An efficient synthesis of 3-substituted isoquinoline and pyridine derivatives by gold catalyzed intramolecular cyclization from o-alkynyloximes

Article abstract of DOI:10.1002/jhet.2109

A one-pot reaction was developed efficiently by AuCl₃ catalyzed intramolecular cyclization of aromatic o-alkynyloximes and 2-alkynylcycloalkene- 1-carbaldoximes leading to the formation of isoquinoline and pyridine derivatives with high yields. This methodology has been applied for aromatic as well as aliphatic systems. Aromatic o-alkynyloximes are benzene and naphthalene, whereas electron-donating groups are 4-methoxybenzene, 4-methylbenzene, and 4-methoxy-5-methylbenzene. There are electron-withdrawing groups such as chloro and nitrobenzene o-alkynyl oximes, and the same methodology has been successfully applied to pyridine and piperonal, which is also extended to aliphatic rings such as five-member, six-member, seven-member, and eight-member 2-alkynylcycloalkene-1-carbaldoximes.

Full text of DOI:10.1002/jhet.2109

July 2014
An Efficient Synthesis of 3-Substituted Isoquinoline and Pyridine Derivatives
by Gold Catalyzed Intramolecular Cyclization from o-Alkynyloximes
1045
*
K. P. V. Subbarao, G. Raveendra Reddy, A. Muralikrishna, and K. V. Reddy
Department of Chemistry, Vikrama Simhapuri University, Nellore 524 003, Andhra Pradesh, India
*
E-mail: kattareddy_org@yahoo.com
Received March 12, 2013
DOI 10.1002/jhet.2109
Published online 16 December 2013 in Wiley Online Library (wileyonlinelibrary.com).
OH
OH
+
OH
Ph
N
N
N
N
AuCl3
1,4-dioxane
800C
Ph
-
Ph
Ph
AuCl3
AuCl3
1a
2a
A one-pot reaction was developed efficiently by AuCl3 catalyzed intramolecular cyclization of aromatic
o-alkynyloximes and 2-alkynylcycloalkene-1-carbaldoximes leading to the formation of isoquinoline and
pyridine derivatives with high yields. This methodology has been applied for aromatic as well as aliphatic
systems. Aromatic o-alkynyloximes are benzene and naphthalene, whereas electron-donating groups are
4-methoxybenzene, 4-methylbenzene, and 4-methoxy-5-methylbenzene. There are electron-withdrawing
groups such as chloro and nitrobenzene o-alkynyl oximes, and the same methodology has been successfully
applied to pyridine and piperonal, which is also extended to aliphatic rings such as five-member,
six-member, seven-member, and eight-member 2-alkynylcycloalkene-1-carbaldoximes.
J. Heterocyclic Chem., 51, 1045 (2014).
INTRODUCTION
80°C, produced isoquinoline and pyridine derivatives with
excellent yields.
N-Heterocycles hold an important and special place
among pharmaceuticals and natural products. Significant
efforts are being carried out to the development of
methodologies for the generation of nitrogen-containing
heterocycles [1,2]. In the last few decades, an intense
attention has been paid continuously to isoquinoline and
pyridine derivatives because of their immense biological
importance in many natural products and small molecule
chemotherapeutics [3–12]. Their biological activities have
made them useful in pharmaceutical properties such as
antitumor, analgesic, antihistaminic, and antifertility
activity [13], and their physical properties make them
beneficial as functional materials [10,11].
Accordingly, a number of synthetic methods for
isoquinolines have been developed; for example, classic
methods, such as the Pomeranz–Fritsch [14], Bischler–
Napieralski [15], and Pictet–Spengler [16] reactions, have
considerable drawbacks such as the use of strong acids
and elevated temperatures. In Bischler–Napieralski and
Pictet–Spengler reactions, an additional step involving
dehydrogenation is required to complete the synthesis of
isoquinoline. Later, the transition metal-catalyzed
synthesis of substituted isoquinolines from phenylacetylene
substrates [17–23] was reported. In recent studies, Larock
et al reported the efficient synthesis of isoquinoline
derivatives via transition metal-catalyzed cyclization of
ortho-alkynylaryl aldimines [24,25]. These reactions have
proven to be extremely efficient in the synthesis of a wide
variety of isoquinolines. However, the development of
additional synthetic methods is still highly desirable.
