One-pot synthesis of benzo[f]quinolin-3-ones and benzo[a]phenanthridein-5- ones by the photoanuulation of 6-chloropyridin-2-ones and 3-chloroisoquinolin-1- ones to phenylacetylene

Article abstract of DOI:10.1039/c1ob05082f

The one-pot synthesis of benzo[f]quinolin-3-ones and benzo[a] phenanthridein-5-ones was achieved by the inter- and intramolecular photoannulation of 6-chloropyridin-2-ones and 3-chloroisoquinolin-1-ones with phenylacetylene or tethered phenylacetylene. The reactions were proceeded by photoaddition of 6-chloropyridin-2-ones and 3-chloroisoquinolin-1-ones to phenylacetylene to give the chlorine-substituted stilbenoids, and then 6π electrocyclization of the stilbenoids and oxidation aromatization to afford the polycyclic products.

Full text of DOI:10.1039/c1ob05082f

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PAPER
One-pot synthesis of benzo[f ]quinolin-3-ones and
benzo[a]phenanthridein-5-ones by the photoanuulation of
6-chloropyridin-2-ones and 3-chloroisoquinolin-1-ones to phenylacetylene†
Ren Wang, Shen-Ci Lu, Yi-Ming Zhang, Zong-jun Shi and Wei Zhang*
Received 16th January 2011, Accepted 18th May 2011
DOI: 10.1039/c1ob05082f
The one-pot synthesis of benzo[f ]quinolin-3-ones and benzo[a]phenanthridein-5-ones was
achieved by the inter- and intramolecular photoannulation of 6-chloropyridin-2-ones and
3-chloroisoquinolin-1-ones with phenylacetylene or tethered phenylacetylene. The reactions were
proceeded by photoaddition of 6-chloropyridin-2-ones and 3-chloroisoquinolin-1-ones to
phenylacetylene to give the chlorine-substituted stilbenoids, and then 6p electrocyclization of the
stilbenoids and oxidation aromatization to afford the polycyclic products.
deacylation or oxidative aromatization to afford the polycyclic
Introduction
heterocycles.
The photochemistry of aryl halides has long received great
The photoinduced coupling reactions of aryl halogens with
attention due to their values in the organic synthesis and
alkynes to give the 1-arylalkynes have been reported by several
the reaction mechanistic investigation.1 Among many photo-
chemical reactions, photoinduced addition reactions of aryl
halogens with alkenes has become a useful tool for the syn-
thesis of aryl-substituted alkylamines, alkanols, ketones and
heterocycles.2 In addition, photoinduced coupling reactions of
aryl halogens with styrenes supply an efficient route to stil-
benes or “stilbenoids”.3 Photocyclization reaction of stilbenes
has widely used in the synthesis of phenanthrenes.4 This re-
action is equally useful for the synthesis of the heterocyclic
analogues of phenanthrenes, the so-called “phenanthrenoids”.5
It is of great interesting to combine these two photoreactions
into “one-pot”. Recently, we reported that one-pot synthesis of
benzo[c]carbazole and benzo[a]phenanthridein-5-one derivatives
by the photoreaction of 2-chloroindole-3-carbaldehydes and 3-
chloroisoquinlin-2-ones with styrenes (Scheme 1).6 These reac-
tions proceeded via photoinduced dechlorinative coupling to
give 2-heteroarylstyrenes firstly, then 6p electrocyclization and
authors,3c,7 but the photoaddition reactions of aryl halogens to
alkynes to give the chloro-substituted 1-phenylalkenes or stilbenes
are not found in literature. We report in this paper the first
investigation on the inter- and intramolecular photoreactions
of 6-chloropyridin-2-ones and 3-chloroisoquinolin-1-ones with
phenylacetylene.
Results and discussion
Similarly to the photoreaction of 3-chloroisoquinolin-1-one with
styrene,6b the intermolecular photoreactions of 6-chloropyridin-
2-one (1a) and 3-chloroisoquinolin-1-one (3a–c) with pheny-
lacetylene were also carried out in dichloromethane (DCM) with
quartz tube (for 6-chloropyridin-2-ones) or Pyrex tube (for 3-
chloroisoquinolin-1-ones) as reaction vessels because the rate of
photoreactions was higher than that in other solvents like acetone
and methanol. It was found that 6-chlorobenzo[f ]quinolin-3-one
(2a) could be obtained as the main product from the photoreaction
of 1a with phenylacetylene and 8-chlorobenzo[a]phenanthridin-5-
ones (4a–c) were obtained as the main product from the photore-
action of 3a–c with phenylacetylene under these conditions (Table
1).
Obviously, the products were all derived from two continuous
photoreactions. The first was the photoaddition of 1a or 3a–c to
phenylacetylene to afford the chlorine-substituted “stilbenoids”;
the second was the photocyclization of “stilbenoids” and oxidative
aromatization to afford 2a or 4a–c. it was found that the
photoreaction rates and yields of products were higher in the
presence of oxygen than those in the absence of oxygen. Thus,
oxygen favors the formation of the cyclization products. All these
Scheme 1 Photoreaction of 3-chloroisoquinlin-2-ones with styrene.
State Key laboratory of Applied Organic Chemistry, Lanzhou University,
Lanzhou, China. E-mail: zhangwei6275@lzu.edu.cn; Fax: +86 (0931)
8625657; Tel: +86 (0931) 8912545
† Electronic supplementary information (ESI) available. CCDC reference
numbers 800642, 806191. For ESI and crystallographic data in CIF or
other electronic format see DOI: 10.1039/c1ob05082f
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by X-ray analysis as depicted in Fig. 1.8 Comparatively, the
intramolecular reactions of 5a–b and 7a–d (Table 2) are more
efficient than the intermolecular photoreactions of 1a or 3a–c
with phenylacetylene (Table 1), not only the yields of products
were increased, but the reaction times were decreased greatly. The
presence of electron-donating substituents as methyl group on
phenylacetylene retarded photoreactions.
Table 1 Photoreaction of 6-chloropyridin-2-one and 3-chloroiso-
quinolin-1-one with phenylacetylene
Entry Substrate
R
Time (h) Convna (%) Product Yieldb (%)
1
2
3
4
1a
3a
3b
3c
—
H
CH3 40
Ph 40
38
40
95
90
93
96
2a
4b
4c
4d
46
53
60
56
a Conversion were based on the 1a or 3a–c. b Isolated yields.
photoreactions proceeded smoothly and the results were listed in
Table 1.
Fig. 1 X-Ray crystal structure of 8d.
