[4+2+1] domino cyclization in water for chemo- and regioselective synthesis of spiro-substituted benzo[b]furo[3,4-e][1,4]diazepine derivatives

Article abstract of DOI:10.1039/c1gc15183e

New regio- and chemoselective [4+2+1] domino cyclization consisting of the formation of two spiro rings and five σ bonds has been developed for the synthesis of spiro-substituted benzo[b]furo[3,4-e][1,4]diazepine derivatives. The reaction is a multicompon

Full text of DOI:10.1039/c1gc15183e

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PAPER
[
4+2+1] Domino cyclization in water for chemo- and regioselective synthesis
of spiro-substituted benzo[b]furo[3,4-e][1,4]diazepine derivatives†
a
a
a
b
Chuang Cheng, Bo Jiang, Shu-Jiang Tu* and Guigen Li*
Received 19th February 2011, Accepted 20th April 2011
DOI: 10.1039/c1gc15183e
New regio- and chemoselective [4+2+1] domino cyclization consisting of the formation of two
spiro rings and five s bonds has been developed for the synthesis of spiro-substituted
benzo[b]furo[3,4-e][1,4]diazepine derivatives. The reaction is a multicomponent domino green
process and can be readily performed by reacting inexpensive starting materials of
benzene-1,2-diamines, tetronic acid and 2,2-dihydroxy-2H-indene-1,3-dione in aqueous solution
under microwave irradiation. The present synthesis shows attractive characteristics, such as the
use of water as reaction media, convenient one-pot operation, short reaction periods of 10–18 min
and reduced waste production without the use of any strong acids or metal promoters. This
synthesis serves as a nice addition to GAP (Group-Assistant-Purification) chemistry in which
purification via chromatography and recrystallization can be avoided, and the pure products were
obtained simply by washing the crude products with 95% EtOH.
Introduction
more, to the best of our knowledge, the synthesis of heterocyclic
compounds containing quinoxaline, benzodiazepine, spiro-ring
with excellent chemo- and regioselectivities has been not re-
ported so far.
In the past several years, our groups and others have developed
various multicomponent domino reactions (MDRs) that can
The search for efficient approaches to chemically and bio-
logically useful products, particularly, those containing C–N
bonds and quaternary carbon centers, starting from common
starting materials has become an important topic in modern
organic synthesis. In this regard, multicomponent domino
reactions (MDR) which can occur in aqueous media have been
extensively pursued in the past decade due to their efficient
1–3
offer easy access to multifunctionalized cyclic structures of
2,8–11
chemical and pharmaceutical interest.
For example, a new
four-component domino reaction was established for an easy ac-
2
atom economy and green characteristics. These processes can
2a
1,6
cess to multifunctionalized quinazoline and tricyclo[6.2.2.0 ]
avoid time-consuming and costly syntheses involving multistep
reactions, protection–deprotection steps, tedious workup and
purifications. In addition, these reactions often give excellent
chemo- and regioselectivies.
There exist a number of biologically active natural prod-
2b
dodecanes derivatives. Very recently, we also found that the
MDR of Meldrum’s acid, aromatic aldehydes and electron-rich
heteroaryl-amines diones in aqueous solution under microwave
irradiation (MW) led to the formation of multifunctionalized
spiro{[1,3]dioxanes-pyridine}-4,6-diones in high chemo- regio-
2,4
5
ucts which contain quaternary carbon atom(s). For example,
2c
and stereoselectivities and good yields.
6
7
quinoxaline and benzodiazepine derivatives are important
classes of nitrogen-containing heterocycles; and they constitute
useful precursors in organic synthesis. Although great progress
has been made in constructing quaternary carbon centers, this
During our continuous efforts on the development of mul-
2,9–10
ticomponent domino reactions,
here we would like to
report another selective green approach to spiro-substituted
benzo[b]furo[3,4-e][1,4]diazepine derivatives by controlling the
ratio of starting materials (Scheme 1). This reaction was achieved
by reacting benzene-1,2-diamines, tetronic acid and 2,2-
dihydroxy-2H-indene-1,3-dione in water under microwave irra-
diation. In this reaction, we foundthat the ratioofreactants, elec-
tronic inductive and conjugative effects of aromatic rings played
a crucial role in controlling the chemo- and regioselectivity.
5
synthesis still remains important and challenging. Further-
a
School of Chemistry and Chemical Engineering, Key Laboratory of
Green Synthetic Chemistry for Functional Materials, Xuzhou Normal
University, Jiangsu, P.R. China.
E-mail: laotu@xznu.edu.cn, guigen.li@ttu.edu; Fax: +86(516)
8
3500065; Tel: +86(516) 83500065
b
Department of Chemistry and Biochemistry, Texas Tech University,
Lubbock, TX, 79409-1061, USA
Results and discussion
†
Electronic supplementary information (ESI) available: CCDC refer-
The 2,2-dihydroxy-2H-indene-1,3-dione 1, possessing three
electrophilic centers, have been proven to be important
ence numbers 814811 and 814812. For ESI and crystallographic data in
CIF or other electronic format see DOI: 10.1039/c1gc15183e
This journal is © The Royal Society of Chemistry 2011
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Table 1 Optimization for the synthesis of 4a under microwave
irradiation
Entry
Amount of HOAc (equiv)
Time (min)
Yield (%)
1
2
3
4
5
0.1
0.2
0.3
0.4
0.5
15
15
14
14
14
85
85
86
86
85
chemical yield, but this reaction was proven to be unsuccessful
in water. Interestingly, when a few drops of acetic acid was
added into the reaction mixture as catalyst under microwave
irradiation, spiro-substituted benzo[b]furo[3,4-e][1,4]diazepine-
◦
1
-ones 4a was generated within 15 min at 140 C in a similar
Scheme 1
chemical yield. Therefore, we employed water as the most
1
3
building blocks for the construction of important heterocyclic
environmentally friendly media for this reaction. The amount
of HOAc was examined on its use in water with the results. As
shown in Table 1, 0.1 equiv was an optimal loading for acetic
acid catalyst to give good chemical yields.
12
frameworks. Our initial attempt to synthesize highly multifunc-
tionalized spiro-substituted benzo[b]furo[3,4-e][1,4]diazepine-1-
ones 4 via the reaction of 2,2-dihydroxy-2H-indene-1,3-dione
with tetronic acid and two equiv of benzene-1,2-diamine
was based on the following considerations: (1) 2,2-dihydroxy-
Under the above optimized conditions, the scope of this MCR
reaction was next examined by employing various benzene-
1,2-diamines (2.0 equiv), such as benzene-1,2-diamine 3a,
4,5-dimethylbenzene-1,2-diamine 3b, 4,5-dichlorobenzene-1,2-
diamine 3c and naphthalene-2,3-diamine 3d as readily available
starting materials. As revealed in Table 2, a range of useful
products 4 (4a–4d) with concomitant formations of up to five
s bonds including four C–N bonds and one quaternary carbon
center can be obtained in good to excellent yields. Interestingly,
when two types of benzene-1,2-diamines (1.0 equiv for each)
were subjected to this reaction under the similar conditions by
controlling their addition sequence, the corresponding products
(4e–o) were formed in good to excellent yields of 79–86%
(Scheme 3).
