NMR (377 MHz,
CDCl ): δ = -113.1 ppm (t, J = 5.7 Hz, 1F); HRMS (ESI): m/z: calcd for C H FNNaO :
3
24 16
3
+
4
4
08.1012 [M+Na] ; found: 408.1005.
.5.28. 2-Methyl-3-(6-(naphthalen-2-yl)-[1,3]dioxolo[4,5-f]benzofuran-7-yl)-1H-indole (4ab).
1
o
Yellow liquid; H NMR (400 MHz, CDCl , 25 C, TMS) δ 8.21 (s, 1H), 8.10 (s, 1H),
3
7
2
3
1
.73–7.69 (m, 2H), 7.61 (d, J = 10.7 Hz, 2H), 7.40–7.35 (m, 3H), 7.20 (dd, J = 12.5, 5.4 Hz,
H), 7.12 (s, 1H), 7.06 (d, J = 7.8 Hz, 1H), 6.71 (s, 1H), 5.96 (d, J = 3.4 Hz, 2H), 2.13 ppm (s,
1
3
o
H); C NMR (100 MHz, CDCl , 25 C) δ 150.8, 149.5, 146.6, 144.5, 135.9, 133.5, 133.2,
3
32.6, 129.1, 128.4, 128.3, 127.9, 127.6, 126.3, 126.1, 124.8, 124.4, 123.5, 121.6, 120.0,
119.7, 111.3, 110.5, 104.5, 101.3, 99.5, 93.4, 12.6 ppm; IR: γ = 3401, 2921, 1733, 1461, 1306,
-1
1
145, 1038, 945, 822, 747 cm ; HRMS (ESI): m/z: calcd for C H NNaO : 440.1263
28 19 3
+
[
M+Na] ; found: 440.1255.
4
.5.29. 3-(6-([1,1'-Biphenyl]-4-yl)-[1,3]dioxolo[4,5-f]benzofuran-7-yl)-2-methyl-1H-indole
1
o
(
4ac). Yellow liquid; H NMR (400 MHz, CDCl , 25 C, TMS) δ 8.14 (s, 1H), 7.70 (d, J =
3
8
.4 Hz, 2H), 7.54 (d, J = 7.5 Hz, 2H), 7.46 (d, J = 8.5 Hz, 2H), 7.38 (d, J = 7.7 Hz, 2H), 7.32
(t, J = 8.0 Hz, 2H), 7.18 (t, J = 7.2 Hz, 2H), 7.09 (s, 1H), 7.07–7.03 (m, 1H), 6.67 (s, 1H),
13
o
5
.95 (d, J = 2.4 Hz, 2H), 2.20 ppm (s, 3H); C NMR (100 MHz, CDCl , 25 C) δ 150.6,
3
1
49.3, 146.5, 144.5, 140.5, 139.8, 135.8, 133.1, 130.5, 128.8, 128.4, 127.9, 127.4, 127.0,
2
1

ACCEPTED MANUSCRIPT
1
26.9, 125.8, 121.6, 120.0, 119.7, 110.8, 110.5, 104.5, 101.3, 99.4, 93.4, 12.7 ppm; IR: γ =
-1
3
399, 2921, 1731, 1460, 1306, 1246, 1146, 1038, 946, 844, 745, 698 cm ; HRMS (ESI): m/z:
+
calcd for C H NNaO : 466.1419 [M+Na] ; found: 466.1415.
3
0
21
3
4
.5.30. 3-(6-(9H-fluoren-2-yl)-[1,3]dioxolo[4,5-f]benzofuran-7-yl)-2-methyl-1H-indole (4ad).
o
1
o
Green solid; mp: 140–143 C; H NMR (400 MHz, CDCl , 25 C, TMS) δ 8.07 (s, 1H), 7.87 (s,
3
1
H), 7.69 (d, J = 7.5 Hz, 1H), 7.59 (d, J = 1.8 Hz, 2H), 7.48 (d, J = 7.3 Hz, 1H), 7.36 (d, J =
.3 Hz, 1H), 7.33 (d, J = 2.9 Hz, 1H), 7.27 (d, J = 7.4 Hz, 1H), 7.19 (t, J = 7.1 Hz, 1H), 7.09
4
(s, 1H), 7.07-7.05 (m, 1H), 6.69 (s, 1H), 5.95 (d, J = 3.3 Hz, 2H), 3.80 (s, 2H), 2.16 ppm (s,
1
3
o
3
1
H); C NMR (100 MHz, CDCl , 25 C) δ 151.3, 149.3, 146.3, 144.5, 143.6, 143.4, 141.4,
3
40.9, 135.8, 133.0, 130.1, 128.2, 126.8, 126.8, 125.0, 124.8, 124.5, 122.0, 121.6, 119.9,
119.8, 119.8, 110.5, 104.7, 101.3, 99.4, 93.3, 37.0, 12.7 ppm; IR: γ = 3401, 2916, 1733, 1461,
-1
1
307, 1244, 1145, 1038, 946, 739 cm ; HRMS (ESI): m/z: calcd for C H KNO : 494.1159
3
1
21
3
+
[
M+K] ; found: 494.1153.