Based on these promising results, we decided to extend
these reactions to intramolecuar mode. Several 6-chloro-N-
(w-phenylethynylalkyl)pyridin-2-ones (5a–b) and 3-chloro-N-(w-
phenylethynylalkyl)isoquinolin-1-ones (7a–d) were synthesized
and their photoreactions were conducted under the same con-
ditions (Table 2). The photoreactions of these phenylacetylene-
tethered 6-chloropyridin-2-one and 3-chloroisoquinolin-1-one all
afforded the fused 6-chlorobenzo[f ]quinolin-3(4H)-one (6a–b)
and 8-chlorobenzo[a]phenanthridin-5(6H)-ones (8a–d) as main
In order to compare the intramolecular photoreactions
of phenylacetylene-tethered 6-chloropyridin-2-ones (5a–b) or
3-chloroisoquinolin-1-ones (7a–d) with styrene-tethered 6-
chloropyridin-2-one or 3-chloroisoquinolin-1-one. We synthesized
the 6-chloro-N-(w-styrylalkyl)pyridin-2-ones (9a–c) or 3-chloro-
N-(w-styrylalkyl)isoquinolin-1-ones (11a–j) and investigated their
photoreaction. All these substrates could also be transformed
to fused benzo[f ]quinolin-3-one (10a–c) benzo[a]phenanthridin-
5-ones (12a–j) in high yields after 8–12 h irradiation (Table 3).
Differently, no chlorine-retained products were detected. It could
be inferred that intermediates “stilbenoids” were produced via two
step reactions: intramolecular addition of 6-chloropyridin-2-one
or 3-chloroisoquinolin-1-one to tethered styrene and subsequent
photodehyrochlorination because it was found that the presence
of pyridine in solution was helpful to the increase of conversion
of reactants and the yields of products.
products (Table 2). The products were identified by 1H NMR, 13
C
NMR and HRMS, and the structure of 8d was further confirmed
Table 2 Photocyclizations of 6-chloro-N-(w-phenylethynylalkyl)pyridin-
2-one and 3-chloro-N-(w-phenylethynylalkyl)isoquinolin-1-one
It could be noticed that the substituents on styrene and the
length of tethers all had similar influences to the results of
photoreactions as to the reactions involving phenylacetylene. The
electron-donating groups like methyl (9a, 11a, 11e) and methoxy
group (11d) retarded the photoreactions; in contrast, the electron-
attracting groups like chlorine (9c, 11c, 11g) and cyano group (11h)
accelerated the photoreactions. This influence of substituents to
the photocyclizations of 6-chloro-N-(w-styrylalkyl)pyridin-2-ones
(9a–c) and 3-chloro-N-(w-styrylalkyl)isoquinolin-1-ones (11a–j)
was consistent with that observed in photocyclizations of stilbenes
with different substituents.9 The conversion of reactants (11a, 11c,
11g, 11j) and the yields of products (12a, 12c, 12g, 12j) were
decreased gradually with the increase of the tether’s length (n = 1
to n = 3).
Entry Substrate
R
n
Time (h) Convna (%) Product Yieldb (%)
1
2
3
4
5
6
5a
5b
7a
7b
7c
7d
CH3
H
CH3
H
CH3
H
2
2
1
1
2
2
12
12
12
12
12
12
90
92
95
98
95
98
6a
6b
8a
8b
8c
8d
55
60
68
72
70
74
Differently from the photoreactions of 11a–11i, the photoreac-
tion of substrate 11j with a tether n = 0 gave only intramolecular
coupling product 13 in both Pyrex tube or reaction flask, no
normal product 12j was detected (Scheme 2). Obviously, it was
difficult to form the highly strained ring system like 11j in this
a Conversion were based on the 1a or 3a–c. b Isolated yields.
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Table 3 Photoreactions of 6-chloro-N-(w-styrylalkyl)pyridin-2-ones and
3-chloro-N-(w-styrylalkyl)isoquinolin-1-ones
Table 4 Photoreactions of 6-chloro-N-(w-furanylethenylalkyl)-iso-
quinolin-1-one and 3-chloro-N-(w-furanylethenylalkyl)isoquinolin-1-one
Entry Substrate
n
Time (h) Convna (%) Product Yieldb (%)
Entry Substrate n
R
Time (h) Convna (%) product Yieldb (%)
1
2
3
13a
15a
15b
2
1
2
15
10
10
88
90
90
14a
16a
16b
52
47
58
1
2
3
5
6
7
8
9
10
11
12
13
9a
2
2
2
1
1
1
2
2
2
2
2
3
CH3
H
Cl
CH3
H
Cl
CH3
OCH3 16
H
16
15
14
16
14
12
16
85
88
90
90
90
95
90
80
91
95
98
80
10a
10b
10c
12a
12b
12c
12d
12e
12f
12g
12h
12i
50
52
56
55
60
63
58
54
61
65
67
45
9b
9c
11a
11b
11c
11d
11e
11f
11g
11h
11i
a Conversion were based on the 1a or 3a–c. b Isolated yields.
15
12
12
16
Cl
CN
H
a Conversion were based on the 1a or 3a–c; b isolated yields.
Fig. 2 X-Ray crystal structure of 14a.
Mechanistic proposal
Scheme 2 Photoreaction of 3-chloro-2-(3-phenylpropenylisoquinolin-2-
ones) (11j).
Similarly to the proposal for the mechanism of photore-
actions between 3-chloroisoquinolin-1(2H)-one and styrenes,6b
the photoreactions between 6-chloropyridin-2-one (1a) or 3-
chloroisoquinolin-1-ones (3b) and phenylacetylene were consid-
ered to be also initiated by the homolytic fission of C–Cl
bond in excited 1a or 3b to give the heteroraryl radical and
chlorine atom as reported by Kaneko in his investigation on the
photolysis of 3b in benzene.11 Then the addition of heteroaryl
radicals to the triple bond of phenylacetylene and the combination
of the newly-produced radical with chlorine atom to afford
the chlorine-substituted “stilbenoid”; photoisomerization of the
trans-stilbenoid, 6p electrocyclization and oxidative aromatization
afforded the product 2a or 4b (Scheme 3).
photoreaction. In addition, this result also indicated the homolysis
of C–Cl bond in 3-chloroisoquinolin-1-one was feasible under the
irradiation of l > 300 nm.