RESULT AND DISCUSSION
The initial precursor, 2-(phenylethynyl) benzaldehyde
oxime (1a), is prepared from 2-bromobenzaldehyde and
phenylacetylene by Sonogashira coupling reaction, and
the resultant compound has been treated with hydroxyl-
amine hydrochloride in the presence of sodium acetate.
Our study is initiated with substrate 1a in the presence of
various late transition metal catalysts. Table 1 shows the
reaction of 1a with different reaction conditions. Although
substrate 1a is treated with AuCl3 and AuCl(PPh3)/AgSbF6
in 1,4-dioxane at room temperature simultaneously for
3 h and 24 h, this has not yielded any reaction product
(entries 1–4). However, when the same reaction is heated
at 80°C for 2 h, the reaction proceeded smoothly, as the
reaction mixture is purified by column chromatography
that has resolved one pure product, that is, 3-
phenylisoquinoline (2a) (entry 5) with 96% yield. In fact,
the reaction speed has been accelerated dramatically at
high temperatures. Further, the same reaction with AuCl
(PPh3)/AgSbF6 in 1,4-dioxane at 80°C, has been
completed within 2 h to obtain exclusively 2a, albeit with
lower yield 91% (entry 6). The compound 2a is well
identified by 1H-NMR, 13C-NMR, and elemental analysis.
Of the two catalysts, AuCl3 is the better choice for this
intramolecular cyclization reaction (Scheme 1).
The scope and generality of the present reaction is
shown in Table 2; further, the reaction has been carried
out with 3-(phenylethynyl)-2-naphthaldehyde oxime (1b)
in 1,4-dioxane at 80°C, which requires longer reaction time
36 h to afford 3-phenylbenzo[g]isoquinoline (2b) with
In this paper, we report that AuCl3 catalyzed intramolecular
cyclization reaction of o-alkynyloximes, in 1,4-dioxane at
© 2013 HeteroCorporation

1046
K. P. V. Subbarao, G. Raveendra Reddy A. Muralikrishna, and K. V. Reddy
Vol 51
Table 1
Screening of the catalytic activity to cyclize 1a under various conditions.
Entry
Catalyst (mol%)
Solvent
Time (h)
Temperature (°C)
Product/yield
1
2
3
4
5
6
AuCl3 (3)
AuCl(PPh3)/AgSbF6 (3)
AuCl3 (3)
AuCl(PPh3)/AgSbF6 (3)
AuCl3 (3)
AuCl(PPh3)/AgSbF6 (3)
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
3
3
24
24
2
RT
RT
RT
RT
80
NR
NR
NR
NR
2a/96
2a/91
2
80
RT, room temperature; NR, no reaction.
Scheme 1
OH
OH
Ph
+
OH
Ph
N
N
N
N
AuCl3
1,4-dioxane
800C
Ph
-
Ph
AuCl3
AuCl3
1a
2a
92% yield (entry 2). It is also noted that the reaction
proceeded with substrates that have electron-donating
groups such as 4-methoxy-2-(phenylethynyl)benzaldehyde
oxime (1c), 4-methyl-2-(phenylethynyl) benzaldehyde
oxime (1d), and 4-methoxy-5-methyl-2-(phenylethynyl)
benzaldehyde oxime (1e), which produced 6-methoxy-3-
phenylisoquinoline (2c), 6-methyl-3-phenylisoquinoline
(2d), and 6-methoxy-7-methyl-3-phenylisoquinoline (2e)
with 96, 96, and 94% yields, respectively (entries 3–5).