2H-indene-1,3-dione 1 are converted to corresponding 11H-
indeno[1,2-b]quinoxalin-11-one 6 with one electrophilic cen-
ter in the presence of benzene-1,2-diamine 3; (2) tetronic
acid 2 can favorably react with benzene-1,2-diamine 3 pro-
viding the 4-(2-aminophenylamino)furan-2(5H)-one A with
three nucleophilic centers; (3) the resulting 11H-indeno[1,2-
b]quinoxalin-11-one 6 can be easily attacked by two nucle-
ophilic centers of 4-(2-aminophenylamino)furan-2(5H)-one A
(
see Scheme 2). Similarly, the 2,2-dihydroxy-2H-indene-1,3-
dione with two active hydroxyl groups can be reacted with 4-(2-
aminophenylamino)furan-2(5H)-one A with three nucleophilic
centers, leading to polyfunctionalized spirotrione 5 that are
12k–n
useful for the drug design and synthesis.
We then studied the regioselectivity by using mono-
substituted benzene-1,2-diamine (4-chlorobenzene-1,2-diamine
3e) as an amino substrate; high yields (78%–88%) and complete
regioselectivity for the formation of products (4q–r) were
achieved readily (Scheme 4).
In addition, we also studied the reaction of 2,2-dihydroxy-2H-
indene-1,3-dione 1 with tetronic acid 2 and benzene-1,2-diamine
◦
3
a in HOAc at 100 C under microwave irradiation. Pleasantly,
the yellow solid 4a was generated within 15 min in 82%
Scheme 2
2
108 | Green Chem., 2011, 13, 2107–2115
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Table 2 Range of products obtained and corresponding yields
1
,3-dione 1 and tetronic acid 2, the reaction also occurred
smoothly to generate 5a in 78% yield. This observation is
attributed to the fact that the electronic inductive and con-
jugative effects of the carboxy group on the phenyl ring would
decrease the nucleophilicity of the two amino groups; which
in turn prevents the reaction with 2,2-dihydroxy-2H-indene-
1
,3-dione 1 to afford 11H-indeno[1,2-b]quinoxalin-11-one 6f.
As anticipated, the 3,4-diaminobenzoic acid with two amino
groups would be able to form two isomeric products, but only
one isomer was observed under the present system to give
excellent chemo- and regioselectivity. Subsequently, when the
ratio of 1, 2 and 3 was changed to 1 : 1 : 1, the corresponding
products 5b–5e were generated in good to excellent yields of
Scheme 3
80%–88% under the same aqueous and microwave irradiation
conditions.
2
Similarly to our previous multicomponent domino processes,
the present reaction displayed the following attractive charac-
teristics: (1) the environmentally friendly reaction can occur in
water; (2) fast reaction rates which enable the reaction to be
completed within 10–18 min, saving energy and manpower for
future industrial production; (3) the convenient work-up which
only needs simple filtration since the products directly precipitate
out after the reaction is finished, which indeed belongs to GAP
Scheme 4
14–18
chemistry;
(4) the use of readily available starting materials to
While 2.0 equiv of 3,4-diaminobenzoic acid 3f was employed
for the reaction with 1.0 equiv of 2,2-dihydroxy-2H-indene-
result in complex heptacyclic-fused products with a quaternary
amine functionality.
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Mechanism hypothesis
The reaction occurred at fast rates and essentially could be
finished within 10–18 min to give good to excellent chemical
The intermediates 6e and 7a formed during the reaction
processes have been successfully isolated and unambiguously
confirmed by X-ray diffractional analysis of their single crystals
yields and complete chemo- and regioselectivities. This work is
14–18
a nice addition to the GAP chemistry
in which purification
via chromatography and recrystallization can be avoided.
(
Fig. 1 and 2). The mechanism of forming spiro-substituted
benzo[b]furo[3,4-e][1,4] diazepine 4 and 5 can be proposed as
shown in Scheme 2. The former involves the ring closure cascade
steps that consists of two condensations (1 to 6, and 2 to A,
respectively), intermolecular nucleophilic addition (A to B) and
intramolecular nucleophilic substitution catalyzed by acetic acid
Experimental
General
Microwave irradiation was carried out with microwave oven
Emrys Creator made by Personal Chemistry, Uppsala, Sweden.
Melting points were determined in open capillaries and were
(
B to 4). The latter involves the condensation reaction to give
intermediate A, which is followed by subsequent intermolecular
nucleophilic addition with 1 (A to 7) and intramolecular nucle-
ophilic substitution (7 to 5). The regioselectivity is controlled
by the nucleophilicity of amino groups on aromatic rings of
the substrates. In fact, the formation of 5a depends on the
higher nucleophilicity of the amino group on the meta position
to carboxyl group rather than on the para position, but the
formation of 4q–r and 5e is controlled by the amino group on
para position of chloro substituted phenyl ring which shows
higher nucleophilic than that its meta position.
1
13
uncorrected. H NMR ( C NMR) spectra were measured on
a Bruker DPX 400 (100) MHz spectrometer in DMSO-d (or
6
CDCl )with chemical shift (d) given in ppm relative to TMS as
3
internal standard. The exact mass measurements were obtained
by high resolution mass instrument (GCT-TOF instrument).
X-Ray crystallographic analysis was performed with a Siemens
SMART CCD and a Semens P4 diffractometer.
General procedure for the synthesis of compounds 4a and 5b
Preparation of compounds 4a. Microwave heating: In a 10-
TM
mL Emrys reaction vial, the 2,2-dihydroxy-2H-indene-1,3-
dione 1 (1 mmol), benzene-1,2-diamine 3a (1 mmol), acetic acid
(
0.1 mmol) and water (2 mL) were mixed and stirred for 10 min,
Subsequently, the tetronic acid 2 (1 mmol) and benzene-1,2-
diamine 3 (1 mmol) were added to the reaction mixture, and the
reaction vial was capped and pre-stirred for 20 s. The mixture
was subjected to microwave irradiation at 200 W (initial power
◦
1
00 W, maximum power 200 W) at 140 C, for a given time. Upon
completion as monitored by TLC, the reaction mixture was
cooled to room temperature, filtered to give the crude product,
which was washed by HOAc to give pure product 4a.
Fig. 1 ORTEP diagram of intermediate product of 6e.