Besides the above styrene-tethered 6-chloropyridin-2-ones (5a–
b) or 3-chloroisoquinolin-1-ones (7a–d), three 6-chloro-N-(w-
furanylethenylalkyl)isoquinolin-1-one (13a) and 3-chloro-N-(w-
furanylethenylalkyl)isoquinolin-1-one (15a–b) were synthesized
and were subjected to photoreactions under the same condi-
tions because styrylfuran is known to undergo photochemical
cyclization and oxidative aromatization to afford the polycyclic
compounds.7 As shown in Table 4, the photocyclization of 13a
and 15a–b could proceed smoothly, but conversion of reactants
and the yields of products were relatively lower as compared with
styrene-tethered 6-chloropyridin-2-ones or 3-chloroisoquinolin-1-
Conclusions
In conclusion, we have developed an efficient one-pot syn-
thesis of benzo[f ]quinolin-3-ones and benzo[a]phenanthridein-
5-ones by the photoannulation of 6-chloropyridin-2-ones
and 3-chloroisoquinolin-1-ones to phenylacetylene or tethered
1
ones. The products were identified by H NMR, 13C NMR and
HRMS, and the structure of 14a was further confirmed by X-ray
analysis as depicted in Fig. 2.10
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General procedure for the photochemical reactions of 3a–c, 7a–d
and 11a–j
6-Chloro-1-(5-phenylpent-4-enyl)pyridin-2-one (3a) (90 mg,
0.5 mmol) was dissolved in 40 mL dry dichloromethane and
dry pyridine (160 mg) was added. The solution was distributed
into two Pyrex tubes and the two tubes were irradiated with a
medium-pressure mercury lamp (500 W) at ambient temperature
for 40 h. The progress of the reaction was monitored by TLC at
regular intervals. After almost all substrate 3a had been consumed,
the solvent was removed under reduced pressure and the residue
was separated by column chromatography on silica gel eluted by
hexane-acetone 10 : 1(v/v) to afford photoreaction product 4a.
Scheme 3 Proposed mechanism for the formation of 2a.
6-Chloro-4-methylbenzo[f ]quinolin-3-ones (2a)
Brown solid; mp: 129–130 ◦C; 1H NMR (CDCl3, 400 MHz) d 8.50
(d, J = 10 Hz, 1H), 8.35 (t, J = 7.6 Hz, 1H), 7.74 (s, 1H), 7.73 (t, J =
7.6 Hz, 1H), 7.64 (t, J = 7.6 Hz, 1H), 6.89 (d, J = 10 Hz, 1H), 3.84
(s, 1H); 13C NMR (CDCl3,100 MHz) d 162.2, 138.8, 136.2, 133.6,
130.7, 128.9, 126.5, 126.3, 125.4, 121.9, 121.0, 115.2, 113.9, 30.3;
FT-IR (KBr,cm-1)3412, 2924, 1548, 1512, 1220, 756. ESI-HMRS:
(m/z) calcd for C14H10ClNO (M+H+): 244.0524, found 244.0529.
phenylacetylene. The photoannulations were proceeded by two-
step photoreactions containing chlorine atom transfer addition of
6-chloropyridin-2-ones and 3-chloroisoquinolin-1-ones to pheny-
lacetylene to give “chloro-stilbenoid” intermediates and 6p elec-
trocyclization and oxidative aromatization. The intramolecular
photoreactions were much more efficient than the intermolecular
photoreactions.
8-Chlorobenzo[a]phenanthridin-5-ones (4a)
White solid; mp: 205–206 ◦C; 1H NMR (DMSO,400 MHz) d 8.83
(d, J = 8.8 Hz, 1H), 8.69 (d, J = 8.4 Hz, 1H), 8.43 (dd, J = 8.0 Hz,
1H), 8.28 (d, J = 7.6 Hz, 1H), 7.92 (td, J = 7.6 Hz, 1H), 7.78 (td, J =
7.6 Hz, 1H), 7.70–7.31 (m, 2H); 13C NMR (DMSO,100 MHz) d
160.1, 134.7, 133.4, 132.1, 131.8, 129.9, 128.0, 127.1, 127.0, 126.4,
126.3, 126.2, 125.1, 125.0, 124.2, 116.4, 110.2; FT-IR (KBr,cm-1)
3405, 1630, 1324, 1142, 888, 784. ESI-HMRS: (m/z) calcd for
C17H10ClNO (M+H+): 280.0524, found 280.0529.
Experimental
General information
All reagents were purchased from commercial suppliers and
used without further purification. All solvents were dried and
redistilled before use. Flash chromatography was carried out with
silica gel (200–300 mesh). Analytical TLC was performed with
silica gel GF254 plates, and the products were visualized by
UV detection. Melting points were determined on a Yanagimoto
melting point apparatus and uncorrected. Elementary analyses
were carried out on a PERKIN-ELMER 2400 II analyzer. 1H and
13C NMR spectra were recorded on a Bruker AM-400 NMR or
a Bruker DRX-300 NMR spectrometers in CDCl3 with TMS as
an internal standard. EI-MS spectra were measured on an HP
5988A spectrometer by direct inlet at 70 eV. The HMRS spectra
were measured on a Burker Dattonics APEXII47e spectrometer
by ESI.
8-Chloro-6-methylbenzo[a]phenanthridein-5-ones (4b)
White solid; mp: 255–256 ◦C; 1H NMR (CDCl3,400 MHz) d
8.74 (d, J = 8.4 Hz,1H), 8.60 (dd, J = 8.0 Hz, 1H), 8.53 (d, J =
8.4 Hz,1H), 8.36 (d, J = 8.4 Hz,1H), 7.76 (td, J = 8.0 Hz, 1H),
7.72 (s, 1H), 7.66–7.58 (m, 3H), 3.86 (s, 3H); 13C NMR (CDCl3,
100 MHz) d 161.8, 136.8, 136.0, 133.8, 131.4, 130.0, 129.6, 128.6,
126.9, 126.8, 126.7, 126.5, 126.3, 124.6, 115.6, 112.6, 30.5; FT-IR
(KBr,cm-1) 3064, 2925, 2864, 1638, 1330, 1150, 890, 786. ESI-
HMRS: (m/z) calcd for C18H12ClNO (M+H+): 294.0680, found
294.0684.
General procedure for the photochemical reactions of 1a and 5a–b
and 9a–c
8-Chloro-6-phenylbenzo[a]phenanthridein-5-ones (4c)
6-Chloro-1-methylpyridin-2-one (1a) (72 mg, 0.5 mmol) was
dissolved in 40 mL dry dichloromethane. The solution was
distributed into two quartz tubes and the two tubes were irradiated
with a medium-pressure mercury lamp (500 W) at ambient
temperature for 36 h. The progress of the reaction was monitored
by TLC at regular intervals. After almost all substrate 1a had been
consumed, the solvent was removed under reduced pressure and
the residue was separated by column chromatography on silica
gel eluted by hexane-acetone 10 : 1(v/v) to afford photoreaction
product 2a.