On the other hand, the reaction has also been treated with
the substrates that have electron-withdrawing groups such
as 4-chloro-2-(phenylethynyl)benzaldehyde oxime (1f)
and 4-nitro-2-(phenylethynyl)benzaldehyde oxime (1g)
giving 6-chloro-3-phenyl isoquinoline (2f) and 6-nitro-3-
phenylisoquinoline (2g) (entries 6 and 7). It is worth noting
that the reaction has good productive yield with 2-(hex-1-
yn-1-yl)benzaldehyde oxime (1h), 2-(phenylethynyl)
nicotinaldehyde oxime (1i) was insoluble in 1,4-dioxane,
and thus, DMSO was used as solvent in entry 9 and
6-(phenylethynyl)-1,3-benzodioxole-5-carbaldehyde oxime
(1j) that gave the cyclized products 3-butylisoquinoline
(2 h) with 61% yield (entry 8), 7-phenyl-1,6-naphthyridine
(2i) with 91% yield (entry 9), and 7-phenyl-[1,3]dioxolo
[4,5-g]isoquinoline (2j) with 89% yield (entry 10).
To substantiate further, this methodology has
been applied for aliphatic ring systems such as five-
member, six-member, seven-member, and eight-member
2-alkynylcycloalkene-1-carbaldoximes. The reaction of 2-
(phenylethynyl)cyclopent-1-ene-1-carbaldehyde oxime (1k),
2-(phenylethynyl)cyclohex-1-ene-1-carbaldehyde oxime (1l),
as 2-(phenylethynyl)cyclohept-1-ene-1-carbaldehyde oxime
(1m), 2-phenylethynyl)cyclooct-1-ene-1-carbaldehyde oxime
(1n) at 80°C for 6 h gave 3-phenyl-6,7-dihydro-5H-cyclopenta
[c]pyridine (2k), 3-phenyl-5,6,7,8-tetrahydroisoquinoline
(2l), 3-phenyl-6,7,8,9-tetrahydro-5H-cyclohepta[c]pyridine
(2m), and 3-phenyl-5,6,7,8,9,10-hexahydrocycloocta[c]-
pyridine (2n), respectively, with excellent yields (entries
11–14). It was observed that the reaction of 2-(phenylethynyl)
benzonitrile (1o) with AuCl3 at 80°C for 24 h did not yield
isoquinoline, and the starting material was recovered.
All the compounds (2a–2n) (Table 2) were characterized by
1H, 13C-NMR, and elemental analysis.
CONCLUSION
In conclusion, we have developed a simple and efficient
one-pot synthesis to prepare isoquinoline and pyridine
derivatives from o-alkynyloximes catalyzed by AuCl3.
This methodology has been applied to electron-donating
and electron-withdrawing groups in aromatic systems.
Similar methodology is also applied for aliphatic 2-
alkynylcycloalkene-1-carbaldoximes.
EXPERIMENTAL
Melting points were determined in open capillaries on a
Mel-Temp apparatus and are uncorrected. Infrared spectra were
measured on a Nicolet Magna-IR 550 spectrometer (Series-II)
as KBr pellets, unless otherwise noted. NMR spectra were
recorded in CDCl3 on a 400-MHz Varian spectrophotometer.
All chemical shifts were reported in parts per million from TMS
as an internal standard. The elemental analysis was performed
by Perkin Elmer 24°C elemental analyzer. Mass spectra were
recorded on a time-of-flight instrument. Starting materials were
prepared according to literature procedure [26].