Preparation of compounds 5b. In a 10 mL of vial, the
benzene-1,2-diamine 3a (1 mmol), tetronic acid 2 (1 mmol),
acetic acid (0.1 mmol) and water (2 mL) were mixed and then
stirred for 15 min. Subsequently, 2,2-dihydroxy-2H-indene-1,3-
dione 1 (1 mmol) was added to the reaction mixture, and the
reaction vial was capped and pre-stirred for 20 s. The mixture
was subjected to microwave irradiation (initial power 100 W,
◦
maximum power 200 W) at 110 C, for a given time. Upon
completion, monitored by TLC, the reaction mixture was cooled
to room temperature, filtered to give the crude product, which
was further washed by 95% EtOH to give pure product 5b.
Fig. 2 ORTEP diagram of intermediate 7a.
4
,9-Dihydrospiro[benzo[b]furo[3,4-e][1,4]diazepine-10,11¢-in-
◦
deno[2,1-b]quinoxalin]-1(3H)-one 4a. Mp: >300 C
Conclusion
IR(KBr):3298, 3267, 1717, 1650, 1624, 1572, 1508, 1489, 1474,
1432, 1388, 1347, 1203, 1062, 991, 913, 863, 790, 749, 689, 607,
In summary, an efficient multicomponent domino approach to
spiro-substituted benzo[b]furo[3,4-e][1,4]diazepine derivatives
with formations of up to five s bonds including four C–N bonds
and a quaternary amine functionality has been established by
performing the reaction in one-pot operation in water under
microwave irradiation. The reactions showed a broad substrate
scope and readily available and inexpensive commercial starting
materials, such as 2,2-dihydroxy-2H-indene-1,3-dione, substi-
tuted benzene-1,2-diamines and tetronic acid could be used.
-
1
564 cm
1
H NMR (400 MHz, DMSO-d ): 10.22 (s, 1H, NH), 8.15 (dd,
6
J = 8.4, 1.1 Hz, 1H, ArH), 8.09 (d, J = 7.2 Hz, 1H, ArH), 7.98
(dd, J = 8.4, 1.2 Hz, 1H, ArH), 7.84–7.80 (m, 1H, ArH), 7.77–
7.73 (m, 1H, ArH), 7.52–7.48 (m, 1H, ArH), 7.41–7.37 (m, 1H,
ArH), 7.17–7.14 (m, 1H, ArH), 6.99–6.94 (m, 1H, ArH), 6.82
(dd, J = 12.8, 4.8 Hz, 2H, ArH), 6.67 (d, J = 6.8 Hz, 1H, ArH),
6.03 (s, 1H, NH), 4.96 (dd, J = 47.6 Hz, 15.2 Hz, 2H, CH
2
).
2
110 | Green Chem., 2011, 13, 2107–2115
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+
1
HRMS (ESI) m/z: calc. for [M+H ] C25
H
17
N
4
O
2
: 405.1347;
H NMR (400 MHz, DMSO-d
6
): 10.20 (s, 1H, NH), 8.04 (d,
found: 405.1345.
J = 7.6 Hz, 1H, ArH), 7.92 (s, 1H, ArH), 7.73 (s, 1H, ArH),
7
8
2
4
3
.49–7.45 (m, 1H, ArH), 7.37–7.33 (m, 1H, ArH), 7.14 (dd, J =
.0, 1.2 Hz, 1H, ArH), 6.97–6.93 (m, 1H, ArH), 6.85–6.78 (m,
H, ArH), 6.68 (dd, J = 8.0, 1.2 Hz, 1H, ArH), 5.99 (s, 1H, NH),
6
,7,7¢,8¢ - Tetramethyl - 4,9 - dihydrospiro [benzo [b ]furo [3,4 - e]
[
1,4]diazepine-10,11¢-indeno[2,1-b]quinoxalin]-1(3H)-one
Mp: >300 C
IR(KBr):3338, 3300, 3120, 2963, 2919, 2862, 1715, 1637, 1621,
575, 1517, 1500, 1399, 1343, 1258, 1219, 1155, 1114, 1050, 1020,
4b.
◦
.95 (dd, J = 43.6, 15.2 Hz, 2H, CH
H, CH ).
3C NMR (100 MHz, DMSO-d
2
), 2.48 (s, 3H, CH ), 2.44 (s,
3
3
1
9
◦
1
6
, 25 C) (d, ppm): 170.83,
-
1
02, 873, 767, 755, 734 cm
1
1
1
1
61.11, 158.90, 153.29, 150.28, 140.55, 139.73, 139.50, 138.86,
37.08, 136.62, 132.25, 130.90, 128.67, 128.35, 127.83, 123.80,
23.46, 123.29, 121.64, 121.44, 119.49, 95.48, 66.44, 64.69, 19.75,
1
H NMR (400 MHz, DMSO-d
J = 7.2 Hz, 1H, ArH), 7.91 (s, 1H, ArH), 7.75 (s, 1H, ArH),
.47–7.43 (m, 1H, ArH), 7.37–7.33 (m, 1H, ArH), 6.89 (s, 1H,
ArH), 6.80 (d, J = 7.6 Hz, 1H, ArH), 6.45 (s, 1H, ArH), 5.80
s, 1H, NH), 4.91 (dd, J = 51.6, 15.2 Hz, 2H, CH ), 2.48 (s, 3H,
CH ), 2.46 (s, 3H, CH ), 2.17 (s, 3H, CH ), 1.99 (s, 3H, CH ).
, 25 C) (d, ppm): 170.93,
6
): 10.06 (s, 1H, NH), 8.02 (d,
7
9.62.
+
HRMS (ESI) m/z: calc. for [M+H ] C27
H
21
N
4
2
O : 433.1660;
(
2
found: 433.1656.
3
3
3
3
1
3
◦
C NMR (100 MHz, DMSO-d
6
6
,7-Dimethyl-4,9-dihydrospiro[benzo[b]furo[3,4-e][1,4] diaze-
1
1
1
1
61.03, 158.80, 153.31, 150.65, 140.64, 139.79, 139.43, 138.78,
37.06, 134.17, 130.86, 129.70, 129.06, 128.49, 128.39, 127.87,
24.18, 123.74, 121.40, 120.43, 95.18, 66.40, 64.66, 19.79, 19.66,
pine-10,11¢-indeno[2,1-b]quinoxalin]-1(3H)-one
>
4f. Mp:
◦
300 C
IR(KBr):3279, 3117, 2968, 1711, 1621, 1573, 1510, 1398, 1345,
8.71, 18.66.
-
1
1265, 1206, 1072, 1049, 1022, 865, 763, 738, 569 cm
+
HRMS (ESI) m/z: calc. for [M+Na ] C29
83.1792; found: 483.1778.