White solid; mp: 260–261 ◦C; 1H NMR (CDCl3,400 MHz) d
8.84 (d, J = 8.4 Hz,1H), 8.66 (d, J = 8.0 Hz, 1H), 8.63 (dd, J =
7.6 Hz,1H), 8.34 (dd, J = 8.6 Hz,1H), 7.85 (td, J = 7.6 Hz,1H),
7.72–7.60 (m, 6 H), 7.34 (d, J = 7.2 Hz, 2H), 7.01 (s,1H); 13C NMR
(CDCl3,100 MHz) d 161.6, 137.8, 136.9, 133.3, 132.0, 130.7, 130.4,
129.1, 129.1, 129.0, 128.0, 127.7, 127.6, 127.2, 126.9, 126.3, 125.7,
125.1, 116.9, 113.0; FT-IR (KBr, cm-1) 3070, 145, 1340, 1154, 893,
790. ESI-HMRS: (m/z) calcd for C23H14ClNO (M+H+): 356.0837,
found 356.0840.
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5,6-Dihydro-7-chloro-11-methylnaphtho[3,2,1-ij]quinolizin-3-one
(6a)
1160, 899, 786. ESI-HMRS: (m/z) calcd for C21H16ClNO (M+H+):
334.0993, found334.0997.
White solid; mp:146–147 ◦C; 1H NMR (CDCl3, 400 MHz) d 8.51
(d, J = 8.4 Hz,1H), 8.22 (d, J = 8.8 Hz,1H), 8.07 (s,1H), 7.41 (d, J =
8.4 Hz,1H), 6.86 (d, J = 10 Hz,1H), 4.28 (t, J = 5.8 Hz, 2H), 3.23 (t,
J = 6.4 Hz, H), 2.59 (s, 3H), 2.20–2.14 (m, 2H); 13C NMR (CDCl3,
100 MHz) d 161.8, 137.8, 136.9, 134.0, 133.6, 129.2, 128.1, 125.0,
124.8, 122.2, 120.9, 120.0, 113.0, 42.27, 26.7, 22.0, 20.4; FT-IR
(KBr,cm-1) 2930, 2848, 1658, 1563, 1508, 1232, 758. ESI-HMRS:
(m/z) calcd for C17H14ClNO (M+H+): 284.0837, found 284.0840.
7,8-Dihydro-9-chlorobenzo[a]pyridine[3,2,1,- de]phenanthridin-
5-ones (8d)
White solid; mp:176–177 ◦C; 1H NMR (CDCl3, 400 MHz) d
8.64 (dd, J = 8.4 Hz,1H), 8.58 (dd, J = 8.0 Hz,1H), 8.50 (d, J =
8.0 Hz,1H), 8.38 (dd, J = 8.0 Hz,1H), 7.75 (td, J = 7.6 Hz,1H),
7.61 (t, J = 7.6 Hz,1H), 7.56 (td, J = 8.4 Hz,1H), 4.32 (td, J =
4 Hz, 2H), 3.26 (t, J = 6.4 Hz, 2H), 2.20–2.14 (m, 2H); 13C NMR
(CDCl3, 100 MHz) d 161.0, 133.8, 133.2, 132.4, 131.4, 129.1, 128.1,
127.5, 127.3, 126.8, 126.3, 126.1, 125.5, 124.8, 124.8, 123.1, 112.9,
42.3, 27.1, 20.4; FT-IR (KBr,cm-1) 3068, 2920, 2860, 1633, 1330,
1153, 894, 782. ESI-HMRS: (m/z) calcd for C20H14ClNO (M+H+):
320.0837, found 320.0842.
5,6-Dihydro-7-chloronaphtho[3,2,1-ij]quinolizin-3-one (6b)
White solid; mp:162–163 ◦C; 1H NMR (CDCl3, 400 MHz) d 8.53
(d, J = 10 Hz,1H), 8.34 (dd, J = 8.4 Hz, 2H), 7.66 (t, J = 7.6 Hz,1H),
7.59 (t, J = 7.6 Hz,1H), 6.89 (d, J = 9.6 Hz,1H), 4.30 (t, J =
5.8 Hz, 2H), 3.26 (t, J = 6.2 Hz, 2H), 2.22–2.17 (m, 2H); 13C NMR
(CDCl3, 100 MHz) d 161.8, 136.8, 134.1, 133.6, 129.1, 127.8, 126.6,
126.1, 125.2, 123.3, 121.4, 120.3, 113.4, 42.2, 26.8, 20.4; FT-IR
(KBr,cm-1) 2935, 2852, 1652, 1560, 1501, 1226, 750. ESI-HMRS:
(m/z) calcd for C16H12ClNO (M+H+):270.0680, found 270.0684.
5,6-Dihydro-10-methylnaphtho[3,2,1-ij]quinolizin-3-one (10a)
White solid; mp:160–161 ◦C; 1H NMR (CDCl3, 400 MHz) d 8.54
(d, J = 10.0 Hz, 1H), 8.06 (s, 1H), 7.31 (d, J = 8.0 Hz, 1H), 6.85 (d,
J = 10.0 Hz, 1H), 4.28 (t, J = 6.0 Hz, 2H), 3.09 (t, J = 6.0 Hz, 2H),
2.57 (s, 3H), 2.13–2.19 (m, 2H);13C NMR (CDCl3, 100 MHz) d
162.1, 136.9, 136.8, 133.9, 129.6, 129.1, 127.7, 127.3, 126.9, 123.9,
120.6, 119.7, 114.1, 43.2, 28.3, 22.1, 20.9; FT-IR (KBr,cm-1) 3022,
2932, 2860, 1660, 1568, 1508, 838, 790. ESI-HMRS: (m/z) calcd
for C17H15NO (M+H+): 250.1227, found 250.1232.
6,7-Dihydro-8-chloro-1-methylbenzo[a]pyrrolo[3,2,1-de]phenan-
thridin-5-ones (8a)
White solid; mp: 154–155 ◦C; 1H NMR (CDCl3, 400 MHz) d 8.74
(d, J = 8.4 Hz,1H), 8.66 (dd, J = 8.0 Hz,1H), 8.59 (s, 1H), 8.24 (d,
J = 7.2 Hz,1H), 7.81 (td, J = 8.4 Hz,1H), 7.62 (t, J = 7.2 Hz,1H),
7.40 (d, J = 8.4 Hz,1H), 4.51 (t, J = 8.0 Hz, 2H), 3.49 (t, J = 8.0 Hz,
2H), 2.61 (s, 3H); 13C NMR (CDCl3, 100 MHz) d 160.1, 139.1,
137.6, 134.7, 132.1, 130.8, 128.7, 128.6, 127.5, 127.0, 126.9, 125.7,
124.8, 124.3, 108.5, 46.2, 26.7, 22.1; FT-IR (KBr,cm-1) 3048, 2917,
2857, 1635, 1336, 1154, 890, 788. ESI-HMRS: (m/z) calcd for
C20H14ClNO (M+H+): 320.0837, found 320.0840.