4
.5.31.N,N-dimethyl-4-(7-(2-methyl-1H-indol-3-yl)-[1,3]dioxolo[4,5-f]benzofuran-6-yl)anili
1
o
ne (4ae). Yellow liquid; H NMR (400 MHz, CDCl , 25 C, TMS) δ 8.10 (s, 1H), 7.51 (d, J =
3
9
.0 Hz, 2H), 7.34 (dd, J = 11.6, 8.0 Hz, 2H), 7.21–7.18 (m, 2H), 7.05 (s, 1H), 6.62 (s, 1H),
13
6
.56 (d, J = 9.0 Hz, 2H), 5.93 (d, J = 2.5 Hz, 2H), 2.90 (s, 6H), 2.17 ppm (s, 3H); C NMR
o
(
100 MHz, CDCl , 25 C) δ 152.0, 149.6, 148.8, 145.5, 144.2, 135.8, 133.1, 128.5, 128.3,
3
1
27.9, 126.6, 126.1, 125.6, 121.3, 119.7, 112.1, 110.3, 104.9, 101.1, 99.0, 93.3, 40.3, 12.6
ppm; IR: γ = 3399, 2922, 1734, 1609, 1516, 1460, 1310, 1171, 1139, 1037, 946, 822, 746
-1
+
cm ; HRMS (ESI): m/z: calcd for C H N NaO : 433.1528 [M+Na] ; found: 433.1523.
2
6
22
2
3
4
.5.32. 2-Methyl-3-(6-(thiophen-2-yl)-[1,3]dioxolo[4,5-f]benzofuran-7-yl)-1H-indole (4af).
1
o
Yellow liquid; H NMR (400 MHz, CDCl , 25 C, TMS) δ 8.16 (s, 1H), 7.37 (d, J = 8.1 Hz,
3
1
H), 7.28 (s, 1H), 7.19–7.16 (m, 3H), 7.12 (d, J = 4.5 Hz, 1H), 7.06 (s, 1H), 6.91 (t, J = 8.0
1
3
Hz, 1H), 6.65 (s, 1H), 5.96 (d, J = 1.5 Hz, 2H), 2.27 ppm (s, 3H); C NMR (100 MHz,
o
CDCl , 25 C) δ 149.1, 147.8, 146.4, 144.6, 135.8, 133.8, 133.3, 128.1, 127.2, 125.1, 124.5,
3
2
2

ACCEPTED MANUSCRIPT
1
24.1, 121.6, 119.9, 119.5, 110.4, 109.7, 103.6, 101.3, 99.2, 93.4, 12.7 ppm; IR: γ = 3401,
-1
2
921, 1727, 1461, 1305, 1144, 1037, 945, 799, 745, 702 cm ; HRMS (ESI): m/z: calcd for
+
C H NNaO S: 396.0670 [M+Na] ; found: 396.0667.
22
15
3
4
.5.33. 3-(6-Isopropyl-[1,3]dioxolo[4,5-f]benzofuran-7-yl)-2-methyl-1H-indole (4ag). Yellow
1
o
liquid; H NMR (400 MHz, CDCl , 25 C, TMS) δ 8.07 (s, 1H), 7.34 (t, J = 8.0 Hz, 1H),
3
7
.22–7.14 (m, 2H), 7.06 (t, J = 7.6 Hz, 1H), 7.02 (s, 1H), 6.61 (s, 1H), 5.93 (d, J = 0.4 Hz,
1
3
2
H), 2.98 (quintet, J =6.8 Hz, 1H), 2.34 (s, 3H), 1.29–1.26 ppm (m, 6H); C NMR (100
o
MHz, CDCl , 25 C) δ 160.1, 149.0, 145.2, 143.9, 135.5, 132.9, 128.3, 123.7, 121.4, 119.7,
3
119.1, 110.3, 107.5, 104.2, 101.0, 99.0, 93.4, 27.1, 21.5, 21.3, 12.5 ppm; IR: γ = 3402, 2923,
-1
1
730, 1461, 1303, 1145, 1037, 945, 848, 801, 745 cm ; HRMS (ESI): m/z: calcd for
+
C H NNaO : 356.1263 [M+Na] ; found: 356.1260.