H
24
N
4
NaO :
2
1
H NMR (400 MHz, DMSO-d ): 10.10 (s, 1H, NH), 8.15 (dd,
6
4
J = 8.4, 1.2 Hz, 1H, ArH), 8.07 (d, J = 7.6 Hz, 1H, ArH), 8.01
(dd, J = 8.4, 1.2 Hz, 1H, ArH), 7.84–7.80 (m, 1H, ArH), 7.78–
7.73 (m, 1H, ArH), 7.50–7.46 (m, 1H, ArH), 7.40–7.36 (m, 1H,
ArH), 6.91 (s, 1H, ArH), 6.81 (d, J = 7.6 Hz, 1H, ArH), 6.44 (s,
1H, ArH), 5.86 (s, 1H, NH), 4.92 (dd, J = 56.4, 15.2 Hz, 2H,
6,7,7¢,8¢ - Tetrachloro - 4,9 - dihydrospiro[benzo[b ]furo[3,4 - e ]
[
1,4]diazepine-10,11¢-indeno[2,1-b]quinoxalin]-1(3H)-one
Mp: >300 C
IR(KBr):3313, 3278, 3091, 1711, 1643, 1567, 1486, 1393, 1345,
4c.
◦
-
1
1
191, 1163, 1145, 1115, 1050, 1018, 1006, 901, 885, 764 cm
CH
2
13
), 2.17 (s, 3H, CH
C NMR (100 MHz, DMSO-d , 25 C) (d, ppm): 171.01,
3
), 2.00 (s, 3H, CH ).
3
◦
1
H NMR (400 MHz, DMSO-d
6
): 10.49 (s, 1H, NH), 8.48 (s,
6
1
7
1
4
H, ArH), 8.34 (s, 1H, ArH), 8.11 (d, J = 7.2 Hz, 1H, ArH),
.60–7.51 (m, 2H, ArH), 7.34 (s, 1H, ArH), 7.01 (d, J = 7.2 Hz,
H, ArH), 6.90 (s, 1H, ArH), 6.47 (s, 1H, NH), 5.00 (dd, J =
161.89, 158.89, 154.28, 150.99, 141.92, 141.00, 136.71, 134.07,
131.37, 130.97, 129.70, 129.60, 129.18, 128.84, 128.68, 128.61,
124.15, 123.77, 121.74, 120.51, 95.09, 66.50, 64.65, 18.71, 18.66.
+
0.0, 15.4 Hz, 2H, CH
HRMS (ESI) m/z: calc. for [M+H ] C25
2
).
HRMS (ESI) m/z: calc. for [M+Na ] C27
H
20
N
4
NaO :
2
+
H
12Cl
4
N
4
NaO
2
:
455.1479; found: 455.1474.
5
62.9607; found: 562.9589.
7
¢,8¢-Dichloro-4,9-dihydrospiro[benzo[b]furo[3,4-e][1,4] diaze-
4
¢,11¢-Dihydrospiro[benzo[g]indeno[2,1-b]quinoxaline-13,12¢-
pine-10,11¢-indeno[2,1-b]quinoxalin]-1(3H)-one
300 C
IR(KBr):3338, 3314, 1718, 1638, 1561, 1475, 1459, 1398, 1348,
4g. Mp:
furo[3,4-e]naphtho[2,3-b][1,4]diazepin]-1¢(3¢H)-one
300 C
IR(KBr):3321, 3289, 3121, 3046, 1718, 1644, 1627, 1566, 1529,
4d. Mp:
◦
>
◦
>
-
1
1
166, 1070, 1011, 902, 883, 763, 748 cm
-
1
1
480, 1471, 1396, 1345, 1235, 1047, 872, 756, 744 cm
1
H NMR (400 MHz, DMSO-d
6
): 10.25 (s, 1H, NH), 8.45 (s,
1
H NMR (400 MHz, DMSO-d
6
): 10.55 (s, 1H, NH), 8.79 (s,
1
(
H, ArH), 8.32 (s, 1H, ArH), 8.08 (d, J = 7.6 Hz, 1H, ArH), 7.52
1
(
7
1
1
H, ArH), 8.61 (s, 1H, ArH), 8.25 (d, J = 8.0 Hz, 1H, ArH), 8.18
dd, J = 7.6, 3.2 Hz, 2H, ArH), 7.81 (d, J = 8.4 Hz, 1H, ArH),
.65–7.60 (m, 3H, ArH), 7.57–7.50 (m, 2H, ArH), 7.43–7.39 (m,
H, ArH), 7.35–7.30 (m, 1H, ArH), 7.25 (dd, J = 10.8, 4.0 Hz,
H, ArH), 7.15 (s, 1H, ArH), 6.92 (d, J = 7.6 Hz, 1H, ArH), 6.48
t, J = 7.6 Hz, 1H, ArH), 7.43 (t, J = 7.6 Hz, 1H, ArH), 7.16 (d,
J = 7.6 Hz, 1H, ArH), 6.98 (t, J = 7.6 Hz, 1H, ArH), 6.84 (t, J =
.0 Hz, 2H, ArH), 6.67 (d, J = 7.6 Hz, 1H, ArH), 6.09 (s, 1H,
NH), 4.96 (dd, J = 44.0, 15.2 Hz, 2H, CH ).
HRMS (ESI) m/z: calc. for [M+Na ] C25
95.0387; found: 495.0376.
8
2
+
H
14Cl
2
N
4
NaO :
2
(
s, 1H, NH), 5.05 (dd, J = 48.8, 15.6 Hz, 2H, CH
2
).
4
1
3
◦
C NMR (100 MHz, DMSO-d
6
, 25 C) (d, ppm): 171.2,
1
1
1
6
63.0, 159.1, 154.8, 150.2, 138.7, 137.9, 137.3, 136.6, 134.0,
33.2, 132.7, 132.0, 130.2, 129.2, 128.2, 128.1, 127.4, 126.8,
26.7, 126.6, 126.4, 125.9, 124.6, 124.4, 122.2, 119.0, 115.5, 96.2,
6
,7-Dichloro-4,9-dihydrospiro[benzo[b]furo[3,4-e][1,4] diaze-
pine-10,11¢-indeno[2,1-b]quinoxalin]-1(3H)-one
300 C
IR(KBr): 3367, 3295, 3104, 1717, 1641, 1620, 1569, 1488,
4h. Mp:
◦
>
6.8, 64.7, 39.9, 39.7, 39.4, 39.2, 39.0.
HRMS (ESI) m/z: calc. for [M+Na ] C33
+
H
20
N
4
NaO :
2
-
1
1
395, 1345, 1302, 1150, 1052, 1014, 766, 566, 550 cm .
5
27.1479; found: 527.1495.
1
H NMR (400 MHz, DMSO-d ): 10.44 (s, 1H, NH), 8.14 (dd,
6
7
¢,8¢-Dichloro-4,9-dihydrospiro[benzo[b]furo[3,4-e][1,4] diaze-
J = 17.2, 7.6 Hz, 2H, ArH), 7.98 (d, J = 8.0 Hz, 1H, ArH), 7.83
(t, J = 7.2 Hz, 1H, ArH), 7.76 (t, J = 7.6 Hz, 1H, ArH), 7.56 (t,
J = 7.6 Hz, 1H, ArH), 7.49 (t, J = 7.6 Hz, 1H, ArH), 7.34 (s, 1H,
ArH), 7.02 (d, J = 7.6 Hz, 1H, ArH), 6.92 (s, 1H, ArH), 6.40 (s,
pine-10,11¢-indeno[2,1-b]quinoxalin]-1(3H)-one
300 C
IR(KBr):3258, 3214, 3091, 1716, 1642, 1575, 1497, 1387, 1346,
208, 1153, 1049, 1010, 908, 873, 753 cm
4e. Mp:
◦
>
-
1
1
1H, NH), 5.00 (dd, J = 42.4, 15.2 Hz, 2H, CH
2
).