General procedure for the preparation of 2a. In a 5-mL
oven-dried test tube, 2-(phenylethynyl)benzaldehyde oxime
1a (100 mg, 0.45 mmol), AuCl3 (7 mg, 0.0226 mmol), and 1,4-
dioxane (1.0 mL) were added at room temperature. The
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

July 2014
An Efficient Synthesis of 3-Substituted Isoquinoline and Pyridine Derivatives by
Gold Catalyzed Intramolecular Cyclization from o-Alkynyloximes
1047
Table 2
Reactions of various o-alkynyloximes.a
Entry
1
Substrate
Product
Time (h)
Yield (%)
1a
2a
2
96
1b
1c
2b
2c
2
3
36
2
92
96
1d
2d
4
2
96
1e
1f
2e
2f
5
6
6
6
94
92
1g
1h
2g
2h
7
8
6
90
61
12
1i
1j
2i
2j
9
12
46
91
89
10
(Continues)
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

1048
K. P. V. Subbarao, G. Raveendra Reddy A. Muralikrishna, and K. V. Reddy
Vol 51
Table 2. (Continued)
Table 2
(Continued)
Entry
Substrate
Product
Time (h)
Yield (%)
1k
2k
11
12
6
96
1l
2l
2m
2n
6
6
92
96
91
1m
13
1n
1o
14
15
6
NR
24
SM recovered
NR, no reaction; SM, starting material.
aAll the reactions were carried out at 80°C in 3-mol% AuCl3 and 1,4-dioxane as solvent except entry 9 in DMSO.
resulting mixture was stirred for 2 h at 80°C, and the solvent was
removed under vacuum. The crude compound was purified by
column chromatography (SiO2, n-hexane/EtOAc = 10:1) to
afford the pure product 2a. The known compounds data were
compared with those reported in the literature [27].
6-Methoxy-3-phenylisoquinoline (2c).
White solid, yield
(90 mg, 96%), mp. 96–97°C, 1H-NMR (400 MHz, CDCl3) δ
9.18 (s, 1H), 8.10 (d, J = 7.2 Hz, 2H), 7.96 (s, 1H), 7.86
(d, J = 8.8 Hz, 1H), 7.50 (t, J = 8.0 Hz, 2H), 7.41 (t, J = 7.2 Hz,
1H), 7.19 (dd, J = 6.8 Hz, 1H) 7.10 (s, 1H), 3.95 (s, 3H);
13C-NMR δ 161.07, 151.75, 151.51, 139.73, 138.57, 129.20,
128.72, 128.44, 126.97, 123.58, 120.14, 115.90, 104.37, 55.45.
Anal. calcd. for C16H13NO: C, 81.68; H, 5.57; N, 5.95. Found:
C, 81.54; H, 5.69; N, 5.91%. HRMS [found: m/z 235.0994
(M+), calcd for C16H13NO: M, 235.0997].
3-Phenylisoquinoline (2a). White solid, yield (89 mg, 96%),
1
mp. 96–97°C; H-NMR (400 MHz, CDCl3) δ 9.34 (s, 1H), 8.13
(d, J = 7.6Hz, 2H), 8.07 (s, 1H), 7.99 (d, J = 8.0 Hz, 1H), 7.87
(d, J = 8.0Hz, 1H), 7.69 (t, J = 7.6 Hz, 1H), 7.58 (t, J = 7.6 Hz,
1H), 7.51 (t, J = 7.6 Hz, 2H), 7.42 (t, J = 7.2 Hz, 1H); 13C-NMR δ
152.40 151.30, 139.60, 136.63, 130.45, 128.77, 128.49, 127.74,
127.54, 127.04, 126.98, 126.89, 116.45. Anal. calcd. for
C15H11N: C, 87.77; H, 5.40; N, 6.82. Found: C, 87.34; H, 5.56;
N, 6.68 %. HRMS [found: m/z 205.0893 (M+), calcd for
C15H11N: M, 205.0891].
6-Methyl-3-phenylisoquinoline (2d).
White solid, yield
1
(89 mg, 96%), mp. 127–128°C, H-NMR (400 MHz, CDCl3) δ
9.28 (s, 1H), 8.03 (d, J = 7.4 Hz, 2H), 7.99 (s, 1H), 7.95
(d, J = 8.2 Hz, 1H), 7.55 (t, J = 8.4 Hz, 2H), 7.47 (t, J = 7.8 Hz,
1H), 7.24 (d, J = 6.7 Hz, 1H) 7.16 (s, 1H), 2.41 (s, 3H);
13C-NMR δ 152.25, 150.71, 140.23, 137.71, 136.37, 129.91,
129.31, 127.66, 127.48, 127.25, 125.23, 123.86, 116.29, 24.75.