21
19
3
4
.5.34. 3-(6-(Tert-butyl)-[1,3]dioxolo[4,5-f]benzofuran-7-yl)-2-methyl-1H-indole (4ah).
1
o
Yellow liquid; H NMR (400 MHz, CDCl , 25 C, TMS) δ 8.01 (s, 1H), 7.32 (d, J = 8.0 Hz,
3
1
6
H), 7.22 (d, J = 9.8 Hz, 1H), 7.14 (t, J = 8.0 Hz, 1H), 7.03 (t, J = 7.4 Hz, 1H), 6.99 (s, 1H),
1
3
.39 (s, 1H), 5.89 (d, J = 3.1 Hz, 2H), 2.26 (s, 3H), 1.24 ppm (s, 9H); C NMR (100 MHz,
o
CDCl , 25 C) δ 162.6, 148.2, 145.4, 144.0, 135.5, 133.2, 130.0, 125.4, 121.3, 119.8, 119.3,
3
110.3, 107.1, 105.5, 101.1, 98.7, 93.2, 34.5, 29.5, 12.4 ppm; IR: γ = 3406, 2963, 2926, 1724,
-1
1
460, 1310, 1243, 1171, 1143, 1038, 946, 819, 745 cm ; HRMS (ESI): m/z: calcd for
+
C H NNaO : 370.1419 [M+Na] ; found: 370.1413.
22
21
3
4
.5.35. 3-(6-(4-(Benzyloxy)phenyl)-[1,3]dioxolo[4,5-f]benzofuran-7-yl)-2-methyl-1H-indole
o
1
o
(
4ai). Yellow solid; mp: 187–190 C; H NMR (400 MHz, CDCl , 25 C, TMS) δ 8.05 (s, 1H),
3
7
.55 (d, J = 8.9 Hz, 2H), 7.38 – 7.28 (m, 7H), 7.20 – 7.14 (m, 2H), 7.05 (s, 1H), 6.81 (d, J =
13
8
.9 Hz, 2H), 6.64 (s, 1H), 5.92 (d, J = 2.5 Hz, 2H), 4.97 (s, 2H), 2.14 ppm (s, 3H); C NMR
o
(
100 MHz, CDCl , 25 C) δ 158.2, 151.0, 149.1, 146.1, 144.4, 136.9, 135.9, 133.1, 128.7,
3
1
1
28.4, 128.1, 128.0, 127.6, 127.0, 124.9, 121.6, 119.9, 119.7, 114.9, 110.5, 109.1, 104.6,
01.3, 99.3, 93.4, 70.0, 12.6 ppm; IR: γ = 3402, 2919, 1732, 1602, 1505, 1460, 1380, 1308,
2
3

ACCEPTED MANUSCRIPT
-1
1
246, 1174, 1146, 1036, 945, 835, 744 cm ; HRMS (ESI): m/z: calcd for C H NNaO :
31 23 4
+
4
96.1525 [M+Na] ; found: 496.1521.
4
.5.36.3-(6-(2,3-Dihydrobenzofuran-5-yl)-[1,3]dioxolo[4,5-f]benzofuran-7-yl)-2-
1
o
methyl-1H-indole (4aj). Yellow liquid; H NMR (400 MHz, CDCl , 25 C, TMS) δ 8.13 (s,
3
1
H), 7.52 (s, 1H), 7.37–7.33 (m, 3H), 7.18 (dd, J = 15.6, 8.1 Hz, 2H), 7.05 (t, J = 3.6 Hz, 2H),
.65 (s, 1H), 6.62 (d, J = 8.5 Hz, 1H), 5.94 (d, J = 3.2 Hz, 2H), 4.52 (t, J = 8.7 Hz, 2H), 3.09
6
1
3
o
(
t, J = 8.7 Hz, 2H), 2.16 ppm (s, 3H); C NMR (100 MHz, CDCl , 25 C) δ 159.6, 151.4,
3
1
1
1
48.9, 145.9, 144.3, 135.8, 133.0, 128.4, 128.2, 127.9, 127.2, 126.1, 124.9, 124.4, 122.4,
21.5, 119.8, 119.7, 110.4, 109.3, 101.2, 99.3, 93.3, 71.4, 29.6, 12.6 ppm; IR: γ = 3401, 2919,
-1
732, 1491, 1460, 1310, 1240, 1173, 1142, 1108, 1038, 944, 840, 746 cm ; HRMS (ESI):
+
m/z: calcd for C H NNaO : 432.1212 [M+Na] ; found: 432.1207.