This journal is © The Royal Society of Chemistry 2011
Green Chem., 2011, 13, 2107–2115 | 2111

View Article Online
1
3
◦
C NMR (100 MHz, DMSO-d
6
, 25 C) (d, ppm): 170.63,
6,7-Dichloro-4,9-dihydrospiro[benzo[b]furo[3,4-e][1,4]dia- ze-
1
1
1
61.73, 158.52, 154.14, 149.77, 141.84, 140.86, 136.87, 136.80,
32.46, 131.83, 129.90, 129.28, 129.21, 129.16, 128.76, 124.05,
pine - 10,13¢ - benzo[g ]indeno[2,1 - b ]quinoxalin] - 1(3H) - one 4l.
Mp: >300 C
◦
24.01, 123.58, 122.63, 121.93, 120.36, 96.21, 66.58, 64.46.
IR(KBr):3363, 3290, 3104, 1717, 1645, 1571, 1486, 1397, 1345,
+
-1
HRMS (ESI) m/z: calc. for [M+H ]
C
25
H
15Cl
2
N
4
O
2
:
1262, 1233, 1200, 1145, 1052, 1013, 901, 865, 756, 705 cm .
1
4
73.0567; found: 473.0544.
H NMR (400 MHz, DMSO-d ): 10.49 (s, 1H, NH), 8.79 (s,
6
1
H, ArH), 8.60 (s, 1H, ArH), 8.27–8.17 (m, 3H, ArH), 7.68–7.53
4
,9-Dihydrospiro[benzo[b]furo[3,4-e][1,4]diazepine-10,13¢-ben-
(
m, 4H, ArH), 7.37 (s, 1H, ArH), 7.11 (d, J = 7.6 Hz, 1H, ArH),
◦
zo[g]indeno[2,1-b]quinoxalin]-1(3H)-one 4i. Mp: >300 C
IR (KBr):3289, 3271, 3082, 1731, 1661, 1574, 1490, 1387,
6
2
.97 (s, 1H, ArH), 6.49 (s, 1H, NH), 5.03 (dd, J = 35.2, 15.2 Hz,
H, CH
2
).
-
1
1
347, 1205, 1073, 1053, 1011, 879, 750 cm .
◦
1
3
C NMR (100 MHz, DMSO-d
6
, 25 C) (d, ppm): 170.77,
1
H NMR (400 MHz, DMSO-d ): 10.25 (s, 1H, NH), 8.77 (s,
6
1
1
1
1
63.03, 158.34, 154.62, 149.99, 138.54, 137.75, 136.90, 136.67,
33.20, 132.74, 132.43, 132.40, 129.49, 128.23, 128.12, 127.43,
26.92, 126.78, 126.67, 124.32, 124.03, 123.58, 122.60, 122.18,
1
8
7
H, ArH), 8.60 (s, 1H, ArH), 8.23 (d, J = 8.0 Hz, 1H, ArH),
.21–8.14 (m, 2H, ArH), 7.66–7.59 (m, 2H, ArH), 7.55 (t, J =
.2 Hz, 1H, ArH), 7.45 (t, J = 7.2 Hz, 1H, ArH), 7.19 (d, J = 8.0
20.37, 96.46, 66.61, 64.29.
Hz, 1H, ArH), 6.97 (dd, J = 17.6, 7.6 Hz, 2H, ArH), 6.84 (t, J =
.2 Hz, 1H, ArH), 6.73 (d, J = 7.6 Hz, 1H, ArH), 6.13 (s, 1H,
NH), 4.99 (dd, J = 44.0, 15.2 Hz, 2H, CH ).
+
HRMS (ESI) m/z: calc. for [M+Na ] C29
H
16Cl
2
N
4
NaO :
2
7
5
45.0543; found: 545.0532.
2
◦
1
3
C NMR (100 MHz, DMSO-d , 25 C) (d, ppm): 171.08,
6
1
1
1
1
63.18, 158.81, 154.85, 150.94, 138.68, 137.93, 136.62, 136.58,
33.10, 132.64, 132.20, 132.01, 128.98, 128.21, 128.11, 127.34,
26.79, 126.62, 126.56, 124.11, 123.43, 123.38, 122.06, 121.72,
7
¢,8¢ - Dichloro - 4,11 - dihydrospiro[furo[3,4 - e]naphtho[2,3 - b]
[
1,4]diazepine-12,11¢-indeno[2,1-b]quinoxalin]-1(3H)-one
Mp: >300 C
IR (KBr):3317, 3035, 1718, 1647, 1614, 1561, 1530, 1470,
396, 1343, 1231, 1165, 1051, 996, 890, 870, 762, 748,
4m.
◦
19.62, 95.66, 66.61, 64.50.
HRMS (ESI) m/z: calc. for [M+Na ] C29
+
H
18
N
4
NaO :
2
1
6
4
77.1322; found: 477.1315.
-
1
69 cm .
1
H NMR (400 MHz, DMSO-d ): 10.54 (s, 1H, NH), 8.47 (s,
6
4
,11-Dihydrospiro[furo[3,4-e]naphtho[2,3-b][1,4]diazepine-12,
◦
1
(
2
H, ArH), 8.35 (s, 1H, ArH), 8.11 (d, J = 7.6 Hz, 1H, ArH), 7.80
d, J = 8.0 Hz, 1H, ArH), 7.62 (s, 1H, ArH), 7.52 (t, J = 8.4 Hz,
H, ArH), 7.39 (t, J = 7.6 Hz, 1H, ArH), 7.32 (t, J = 7.2 Hz, 1H,
ArH), 7.26 (t, J = 7.2 Hz, 1H, ArH), 7.12 (s, 1H, ArH), 6.85 (d,
J = 7.6 Hz, 1H, ArH), 6.44 (s, 1H, NH), 5.03 (dd, J = 49.2, 15.2
11¢-indeno[2,1-b]quinoxalin]-1(3H)-one 4j. Mp: >300 C
IR(KBr):3273, 3087, 1731, 1649, 1613, 1562, 1525, 1499, 1469,
1
7
395, 1345, 1231, 1169, 1114, 1098, 1072, 1045, 1009, 895, 767,
52 cm .
-
1
1
H NMR (400 MHz, DMSO-d ): 10.53 (s, 1H, NH), 8.19–
6
Hz, 2H, CH
2
).