Anal. calcd. for C16H13N: C, 87.64; H, 5.98; N, 6.39. Found:
C, 87.55; H, 6.09; N, 6.43%. HRMS [found: m/z 219.1052
(M+), calcd for C16H13N: M, 219.1048].
3-Phenylbenzo[g]isoquinoline (2b).
White solid, yield
1
(87 mg, 92%), mp. 110–111°C, H-NMR (400 MHz, CDCl3) δ
9.31 (s, 1H), 8.83 (s, 1H), 8.78–8.76 (m, 1H), 8.19 (d,
J = 7.2 Hz, 2H), 7.95–7.93 (m, 1H), 7.82 (s, 2H), 7.75–7.71 (m,
2H), 7.55 (t, J = 7.2 Hz, 2H), 7.45 (t, J = 7.6 Hz, 1H); 13C NMR
δ 153.37, 151.60, 140.05, 135.58, 133.73, 128.85, 128.74,
128.70, 128.68, 128.17, 127.20, 127.12, 125.90, 124.62,
123.17, 112.50. Anal. calcd. for C19H13N: C, 89.38; H, 5.13; N,
5.49. Found: C, 89.30; H, 5.19; N, 5.41%. HRMS [found: m/z
255.1050 (M+), calcd for C19H13N: M, 255.1048].
6-Methoxy-7-methyl-3-phenylisoquinoline (2e).
White
1
solid, yield (89 mg, 94%), mp. 122–123°C; H-NMR (400 MHz,
CDCl3) δ 9.12 (s, 1H), 8.09 (d, J = 8.0 Hz, 2H), 7.95 (s, 1H),
7.70 (s, 1H), 7.49 (t, J = 7.6 Hz, 2H), 7.39 (t, J = 7.2 Hz, 1H),
7.06 (s, 1H), 3.99 (s, 3H), 2.40 (s, 3H); 13C-NMR δ 160.40,
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

July 2014
An Efficient Synthesis of 3-Substituted Isoquinoline and Pyridine Derivatives by
Gold Catalyzed Intramolecular Cyclization from o-Alkynyloximes
1049
150.89, 150.70, 139.94, 137.39, 130.24, 128.70, 128.25, 126.90,
123.49, 115.62, 103.11, 55.52, 17.00. Anal. calcd. for C17H15NO:
C, 81.90; H, 6.06; N, 5.62. Found: C, 82.12; H, 5.94; N, 5.58%.
HRMS [found: m/z 249.1158 (M+), calcd for C17H15NO:
M, 249.1154].
3-Phenyl-5,6,7,8-tetrahydroisoquinoline (2l).
Colorless
1
liquid, yield (68 mg, 92%); H-NMR (400 MHz, CDCl3) δ 8.37
(s, 1H), 7.94 (d, J = 7.2 Hz, 2H), 7.46–7.35 (m, 4H), 2.79
(t, J = 4.8 Hz, 4H), 1.84 (t, J = 3.2 Hz, 4H); 13C-NMR δ 154.38,
150.23, 146.70, 139.71, 131.65, 128.58, 128.32, 126.66,
120.67, 28.94, 26.03, 22.68, 22.46. Anal. calcd. for C15H15N:
C, 86.08; H, 7.22; N, 6.69. Found: C, 85.94; H, 7.31;
N, 6.64%. HRMS [found: m/z 209.1207 (M+), calcd for
C15H15N: M, 209.1204].