5,6-Dihydronaphtho[3,2,1-ij]quinolizin-3-one (10b)
White solid, mp: 104–105 ◦C; 1H NMR (CDCl3, 400 MHz) d 8.48
(d, J = 9.6 Hz, 1H), 8.24 (d, J = 8.4 Hz, 1H), 7.76 (d, J = 8.0 Hz,
1H), 7.67 (s, 1H), 7.57 (td, J = 7.6 Hz), 7.47 (t, J = 7.2 Hz, 1H), 6.84
(d, J = 9.6 Hz, 1H), 4.25 (t, J = 6.0 Hz, 2H), 3.07 (t, J = 6.0 Hz,
2H), 2.11–2.17 (m, 2H);13C NMR (CDCl3, 100 MHz) d 162.1,
136.7, 133.7, 129.7, 128.9, 128.7, 127.8, 126. 9, 125.2, 124.9, 121.1,
120.1, 114.3, 43.1, 28.3, 20.7; FT-IR (KBr,cm-1) 3035, 2941, 2869,
1652, 1562, 1500, 833, 788. ESI-HMRS: (m/z)calcd for C16H13NO
(M+H+): 236.1070, found 236.1074.
6,7-Dihydro-8-chlorobenzo[a]pyrrolo[3,2,1-de] phenanthridin-5-
ones (8b)
◦
1
White solid; mp: 249–250 C; H NMR (CDCl3, 400 MHz) d
8.77 (d, J = 8.4 Hz,1H), 8.69 (d, J = 8.4 Hz,1H), 8.64 (dd, J =
8.0 Hz,1H), 8.34 (d, J = 7.6 Hz,1H), 7.78 (td, J = 7.6 Hz,1H),
7.65–7.55 (m, 3H), 4.48 (t, J = 8.0 Hz, 2H), 3.47 (t, J = 8.0 Hz, 2H);
13C NMR (CDCl3, 100 MHz) d 160.0, 139.0, 134.5, 132.1, 130.6,
129.8, 128.8, 128.7, 128.6, 127.6, 127.5, 127.0, 125.7, 125.1, 125.0,
124.7, 108.9, 46.2, 26.8; FT-IR (KBr,cm-1) 3060, 2928, 2850, 1630,
1328, 1148, 886, 784. ESI-HMRS: (m/z) calcd for C19H12ClNO
(M+H+): 306.0680, found 306.0684.
5,6-Dihydro-10-chloronaphtho[3,2,1-ij]quinolizin-3-one (10c)
◦
1
White solid; mp: 156–157 C; H NMR (CDCl3, 400 MHz) d
8.36 (d, J = 10 Hz, 1H), 8.17 (s, 1H), 7.67 (d, J = 8.4 Hz, 1H),
7.63 (s, 1H), 7.39 (dd, J = 8.4 Hz, 1H), 6.83 (d, J = 9.6 Hz,
1H), 4.25 (t, J = 6.0 Hz, 2H), 3.07 (t, J = 6.0 Hz, 2H), 2.12–
2.18(m, 2H);13C NMR (CDCl3, 100 MHz) d 161.9, 137.2, 133.5,
133.1, 129.8, 129.3, 129.2, 126.9, 125.9, 125.2, 120.6, 120.3, 113.5,
43.1, 28.2, 21.6; FT-IR (KBr,cm-1) 3026, 2928, 2858, 1648, 1560,
1512, 840, 786. ESI-HMRS: (m/z)calcd for C16H12NOCl (M+H+):
260.0680, found 260.0684.
7,8-Dihydro-9-chloro-12-methylbenzo[a]pyridine[3,2,1-de]phenan-
thridin-5-ones (8c)
7,8-Dihydro-11-methylbenzo[a]pyrrolo[3,2,1- de]phenanthridin-
5-ones (12a)
White solid; mp: 155–156 ◦C; 1H NMR (CDCl3, 400 MHz) d 8.56
(dd, J = 8.0 Hz,1H), 8.47 (d, J = 8.4 Hz,1H), 8.38 (s,1H), 8.23 (d,
J = 8.4 Hz,1H), 7.73 (td, J = 7.6 Hz,1H), 7.59 (t, J = 7.2 Hz,1H),
7.36 (dd, J = 8.4 Hz,1H), 4.30 (td, J = 4 Hz, 2H), 3.22 (t, J =
6.6 Hz, 2H), 2.52 (s, 3H), 2.17–2.11 (m, 2H); 13C NMR (CDCl3,
100 MHz) d 161.0, 136.7, 133.9, 133.4, 132.4, 131.3, 129.3, 128.1,
127.5, 127.4, 127.1, 126.3, 125.6, 125.3, 124.7, 122.0, 112.4, 42.3,
27.0, 21.9, 20.5; FT-IR (KBr,cm-1) 3064, 2914, 2852, 1638, 1334,
White solid; mp: 168–169 ◦C; 1H NMR (CDCl3,400 MHz) d 8.75
(d, J = 7.6 Hz, 1H), 8.63 (d, J = 8 Hz, 1H), 8.53 (s, 1H), 7.78 (t,
J = 8 Hz, 1H),7.70 (d, J = 8.0 Hz, 1H), 7.58 (t, J = 8.0 Hz, 1H),
7.28 (s, 1H), 4.43 (t, J = 7.6 Hz, 2H), 3.37 (t, J = 6.8 Hz, 2H), 2.25
(s, 3H); 13C NMR (CDCl3, 100 MHz) d 160.0, 139.5, 136.7, 135.1,
131.8, 130.1, 129.4, 129.0, 128.5, 127.5, 126.5, 126.1, 125.6, 124.9,
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123.9, 109.4, 46.4, 26.1, 22.2; FT-IR (KBr,cm-1) 3054, 2924, 2848,
1652, 1340, 1150, 890, 788. ESI-HMRS: (m/z) calcd for C20H15NO
(M+H+): 286.1227, found 286.1232.
161.3, 133.8, 133.8, 131.2, 129.9, 129.0, 128.8, 128.1, 127.7, 127.2,
127.0, 126.3, 126.2, 125.8, 124.9, 124.6, 113.7, 43.49, 28.69, 20.68;
FT-IR (KBr,cm-1) 3064, 2929, 2860, 1636, 1326, 1155, 891, 785.
ESI-HMRS: (m/z) calcd for C20H15NO (M+H+):286.1226, found
286.1233.