8.15 (m, 1H, ArH), 8.11 (d, J = 7.6 Hz, 1H, ArH), 8.00 (d, J =
7.2 Hz, 1H, ArH), 7.85–7.73 (m, 3H, ArH), 7.61 (s, 1H, ArH),
7.50 (t, J = 8.8 Hz, 2H, ArH), 7.33 (dd, J = 15.2, 7.6 Hz, 2H,
1
3
◦
C NMR (100 MHz, DMSO-d
6
, 25 C) (d, ppm): 171.02,
1
1
1
1
63.43, 159.31, 155.62, 150.13, 141.05, 139.94, 137.08, 136.00,
33.92, 132.39, 132.15, 131.49, 130.18, 130.02, 129.51, 129.23,
29.18, 126.39, 125.90, 124.65, 124.45, 124.18, 122.26, 119.02,
15.63, 95.53, 66.84, 64.80.
HRMS (ESI) m/z: calc. for [M+Na ] C H Cl N NaO :
ArH), 7.26 (t, J = 7.2 Hz, 1H, ArH), 7.10 (s, 1H, ArH), 6.82 (d,
J = 7.6 Hz, 1H, ArH), 6.39 (s, 1H, NH), 5.02 (dd, J = 54.4, 15.2
Hz, 2H, CH ).
2
+
+
HRMS (ESI) m/z: calc. for [M+Na ] C29
H
18
N
4
NaO
2
:
29
16
2
4
2
5
45.0543; found: 545.0526.
4
77.1322; found: 477.1316.
7¢,8¢ - Dimethyl - 4,11 - dihydrospiro[furo[3,4 - e]naphtho[2,3 - b]
[
1,4]diazepine-12,11¢-indeno[2,1-b]quinoxalin]-1(3H)-one
4k.
7¢,8¢ - Dichloro - 6,7 - dimethyl - 4,9 - dihydrospiro[benzo[b ]furo
◦
Mp: >300 C
[3,4-e][1,4]diazepine-10,11¢-indeno[2,1-b]quinoxalin]-1(3H)-one
◦
IR(KBr):3293, 3050, 2948, 1718, 1654, 1625, 1561, 1525, 1498,
4n. Mp: >300 C
-
1
1
471, 1231, 1220, 1170, 1152, 1050, 1010, 901, 872, 754, 669 cm .
IR(KBr):3320, 3017, 2918, 1717, 1643, 1560, 1541, 1481, 1386,
1
-1
H NMR (400 MHz, DMSO-d
J = 7.6 Hz, 1H, ArH), 7.93 (s, 1H, ArH), 7.79 (d, J = 8.0 Hz,
H, ArH), 7.73 (s, 1H, ArH), 7.60 (s, 1H, ArH), 7.48 (t, J = 8.8
6
): 10.48 (s, 1H, NH), 8.06 (d,
1225, 1170, 1042, 1001, 889, 768, 751 cm .
1
H NMR (400 MHz, DMSO-d ): 10.13 (s, 1H, NH), 8.46 (s,
6
1
1H, ArH), 8.36 (s, 1H, ArH), 8.07 (d, J = 7.2 Hz, 1H, ArH),
7.52–7.48 (m, 1H, ArH), 7.45–7.41 (m, 1H, ArH), 6.91 (s, 1H,
ArH), 6.82 (d, J = 7.6 Hz, 1H, ArH), 6.43 (s, 1H, ArH), 5.93
Hz, 2H, ArH), 7.31 (t, J = 7.6 Hz, 2H, ArH), 7.25 (t, J = 7.2
Hz, 1H, ArH), 7.13 (s, 1H, ArH), 6.85 (d, J = 7.6 Hz, 1H, ArH),
6
3
.33 (s, 1H, NH), 5.01 (dd, J = 45.6, 15.2 Hz, 2H, CH
H, CH ), 2.42 (s, 3H, CH ).
C NMR (100 MHz, DMSO-d
2
), 2.47 (s,
(s, 1H, NH), 4.93 (dd, J = 53.2, 15.2 Hz, 2H, CH
CH ), 2.01 (s, 3H, CH ).
C NMR (100 MHz, DMSO-d , 25 C) (d, ppm): 171.07,
2
), 2.17 (s, 3H,
3
3
3
13
3
1
3
◦
◦
6
, 25 C) (d, ppm): 170.87,
6
1
1
1
1
60.93, 159.15, 153.27, 149.51, 140.67, 139.75, 139.61, 138.94,
37.45, 137.07, 134.07, 130.89, 130.14, 129.15, 128.83, 128.37,
27.89, 126.35, 125.84, 124.51, 124.29, 124.05, 121.53, 118.95,
163.58, 158.96, 155.68, 151.27, 141.01, 139.97, 136.00, 133.87,
132.23, 132.15, 131.35, 131.14, 130.00, 129.65, 129.45, 129.38,
128.86, 124.12, 123.90, 122.12, 120.62, 94.76, 66.62, 64.64, 18.70,
15.32, 95.94, 66.62, 64.80, 19.80, 19.64.
18.66.
+
+
HRMS (ESI) m/z: calc. for [M+H ] C31
H
23
N
4
O
2
: 483.1816;
HRMS (ESI) m/z: calc. for [M+Na ] C27
H
18Cl
2
N
4
NaO :
2
found: 483.1817.
112 | Green Chem., 2011, 13, 2107–2115
523.0700; found: 523.0692.
2
This journal is © The Royal Society of Chemistry 2011

View Article Online
6,7 - Dichloro - 7¢,8¢ - dimethyl - 4,9 - dihydrospiro[benzo[b ]furo
7¢-Chloro-6,7-dichloro-4,9-dihydrospiro[benzo[b]furo[3,4-e]-
[
4
3,4-e][1,4]diazepine-10,11¢-indeno[2,1-b]quinoxalin]-1(3H)-one
o. Mp: >300 C
[1,4]diazepine-10,11¢-indeno[2,1-b]quinoxalin]-1(3H)-one
Mp: >300 C
4r.
◦
◦
IR (KBr):3299, 3201, 3102, 1718, 1642, 1619, 1568, 1489,
397, 1344, 1219, 1201, 1150, 1052, 1013, 903, 873, 766, 721
cm .
IR(KBr):3299, 3200, 3096, 1716, 1644, 1621, 1568, 1488, 1395,
1346, 1253, 1194, 1165, 1051, 1014, 895, 876, 836, 763, 721, 669
1
-
1
-1
cm .
1
1
H NMR (400 MHz, DMSO-d
J = 7.2 Hz, 1H, ArH), 7.92 (s, 1H, ArH), 7.72 (s, 1H, ArH),
.56–7.52 (m, 1H, ArH), 7.48–7.44 (m, 1H, ArH), 7.32 (s, 1H,
ArH), 7.01 (d, J = 7.6 Hz, 1H, ArH), 6.94 (s, 1H, ArH), 6.35
s, 1H, NH), 4.98 (dd, J = 36.0, 15.2 Hz, 2H, CH ), 2.47 (s, 3H,
CH ), 2.43 (s, 3H, CH ).