3-Phenyl-6,7,8,9-tetrahydro-5H-cyclohepta[c]pyridine
(2m). Colorless liquid, yield (71 mg, 96%); 1H-NMR (400 MHz,
CDCl3) δ 8.38 (s, 1H), 7.96 (d, J = 6.8 Hz, 2H), 7.47–7.43 (m,
3H), 7.38 (t, J = 7.2 Hz, 1H), 2.82 (dd, J = 7.6 Hz, 4H), 1.89
(quintet, J = 5.6Hz, 2H), 1.69 (t, J = 4.8 Hz, 4H); 13C-NMR δ
155.61, 152.71, 149.20, 139.57, 137.26, 128.60, 128.44, 126.70,
120.76, 36.55, 32.96, 32.61, 28.04, 27.55. Anal. calcd. for
C16H17N: C, 86.05; H, 7.67; N, 6.27. Found: C, 86.12; H, 7.59;
N, 6.29%. HRMS [found: m/z 223.1358 (M+), calcd for C16H17N:
M, 223.1361].
3-Phenyl-5,6,7,8,9,10-hexahydrocycloocta[c]pyridine (2n).
Colorless liquid, yield (85 mg, 91%); 1H-NMR (400 MHz,
CDCl3) δ 8.39 (s, 1H), 7.97 (d, J = 7.6 Hz, 2H), 7.47–7.44
(m, 3H), 7.38 (t, J = 7.6 Hz, 1H), 2.79 (sextet, J = 3.6 Hz, 4H),
1.77–1.70 (m, 4H), 1.45–1.35 (m, 4H); 13C-NMR δ 155.43,
150.71, 149.78, 139.53, 135.59, 128.61, 128.43, 126.63,
120.64, 32.08, 31.74, 31.45, 29.09, 25.85, 25.50. Anal.
calcd. for C17H19N: C, 86.03; H, 8.07; N, 5.90. Found: C,
86.11; H, 8.14; N, 5.85%. HRMS [found: m/z 237.1520
(M+), calcd for C17H19N: 237.1517].
6-Chloro-3-phenylisoquinoline (2f). White solid, yield
1
(90 mg, 96%), mp. 130–131°C; H-NMR (400 MHz, CDCl3) δ
9.29 (s, 1H), 8.11 (d, J = 7.2 Hz, 2H), 7.93 (s, 1H), 8.04
(d, J = 7.8 Hz, 1H), 7.75 (d, J = 7.8 Hz, 1H), 7.84 (s, 1H), 7.52
(t, J = 7.4 Hz, 2H), 7.44 (t, J = 7.1 Hz, 1H); 13C-NMR δ 152.25,
151.12, 138.54, 136.70, 131.36, 128.94, 128.50, 127.71,
127.49, 127.07, 126.77, 126.61, 116.58. Anal. calcd. for
C15H10ClN: C, 75.16; H, 4.21; N, 5.84. Found: C, 75.24;
H, 4.14; N, 5.91%. HRMS [found: m/z 239.0506 (M+),
calcd for C15H10ClN: M, 239.0502].
6-Nitro-3-phenylisoquinoline (2g). White solid, yield (84 mg,
90%), mp. 140–141°C; 1H-NMR (400 MHz, CDCl3) δ 9.39
(s, 1H), 8.12 (d, J = 7.2 Hz, 2H), 8.33 (s, 1H), 8.18
(d, J = 7.8 Hz, 1H), 8.25 (d, J = 7.8 Hz, 1H), 7.93 (s, 1H), 7.53
(t, J = 7.4 Hz, 2H), 7.45 (t, J = 7.1 Hz, 1H); 13C-NMR δ
152.45, 151.42, 138.56, 134.70, 150.36, 128.92, 129.50,
121.71, 127.51, 127.11, 124.75, 129.67, 120.42. Anal. calcd.
for C15H10N2O2: C, 71.99; H, 4.03; N, 11.19. Found: C,
72.27; H, 4.12; N, 11.15%. HRMS [found: m/z 250.0745
(M+), calcd for C15H10N2O2: M, 250.0742].
3-Butylisoquinoline (2h).