7,8-Dihydrobenzo[a]pyrrolo[3,2,1-de]phenanthridin-5-ones (12b)
White solid; mp:142–143 ◦C; 1H NMR (CDCl3,400 MHz) d 8.79
(t, J = 4 Hz, 2H), 8.65 (dd, J = 8.0 Hz, 1H), 7.84 (d, J = 8 Hz, 1H),
7.80 (td, J = 8 Hz, 1H), 7.76 (s, 1H), 7.57 (td, J = 8 Hz, 2H), 7.46 (t,
J = 7.6 Hz, 1H), 4.74 (t, J = 8.0 Hz, 2H), 3.43 (t, J = 8.0 Hz, 2H);13C
NMR (CDCl3,100 MHz) d 160.1, 139.4, 135.0, 132.0, 131.9, 131.2,
129.3, 129.2, 128.5, 127.5, 126.9, 126.8, 125.7, 125.2, 124.4, 124.3,
109.9, 46.4, 26.3, FT-IR (KBr,cm-1) 3047, 2918, 2850, 1647, 1342,
1118, 887, 784. ESI-HMRS: (m/z) calcd for C19H13NO (M+H+):
272.1070, found272.1074.
8,9-Dihydro-12-chlorobenzo[a]pyridino[3,2,1-de]phenanthridin-5-
ones (12g)
White solid; mp 150–151 ◦C; 1H NMR (CDCl3, 400 MHz) d 8.63
(s, 1H), 8.59 (d, J = 8.0 Hz, 1H), 8.52 (d, J = 8.4 Hz, 1H), 7.79 (t, J =
8.0 Hz, 1H), 7.72 (d, J = 8.4 Hz, 1H), 7.62 (d, J = 5.6 Hz, 1H), 7.38
(dd, J = 8.4 Hz, 1H), 4.31 (t, J = 6.0 Hz, 2H), 3.11 (t, J = 6.0 Hz,
2H), 2.13–2.16 (m, 2H);13C NMR (CDCl3, 100 MHz) d 161.3,
134.5, 133.4, 132.5, 131.7, 129.7, 129.2, 128.5, 128.3, 128.1, 127.3,
126.7, 126.3, 125.3, 125.3, 124.9, 113.0, 43.5, 28.6, 20.7; FT-IR
(KBr,cm-1) 3073, 2922, 2866, 1630, 1330, 1147, 896, 784. ESI-
HMRS: (m/z) calcd for C20H14NOCl (M+H+): 320.0837, found
320.0834.
7,8-Dihydro-11-chlorobenzo[a]pyrrolo[3,2,1-de]phenanthridin-5-
ones (12c)
White solid; mp:146–147 ◦C; 1H NMR (CDCl3, 400 MHz) d 8.58
(d, J = 8 Hz, 2H), 8.51 (d, J = 8.4 Hz, 1H), 7.75 (td, J = 8.4 Hz,
1H), 7.67 (d, J = 8.8 Hz, 1H), 7.58 (td, J = 8.0 Hz, 1H), 7.51 (s, 1H),
7.36 (dd, J = 8.8 Hz, 1H), 4.40 (t, J = 8.0 Hz, 2H), 3.36 (t,7.6 Hz,
2H);13C NMR (CDCl3, 100 MHz) d 159.9, 139.9, 132.9, 132.1,
131.5, 130.1, 129.8, 128.5, 127.4, 127.0, 125.1, 124.7, 123.5, 108.9,
46.4, 26.1; FT-IR (KBr,cm-1) 3030, 2910, 2842, 1640, 1328, 1132,
885, 782. ESI-HMRS: (m/z) calcd for C19 H12NOCl (M+H+):
306.0680, found 306.0683.
8,9-Dihydro-12-cyanobenzo[a]pyridino[3,2,1-de]phenanthridin-5-
ones (12h)
White solid; mp: 212–231 ◦C; 1H NMR(CDCl3, 400 MHz) d 9.01
(s, 1H), 8.62 (dd, J = 8.0 Hz, 1H), 8.45 (d, J = 8.0 Hz, 1H), 7.89 (d,
J = 8.4 Hz, 1H), 7.89 (d, J = 7.6 Hz, 1H), 7.86 (td, J = 7.2 Hz, 1H),
7.73 (s, 1H), 7.68 (td, J = 7.2 Hz, 1H), 7.60 (d, J = 8.0 Hz, 1H),
4.35 (t, J = 6.0 Hz, 2H), 3.19 (t, J = 6.0 Hz, 2H), 2.17–2.22 (m,
2H); 13C NMR (CDCl3, 100 MHz) d 161.2, 134.8, 132.8, 132.1,
131.8, 131.3, 128.9, 128.7, 128.5, 128.4, 128.2, 128.0, 126.9, 126.6,
125.4, 119.6, 113.8, 109.6, 43.5, 28.9, 20.5; FT-IR (KBr,cm-1) 3035,
2937, 2894, 1645, 1330, 1150, 898, 784. ESI-HMRS: (m/z) calcd
for C21H14N2O (M+H+): 311.1179, found 311.1184
8,9-Dihydro-12-methoxybenzo[a]pyridino[3,2,1-de]phenanthridin-
5-ones ((12d)
Yellow syrup; 1H NMR (CDCl3, 400 MHz) d 8.69 (d, J = 8.4 Hz,
1H), 8.60 (d, J = 8.0 Hz, 1H), 8.11 (s, 1H), 7.69–7.75 (m, 2H), 7.56–
7.59 (m, 2H), 4.32 (t, J = 6.0, 2H), 3.94 (s,3H), 3.09 (t, J = 6.0 Hz,
2H), 2.12–2.17 (m, 2H);13C NMR (CDCl3, 100 MHz) d 161.3,
158.3, 134.4, 134.1, 131.2, 130.2, 129.3, 128.7, 126.8, 126.3, 125.3,
122.4, 116.0, 112.9, 106.3, 55.4, 43.5, 28.5, 20.9; FT-IR (KBr,cm-1)
3056, 2927, 2846, 1639, 1330, 1157, 896, 788. ESI-HMRS: (m/z)
calcd for C21H17NO2 (M+H+): 316.1332, found 316.1338.
6,7,8,9-Tetrahydrobenzo[a]azepino[3,2,1-de]phenanthridin-5-one
(12i)
White solid; mp: 40–41 ◦C; 1H NMR (CDCl3,400 MHz) d 8.57–
8.62 (m, 3H), 7.81 (d, J = 8.4 Hz, 1H), 7.75 (td, J = 7.6 Hz, 1H),
7.65 (s, 1H), 7.59 (td, J = 7.6 Hz, 1H), 7. 54 (td, J = 8.0 Hz,
1H), 7.46 (td, J = 8.0 Hz, 1H), 4.56 (t, J = 5.2 Hz, 2H), 3.31 (t,
J = 5.2 Hz, 2H), 2.10–2.15 (m, 2H), 1.99–2.05 (m, 2H);13C NMR
(CDCl3, 100 MHz) d 162.1, 138.9, 134.0, 131.5, 130.8, 130.2, 130.2,
128.5, 128.4, 127.5, 127.2, 127.1, 126.3, 125.9, 125.8, 124.8, 115.6,
44.5, 33.8, 25.7, 23.2; FT-IR (KBr,cm-1) 3072, 2935, 2882, 1647,
1588, 1444, 1172, 819, 748. ESI-HMRS: (m/z) calcd for C21H17NO
(M+H+): 300.1383, found 300.1388.