C NMR (100 MHz, DMSO-d
6
): 10.42 (s, 1H, NH), 8.07 (d,
H NMR (400 MHz, DMSO-d ): 10.46 (s, 1H, NH), 8.23 (d,
6
J = 1.6 Hz, 1H, ArH), 8.11 (d, J = 7.6 Hz, 1H, ArH), 8.00 (d,
J = 8.8 Hz, 1H, ArH), 7.78 (dd, J = 8.8, 1.6 Hz, 1H, ArH),
7.57–7.51(m, 2H, ArH), 7.34 (s, 1H, ArH), 7.02 (d, J = 7.2 Hz,
1H, ArH), 6.90 (s, 1H, ArH), 6.41 (s, 1H, NH), 5.06–4.92 (m,
7
(
2
3
3
3
2H, CH
2
).
1
◦
13
◦
6
, 25 C) (d, ppm): 170.54,
C NMR (100 MHz, DMSO-d
6
, 25 C) (d, ppm): 170.66,
1
1
1
60.90, 158.42, 153.19, 149.36, 140.53, 139.84, 139.66, 139.22,
37.13, 136.97, 132.43, 131.33, 129.17, 128.33, 127.90, 123.98,
162.30, 158.59, 155.11, 150.01, 142.32, 139.50, 136.72, 136.32,
134.22, 132.41, 132.32, 130.87, 129.58, 129.41, 127.50, 124.18,
23.57, 122.51, 121.58, 120.25, 96.30, 66.46, 64.48, 19.77, 19.61.
124.08, 123.60, 122.80, 122.21, 120.43, 96.00, 66.64, 64.43.
+
+
HRMS (ESI) m/z: calc. for [M+Na ] C27
H
18Cl
2
N
4
NaO
2
:
HRMS (ESI) m/z: calc. for [M+H ]
C
25
H
14Cl
3
N
4
2
O :
5
23.0700; found: 523.0693.
507.1077; found: 507.1070.
1
,1¢,3¢-trioxo-1,1¢,3,3¢,4,9-hexahydrospiro[benzo[b]furo[3,4-e]-
7
-Chloro-4,9-dihydrospiro[benzo[b]furo[3,4-e][1,4]diazepine-
[
1,4]diazepine-10,2¢-indene]-6-carboxylic acid 5a. Mp: 269–
71 C
IR(KBr):3336, 3296, 1706, 1649, 1578, 1508, 1401, 1349, 1242,
◦
1
0,11¢-indeno[2,1-b]quinoxalin]-1(3H)-one 4p. Mp: >300 C
IR (KBr):3283, 3088, 1715, 1638, 1582, 1495, 1404,
349, 1205, 1102, 1075, 1053, 1005, 905, 864, 806,
◦
2
1
1
1
7
-
1
052, 981, 772, 764, 649 cm .
-
1
59 cm
1
H NMR (400 MHz, DMSO-d ): 12.63 (s, 1H, OH), 10.57 (s,
6
1
H NMR (400 MHz, DMSO-d
J = 8.0, 1.2 Hz, 1H, ArH), 8.11 (d, J = 7.6 Hz, 1H, ArH), 7.98
dd, J = 8.0, 1.2 Hz, 1H, ArH), 7.85–7.80 (m, 1H, ArH), 7.78–
.73 (m, 1H, ArH), 7.56–7.52 (m, 1H, ArH), 7.48–7.44 (m, 1H,
ArH), 7.16 (d, J = 8.8 Hz, 1H, ArH), 7.00 (dd, J = 8.8, 2.4 Hz,
6
): 10.35 (s, 1H, NH), 8.16 (dd,
H, NH), 8.01 (d, J = 9.2 Hz, 4H, ArH), 7.74 (s, 1H, ArH), 7.45
d, J = 8.0 Hz, 1H, ArH), 6.99 (s, 1H, NH), 6.93 (d, 1H, J = 8.0
(
(
7
Hz, ArH), 5.01 (s, 2H, CH
2
).
1
3
◦
C NMR (100 MHz, DMSO-d
6
, 25 C) (d, ppm):197.55,
1
1
71.25, 166.85, 159.54, 140.70, 136.53, 129.08, 124.34, 123.33,
21.75, 121.31, 90.93, 67.11, 65.05.
HRMS (ESI) m/z: calc. for [M+H ] C20
found: 377.0764.
1
1
H, ArH), 6.94 (d, J = 7.6 Hz, 1H, ArH), 6.74 (d, J = 2.4 Hz,
H, ArH), 6.26 (s, 1H, NH), 4.97 (dd, J = 41.6, 15.2 Hz, 2H,
+
H
13
N
2
6
O : 377.0769;
CH ).
2
1
3
◦
C NMR (100 MHz, DMSO-d
6
, 25 C) (d, ppm):
1
1
1
6
70.75, 161.83, 158.71, 154.18, 150.17, 141.84, 140.90,
37.89, 136.78, 131.67, 131.22, 129.82, 129.20, 129.07, 128.73,
26.42, 123.87, 122.10, 121.88, 121.27, 120.98, 95.47, 66.53,
spiro[benzo[b]furo[3,4-e][1,4]diazepine-10,2¢-indene]-1,1¢,3¢-
3H,4H,9H)-trione 5b. Mp: >300 C
◦
(
IR(KBr):3318, 3303, 3156, 3109, 1720, 1703, 1654, 1597, 1563,
4.55.
-
1
1
486, 1391, 1359, 1258, 1065, 1050, 880, 765, 752, 650 cm .
+
HRMS (ESI) m/z: calc. for [M+Na ] C25
H
15ClN
4
NaO :
2
1
H NMR (400 MHz, DMSO-d
.95 (m, 4H, ArH), 7.06 (d, J = 7.6 Hz, 1H, ArH), 6.93–6.85 (m,
H, ArH), 6.49 (s, 1H, NH), 4.98 (s, 2H, CH ).
, 25 C) (d, ppm):197.86,
6
): 10.32 (s, 1H, NH), 8.03–
4
61.0776; found: 461.0777.
7
3
2
1
3
◦
7
¢-Chloro-4,9-dihydrospiro[benzo[b]furo[3,4-e][1,4] diazepine-
C NMR (100 MHz, DMSO-d
6
◦
10,11¢-indeno[2,1-b]quinoxalin]-1(3H)-one 4q. Mp: >300 C
171.53, 159.71, 140.68, 136.48, 136.36, 130.45, 123.35, 123.23,
IR (KBr):3281, 3158, 3108, 1716, 1633, 1571, 1495, 1434,
122.42, 121.09, 119.74, 91.18, 67.19, 64.95.
HRMS (ESI) m/z: calc. for [M+H ] C19
found: 333.0869.
-
1
+
1
390, 1346, 1254, 1197, 1161, 1060, 928, 835, 753 cm .