Colorless liquid, yield (56 mg,
61%); 1H-NMR (400 MHz, CDCl3) δ 9.21 (s, 1H), 7.92
(d, J = 8.4 Hz 1H), 7.74 (d, J = 8.4 Hz, 1H), 7.64 (t, J = 7.6 Hz,
1H), 7.52 (t, J = 8.0 Hz, 1H), 7.47 (s, 1H), 2.94 (t, J = 7.2 Hz,
2H), 1.80 (quintet, J = 7.6 Hz, 2H), 1.42 (sextet, J = 7.2 Hz, 2H),
0.96 (t, J = 7.6 Hz, 3H); 13C-NMR δ 155.87, 152.00, 136.51,
130.17, 127.48, 126.24, 126.06, 118.05, 117.89, 37.84, 32.13,
22.47, 13.97. Anal. calcd. for C13H15N: C, 84.28; H, 8.16;
N, 7.56. Found: C, 84.39; H, 8.05; N, 7.61%. HRMS [found:
m/z 185.1207 (M+), calcd for C13H15N: M, 185.1204].
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2004, 5, 508.
7-Phenyl-1,6-naphthyridine (2i). White solid, yield (85 mg,
91%), mp. 131–132°C; 1H-NMR (400 MHz, CDCl3) δ 9.36
(s, 1H), 9.10 (dd, J = 1.6 Hz, 1H), 8.35 (s, 1H), 8.31
(d, J = 8.0 Hz, 1H), 8.18 (d, J = 7.6 Hz, 2H), 7.56–7.50 (m, 3H),
7.45 (t, J = 6.8 Hz, 1H); 13C-NMR δ 155.92, 155.74, 153.36,
152.08, 139.55, 136.29, 129.86, 129.61, 127.90, 123.37,
122.88, 118.50. Anal. calcd. for C14H10N2: C, 81.53; H, 4.89;
N, 13.58. Found: C, 81.64; H, 4.82; N, 13.64%. HRMS [found:
m/z 206.0841 (M+), calcd for C14H10N2: M, 206.0844].
7-Phenyl-[1,3]dioxolo[4,5-g]isoquinoline (2j). Yellow solid,
yield (84mg, 89%), mp. 117–118°C, 1H-NMR (400 MHz,
CDCl3) δ 9.08 (s, 1H), 8.06 (d, J = 7.6 Hz, 2H), 7.90 (s, 1H), 7.49
(t, J = 7.6Hz, 2H), 7.40 (t, J = 7.2 Hz, 1H), 7.21 (s, 1H), 7.12
(s, 1H), 6.10 (s, 2H); 13C-NMR δ 151.15, 150.60, 150.13, 148.37,
139.62, 135.11, 128.72, 128.30, 126.82, 125.03, 116.44, 103.13,
102.80, 101.62. Anal. calcd. for C16H11NO2: C, 77.10; H, 4.45;
N, 5.62. Found: C, 77.16; H, 4.39; N, 5.64%. HRMS [found: m/z
249.0793 (M+), calcd for C16H11NO2: M, 249.0790].
3-Phenyl-6,7-dihydro-5H-cyclopenta[c]pyridine (2k). Colorless
liquid, yield (89 mg, 96%); 1H-NMR (400 MHz, CDCl3) δ 8.53 (s,
1H), 7.95 (d, J =7.6 Hz, 2H), 7.60 (s, 1H), 7.45 (t, J = 7.2 Hz, 2H),
7.38 (t, J = 7.6 Hz, 1H), 2.97 (t, J = 8.0Hz, 4H), 2.14 (quintet,
J = 7.6Hz, 2H); 13C-NMR δ 155.41, 154.60, 145.34, 139.98,
138.71, 128.59, 128.36, 126.87, 116.81, 32.71, 29.98, 25.07.
Anal. calcd. for C14H13N: C, 86.12; H, 6.71; N, 7.17. Found: C,
85.98; H, 6.89; N, 7.12%. HRMS [found: m/z 195.1052 (M+),
calcd for C14H13N: M, 195.1048].
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