8,9-Dihydro-12-methylbenzo[a]pyridino[3,2,1-de]phenanthridin-5-
ones (12e)
Yellow syrup; 1H NMR (CDCl3, 400 MHz) d 8.59 (dt, J = 4 Hz,
2H), 8.43 (s, 1H), 7.73 (td, J = 5.6 Hz, 1H), 7.67 (d, J = 7.6 Hz,
1H), 7.57 (td, J = 5.6 Hz, 2H), 7.26 (dd, J = 6.0 Hz, 1H), 4.30
(t, J = 6.0 Hz, 2H), 3.07 (t, J = 6.0 Hz, 2H), 2.53 (s, 3H), 2.08–
2.14 (m, 2H);13C NMR (CDCl3,100 MHz) d 161.3, 135.9, 133.9,
133.9, 131.2, 129.2, 128.6, 128.1, 128.1, 127.6, 127.1, 126.6, 125.1,
123.8, 113.2, 43.4, 28.6,20.9; FT-IR(KBr,cm-1) 3047, 2921, 2852,
1632, 1324, 1152, 893, 785. ESI-HMRS: (m/z) calcd for C21H17NO
(M+H+): 300.1083, found 300.1390.
Benzo[3,4]azepino[1,2-b]isoquinolin-9-one (13)
White solid; mp:118–119 ◦C; 1H NMR (CDCl3, 400 MHz) d 8.44
(d, J = 8.4 Hz, 1H), 7.74 (dd, J = 8.0 Hz, 1H), 7.60 (t, J = 8.0 Hz,
1H), 7.38–7.51 (m, 4 H), 7.30 (d, J = 7.6 Hz, 1H), 6.88 (d, J =
9.6 Hz, 1H), 6.57 (s, 1H), 6.47 (m, 1H), 5.75 (dd, J = 6.8 Hz, 1H),
3.50 (qd, J = 6.8 Hz, 1H); 13C NMR (CDCl3, 100 MHz) d 161.1,
142.8, 136.4, 135.9,135.8, 134.5, 132.0, 129.7, 129.5, 129.0, 128.9,
127.8, 127.8, 126.4, 126.0, 124.2, 108.1, 39.5; FT-IR (KBr,cm-1)
3056, 3025, 2921, 1637, 1588, 1444, 1172, 819, 748. ESI-HMRS:
(m/z) calcd for C18H13NO (M+H+): 260.1070, found 260.1073.
8,9-Dihydrobenzo[a]pyridino[3,2,1-de]phenanthridin-5-ones (12f)
White solid; mp 90–91 ◦C; 1H NMR (CDCl3, 400 MHz) d 8.66 (d,
J = 8.8 Hz, 1H), 8.60 (d, J = 8 Hz, 2H), 7.79 (d, J = 7.6 Hz, 1H), 7.74
(t, J = 8.0 Hz, 1H), 7.65 (s, 1H),7.59(t, J = 8 Hz, 1H), 7.51 (t, J =
6.0 Hz, 2H), 7.44 (t, J = 7.6 Hz, 1H), 4.32 (t, J = 6.0 Hz, 2 H), 3.11 (t,
J = 6.0 Hz, 2H), 2.11–2.13 (m, 2H); 13C NMR (CDCl3, 100 MHz) d
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5,6-Dihydrofurano[1,2-f ]pyridino[3,2,1-de]quinolin-5-ones (14a)
2 (a) V. Dichiarante, M. Fagnoni and A. Albini, Angew. Chem., Int. Ed.,
2007, 46, 6495; (b) S. Protti, M. Fagnoni and A. Albini, J. Am. Chem.
Soc., 2006, 128, 10670; (c) V. Dichiarante, M. Fagnoni, M. Mella and
A. Albini, Chem.–Eur. J., 2006, 12, 3905; (d) S. Protti, M. Fagnoni, M.
Mella and A. Albini, J. Org. Chem., 2004, 69, 3465; (e) A. Fraboni, M.
Fagnoni and A. Albini, J. Org. Chem., 2003, 68, 4886; (f) M. A. Clyne
and F. Aldabbagh, Org. Biomol. Chem., 2006, 4, 268; (g) S. M. Barolo,
X. Teng, G. D. Cuny and R. A. Rossi, J. Org. Chem., 2006, 71, 8493;
(h) T.-I. Ho, C.-K. Ku and R. S. H. Liu, Tetrahedron Lett., 2001, 42,
715; (i) S.-C. Lu, X.-Y. Duan, Z.-J. Shi, B. Li and W. Zhang, Org. Lett.,
2009, 11, 3902–3905; (j) Q. Liu, B. Han, W. Zhang, L. Yang, Z.-L. Liu
and W. Yu, Synlett, 2005, 2248.
Brown solid; mp: 203–204 ◦C; 1H NMR(CDCl3, 400 MHz) d 7.98
(d, J = 9.6 Hz, 1H), 7.69 (s, 1H), 7.47 (s, 1H), 7.01 (s, 1H), 6.80 (d,
J = 9.6 Hz, 1H), 4.25 (t, J = 6.0 Hz, 2H), 3.08 (t, J = 6.0 Hz, 2H),
2.11–2.18 (m, 2H);13C NMR(CDCl3, 100 MHz) d 161.8, 149.8,
145.6, 134.9, 133.5, 123.0, 122.2, 121.1, 113.5, 113.3, 104.6, 42.7,
28.5, 20.9; FT-IR(KBr,cm-1) 3134, 3112, 2937, 1649, 1589, 1413,
1130, 837, 783. ESI-HMRS: (m/z) calcd for C17H11NO2 (M+H+)
262.0863, found 262.0868.
3 (a) D. Mangion and D. R. Arnold, Can. J. Chem., 1999, 77, 1655;
(b) M. Mella, P. Coppo, B. Guizzardi, M. Fagnoni, M. Freccero and
A. Albini, J. Org. Chem., 2001, 66, 6344; (c) M. D’Auria, G. Piancatelli
and T. Ferri, J. Org. Chem., 1990, 55, 4019.
6,7-Dihydrofurano[1,2-f ]pyrrolo[3,2,1-de]phenanthridin-5-ones
(16a)
4 (a) F. B. Mallory and C. W. Mallory, Org. React., 1984, 30, 1; (b) W.