2
6
19
4
4
.5.37. 6-Phenyl-7-(2,4,5-trimethoxyphenyl)-[1,3]dioxolo[4,5-f]benzofuran (7a). Yellow
1
o
liquid; H NMR (400 MHz, CDCl , 25 C, TMS) δ 7.59 (d, J = 7.2 Hz, 2H), 7.29–7.27 (m,
3
1
H), 7.21 (dd, J = 5.9, 3.8 Hz, 1H), 7.03 (s, 1H), 6.83 (s, 1H), 6.69 (d, J = 9.6 Hz, 2H), 5.95
1
3
o
(
s, 2H), 3.98 (s, 3H), 3.75 (s, 3H), 3.64 ppm(s, 3H); C NMR (100 MHz, CDCl , 25 C) δ
3
1
54.3, 151.9, 150.5, 149.7, 149.1, 146.3, 144.6, 143.5, 131.3, 128.3, 127.6, 125.7, 124.2,
1
1
4
14.9, 114.3, 101.2, 99.0, 98.5, 93.3, 56.6, 56.5, 56.1 ppm; IR: γ = 2905, 1605, 1513, 1462,
-1
311, 1210, 1160, 1134, 1035, 944, 813, 694 cm ; HRMS (ESI): m/z: calcd for C H NaO :
24
20
6
+
27.1158 [M+Na] ; found: 427.1153.
1
4
.5.38. 6-Phenyl-7-(phenylthio)-[1,3]dioxolo[4,5-f]benzofuran(9a). Yellow liquid; H NMR
o
(
400 MHz, CDCl , 25 C, TMS δ 8.15 (d, J = 8.1 Hz, 2H), 7.40 (t, J = 7.5 Hz, 2H), 7.33 (t, J
3
=
7.3 Hz, 1H), 7.18 (d, J = 5.9 Hz, 4H), 7.11–7.08 (m, 1H), 7.02 (s, 1H), 6.82 (s, 1H), 5.94
1
3
o
ppm (s, 2H); C NMR (100 MHz, CDCl , 25 C) δ 157.1, 149.2, 147.0, 145.2, 136.1, 130.0,
3
1
2
29.1, 128.9, 128.6, 126.8, 126.5, 125.6, 124.6, 105.0, 101.5, 98.9, 93.6 ppm; IR: γ = 3060,
-1
897, 1582, 1461, 1442, 1378, 1308, 1160, 1100, 1038, 946, 860, 766, 739, 690 cm ; HRMS
+
(
ESI): m/z: calcd for C H NaO S: 369.0561 [M+Na] ; found: 369.0554.
2
1
14
3
2
4

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Acknowledgements
The authors thank for National Natural Science Foundation of China for the financial support
21173089 and 21373093) and also for the Analytical and Testing Center of HUST. Chutian
(
Scholar Program of the Hubei Provincial Government and the Cooperative Innovation Center
of Hubei Province are also acknowledged. This work is also supported by
the Fundamental Research Funds for the Central Universities of China (2014ZZGH019).
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a
Table 1. One-pot three-component reaction of 5a, 2a and 3a in I /DMSO system
2
OH
O
3a
H
O
O
N
+
I2 (1.0 equiv.)
O
O
DMSO, 80 oC, 10 h
+
O
N
H
5
a
2a
4a
b
o
entry
co-catalyst
temp ( C)
yield (%)
trace
c
1
—
60
80
90
80
80
80
80
80
80
d
2
3
—
24 (20)
—
trace
24
e
4
—
f
5
—
23
6
7
8
CuCl2
FeCl3
Sc(OTf)3
PTSA
13
14
23
9
21
a
b
5
a: 0.5 mmol, 2a: 0.5 mmol, 3a: 0.5 mol, I : 1.0 equiv, solvent: 1.0 ml. co-catalyst: 20
2
c
d
e
f
mol%. 18 h. 12 h. 1a: 0.6 mmol, 2a: 0.5 mmol , 3a: 0.5 mmol. I : 2.0 equiv
2
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S2