H
13
N
2
4
O : 333.0870;
1
H NMR (400 MHz, DMSO-d
6
): 10.24 (s, 1H, NH), 8.20 (dd,
J = 21.2, 5.6 Hz, 1H, ArH), 8.05 (dd, J = 28.0, 8.0 Hz, 2H,
ArH), 7.87–7.76 (m, 1H, ArH), 7.51 (t, J = 7.6 Hz, 1H, ArH),
6,7-dimethylspiro[benzo[b]furo[3,4-e][1,4]diazepine-10,2¢-inde-
ne]-1,1¢,3¢(3H,4H,9H)-trione 5c. Mp: 258–259 C
◦
7
.45–7.37 (m, 1H, ArH), 7.16 (d, J = 8.0 Hz, 1H, ArH), 6.97 (t,
J = 7.6 Hz, 1H, ArH), 6.84 (t, J = 7.6 Hz, 2H, ArH), 6.67 (d, J =
IR(KBr):3323, 3284, 3121, 2973, 1719, 1637, 1619, 1571, 1496,
-
1
7
2
.6 Hz, 1H, ArH), 6.07 (s, 1H, NH), 4.96 (dd, J = 47.2, 15.2 Hz,
1403, 1347, 1255, 1213, 1197, 1054, 1043, 851, 741, 669 cm .
1
H, CH
2
).
H NMR (400 MHz, DMSO-d
6
): 10.16 (s, 1H, NH), 8.04–
1
3
◦
C NMR (100 MHz, DMSO-d
6
, 25 C) (d, ppm):
7.92 (m, 4H, ArH), 6.80 (s, 1H, ArH), 6.61 (s, 1H, ArH), 6.29
1
1
1
6
70.95, 162.49, 159.03, 155.26, 150.94, 142.38, 141.35, 140.57,
39.59, 136.42, 136.29, 133.92, 133.10, 132.21, 131.89, 130.89,
28.90, 127.46, 123.88, 123.43, 121.82, 119.64, 95.15, 66.61,
(s, 1H, NH), 4.95 (s, 2H, CH
CH ).
2
), 2.14 (s, 3H, CH ), 2.05 (s, 3H,
3
3
3
1
◦
C NMR (100 MHz, DMSO-d
6
, 25 C) (d, ppm):
4.62.
197.90, 171.59, 159.65, 140.64, 136.26, 134.09, 130.99, 128.72,
128.18, 123.30, 123.19, 120.55, 90.78, 67.14, 64.86, 18.71,
18.56.
+
HRMS (ESI) m/z: calc. for [M+Na ] C25
H
15ClN
4
NaO :
2
4
61.0776; found: 461.0764.
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Green Chem., 2011, 13, 2107–2115 | 2113

View Article Online
+
HRMS (ESI) m/z: calc. for [M+Na ] C21
83.1003; found: 383.0996.
H
16
N
2
NaO
4
:
Concepts in Chemistry, F. Vogtle, J. F. Stoddart and M. Shibasaki,
ed., Wiley-VCH: Weinheim, Germany, 2000, pp 39–64.
3
5
6
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,7-Chlorospiro[benzo[b]furo[3,4-e][1,4]diazepine-10,2¢-inde-
ne]-1,1¢,3¢(3H,4H,9H)-trione 5d. Mp: >300 C
IR(KBr):3320, 3288, 3098, 1744, 1719, 1706, 1642, 1615, 1567,
489, 1398, 1348, 1255, 1148, 1058, 1046, 989, 859, 761, 593 cm .
): 10.55 (s, 1H, NH), 8.06–
.98 (m, 4H, ArH), 7.25 (s, 1H, ArH), 7.07 (s, 1H, ArH), 6.79
◦
-
1
1
1
H NMR (400 MHz, DMSO-d
6
(a) E. D. Brock, D. M. Lewis, T. I. Yousaf and H. H. Harper, WO
7
9
951688, 1999; (b) A. Gazit, H. App, G. McMahon, J. Chen, A.
(
s, 1H, NH), 5.02 (s, 2H, CH
C NMR (100 MHz, DMSO-d
71.13, 159.40, 140.62, 136.85, 136.68, 130.69, 124.16, 123.43,
22.78, 122.11, 120.46, 92.15, 67.22, 64.86.
HRMS (ESI) m/z: calc. for [M+Na ] C19
22.9910; found: 422.9915.
2
).
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1
3
◦
6
, 25 C) (d, ppm): 197.17,
1
1
+
H
10Cl
2
N
2
NaO :
4
4
7
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-Chlorospiro[benzo[b]furo[3,4-e][1,4]diazepine-10,2¢-indene]-
◦
1
,1¢,3¢(3H,4H,9H)-trione 5e. Mp: 219–220 C
IR(KBr):3303, 3117, 1711, 1638, 1592, 1572, 1404, 1348, 1262,
-
1
1
059, 1044, 986, 860 cm .
2
008, 10, 595; (e) K. Murai, R. Nakatani, Y. Kita and H. Fujioka,
1
H NMR (400 MHz, DMSO-d ): 10.43 (s, 1H, NH), 8.04–
6
Tetrahedron, 2008, 64, 11034; (f) R. Ookura, K. Kito, T. Ooi, M.
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7
2
.97 (m, 4H, ArH), 7.08 (s, 1H, ArH), 6.89 (dd, J = 24.4, 9.2 Hz,
H, ArH), 6.64 (s, 1H, NH), 5.01 (s, 2H, CH ).
, 25 C) (d, ppm): 197.49,
2
1
3
◦
C NMR (100 MHz, DMSO-d
6
1
1
71.28, 159.51, 140.66, 136.50, 135.60, 131.59, 124.42, 123.31,
22.88, 118.83, 67.20, 64.84.
HRMS (ESI) m/z: calc. for [M+Na ] C19
89.0300; found: 389.0294.
+
H
11ClN
2
NaO :
4
8
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3
Acknowledgements
We are grateful for financial support from the NSFC (Nos.
0928001, 21072163 and 21002083), and Sci. Foundation in In-
2
(
f) B. Jiang, F. Shi and S.-J. Tu, Curr. Org. Chem., 2010, 14, 357.
terdisciplinary Major Res. Project of XZNU (No. 09XKXK01),
PAPD of Jiangsu Higher Ed. Inst., Doctoral Research Founda-
tion of Xuzhou Normal Univ. (XZNU, No. 10XLR20), Robert
A. Welch Foundation (D-1361) and NIH (R03DA026960).
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1
1, 612; (c) B. Jiang, W.-J. Hao, X. Wang, F. Shi and S.-J. Tu, J. Comb.
Chem., 2009, 11, 846.
1
0 (a) S.-J. Tu, X.-H. Zhang, Z.-G. Han, X.-D. Cao, S.-S. Wu, S. Yan,
W.-J. Hao and N. Ma, J. Comb. Chem., 2009, 11, 428; (b) B. Jiang,
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