H. Laarhoven, Pure Appl. Chem., 1984, 56, 1225; (c) W. H. Laarhoven,
Org. Photochem., 1989, 10, 163–308; (d) H. T. Meier, Angew. Chem.,
Int. Ed. Engl., 1992, 31, 1399–1420; (e) F. D. Lewis, R. S. Kalgutkar
and J.-S. Yang, J. Am. Chem. Soc., 2001, 123, 3878; (f) A. G. Neo, C.
Lopez, V. Romero, B. Antelo, J. Delamano, A. Perez, D. Fernandez,
J. F. Almeida, L. Castedo and G. Tojo, J. Org. Chem., 2010, 75,
6764.
5 (a) A. G. Neo, C. Lopez, V. Romero, B. Antelo, J. Delamano, A.
Perez, D. Fernandez, J. F. Almeida, L. Castedo and G. Tojo, J. Org.
Chem., 2010, 75, 6764; (b) M. Austin, O. J. Egan, R. Tully and A.
C. Pratt, Org. Biomol. Chem., 2007, 5, 3778; (c) M. J. E. Hewlins
and R. Salter, Synthesis, 2007, 2164; (d) S. Abbate, C. Bazzini, T.
Caronna, F. Fontana, C. Gambarotti, F. Gangemi, G. Longhi, A. Mele,
I. N. Sora and W. Panzeri, Tetrahedron, 2006, 62, 139; (e) J. T. Link,
S. Raghavan and S. J. Danishefsky, J. Am. Chem. Soc., 1995, 117,
552.
◦
1
Brown solid, mp: 216–217 C; H NMR(CDCl3, 400 MHz) d
8.61 (dd, J = 8.0 Hz, 1H), 8.38 (d, J = 8.0 Hz, 1H), 7.80 (td,
J = 9.2 Hz, 2H), 7.61 (t, J = 7.2 Hz, 1H), 7.48 (s, 1H), 7.37 (s,
1H), 4.52 (t, J = 8.0 Hz, 2H), 3.46 (t, J = 8.0 Hz, 2H); 13C NMR
(CDCl3,100 MHz) d 159.7, 152,7, 145.8, 136.5, 134.4, 132.0, 128.5,
128.4, 127.3, 127.2, 124.2, 120.5, 109.3, 106.5, 46.9, 26.8; FT-IR
(KBr,cm-1) 3118, 2920, 2868, 1625, 1600, 1342, 1149, 1033, 789.
ESI-HMRS: (m/z) calcd for C17H11NO2 (M+H+) 276.1019, found
276.1023.
7,8-Dihydrofurano[1,2-f ]pyrrolo[3,2,1-de]phenanthridin-5-ones
(16b)
Brown solid, mp:134–135 ◦C; 1H NMR(CDCl3, 400 MHz) d 8.61
(dd, J = 8.0 Hz, 1H), 8.51 (d, J = 8.4 Hz, 1H), 7.77 (t, J = 7.6 Hz,
1H), 7.74 (s, 1H), 7.59 (t, J = 7.6 Hz, 1H), 7.46 (s, 1H), 7.45
(s, 1H), 4.34 (t, J = 6 Hz, 2H), 3.10 (t, J = 6.0 Hz, 2H), 2.10–
2.16 (m, 2H);13C NMR (CDCl3,100 MHz) d 160.9, 150.8, 145.5,
134.2, 132.0, 131.4, 128.5, 127.3, 125.6, 124.4, 123.0, 121.2, 112.8,
112.7, 107.4, 43.5, 29.3, 20.8; FT-IR (KBr,cm-1) 3124, 2929, 2873,
1627, 1602, 1346, 1149, 1035, 790. ESI-HMRS: (m/z) calcd for
C18H13NO2 (M+H+) 276.1019, found 276.1023.
6 (a) C.-L. Wang, W. Zhang, S.-C. Lu, J.-F. Wu and Z.-J. Shi, Chem.
Commun., 2008, 5176–5178; (b) B. Li, B. Han, Z.-J. Shi, Y.-W.
Ren, S.-C. Lu and W. Zhang, Tetrahedron Lett., 2010, 51, 3748–
3751.
7 (a) S. Protti, M. Fagnoni and A. Albini, Angew. Chem., Int. Ed., 2005,
44, 5675; (b) N. A. Gordeeva, M. A. Kirpichenok, D. S. Yufit, Yu. T.
Struchkov and I. I. Grandberg, Chem. Heterocycl. Compd., 1990, 26,
863.
8 Crystal data for compound 8d (recrystallized from acetone-hexane):
˚
C20H14ClNO, M = 319.77, orthorhombic, a = 7.272(4) A, b = 11.909(6)
◦
3
˚
˚
˚
A, c = 17.041(8) A,b = 90 , V = 1475.9(12) A , colorless plates, r =
1.439 g cm-3, T = 296(2)K, space group P212121, Z = 4, m (MoK\a) =
0.263 mm-1 2qmax = 50.80, 7084 reflection collected, 2705 unique (Rinit
=
0.05 12) which was used in all calculations. Final wR (F2) = 0.1772 (all
data). CCDC file No. 806191.
Acknowledgements
9 (a) H. R. Talele, M. J. Gohil and A. V. Bedekar, Bull. Chem. Soc. Jpn.,
2009, 82, 1182; (b) P. H. G. op het Veld and W. H. Laarhoven, J. Chem.
Soc., Perkin Trans. 2, 1978, 922.
We thank the National Natural Science Foundation of China
(20472027) for financial support
10 Crystal data for compound 14a (recrystallized from acetone-hexane):
˚
˚
C14H11NO2, M = 225.24, orthorhombic, a = 7.168(3 A, b = 15.046(7) A,
References
3
-3
˚
˚
c = 9.688(4) A,b = 90, V = 1044.8(8) A , colorless plates, r = 1.432 g cm ,
T = 296 (2)K, space group Pna2(1), Z = 4, m (MoK\a) = 0.097 mm-1,
2qmax = 51.96, 5818 reflection collected, 2025 unique (Rinit = 0.0426)
which was used in all calculations. Final wR (F2) = 0.0966 (all data).
CCDC file No. 800642.
1 (a) M. Fagnoni and A. Albini, Acc. Chem. Res., 2005, 38, 713; (b) A.
R. Roberto, B. P. Adriana and B. P. Alicia, Chem. Rev., 2003, 103,
71–167; (c) V. Dichiarante and M. Fagnoni, Synlett., 2008, 787–800;
(d) M. Fagnoni, Heterocycles, 2003, 60, 1921–1958; (e) A. D’. Maurizio,
Trends Photochem. Photobiol., 1994, 3, 1–18; (f) J. Grimshaw and A. P.
De Silva, Chem. Soc. Rev., 1981, 10, 181–203.
11 C. Kaneko, T. Naito and C. Miwo, Chem. Pharm. Bull., 1982, 30,
752.
5808 | Org. Biomol. Chem., 2011, 9, 5802–5808
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