Synthesis of pyrrolo[2,1-a]isoquinolines by a tandem 1,5- electrocyclisation-oxidation process

Article abstract of DOI:10.1055/s-2007-965959

A simple protocol for the convenient synthesis of 5,6-dihydropyrrolo[2,1-a] isoquinolines, utilising a one-pot, sequential azomethine ylide 1,5-electrocyclisation-oxidation process is described. Georg Thieme Verlag Stuttgart.

Full text of DOI:10.1055/s-2007-965959

PAPER
1003
Synthesis of Pyrrolo[2,1-a]isoquinolines by a Tandem 1,5-Electrocyclisation–
Oxidation Process
S
ynthesis
u
of Pyrrolo[2
d
,1-
a
]isoquino
i
lines t Tóth,a Andrea Nedves,a András Dancsó,b Gábor Blaskó,b László Tőke,a Miklós Nyerges*a
a
Research Group of the Hungarian Academy of Sciences, Department of Organic Chemical Technology, Technical University of
Budapest, P.O.B. 91, Budapest 1521, Hungary
Fax +361(463)3648; E-mail: mnyerges@mail.bme.hu
EGIS Pharmaceuticals Ltd., P.O.B. 100, Budapest 1475, Hungary
b
Received 14 December 2006
tramolecular Heck reactions8 and cyclisation of 1- or 2-
benzylisoquinolines.9,10
Abstract: A simple protocol for the convenient synthesis of 5,6-di-
hydropyrrolo[2,1-a]isoquinolines, utilising a one-pot, sequential
azomethine ylide 1,5-electrocyclisation–oxidation process is de-
scribed.
Our own interest in the development of new protocols for
the synthesis of nitrogen-containing heterocycles by 1,5-
Key words: alkaloids, azomethine ylides, electrocyclic reaction, or 1,7-electrocyclisation of azomethine ylides,11 prompt-
cycloaddition, pyrroles
ed us to investigate the feasibility of a tandem electrocy-
clisation–oxidation process for the synthesis of
pyrrolo[2,1-a]isoquinolines using our recent observations
on the reactivity of various stabilised a,b:g,d-unsaturated
azomethine ylides generated, by the deprotonation meth-
od, from isoquinolinium salts.12 We report here a practical
and general method for the synthesis of 1,2-diaryl-5,6-di-
hydropyrrolo[2,1-a]isoquinolines.
Considerable interest has been shown in substituted pyr-
rolo[2,1-a]isoquinolines due to their diverse biological
activities. They are constituents of several natural prod-
ucts such as erythrina,1 lamellarin2 and jamtine3 alkaloids
(Figure 1).
Initially, the required 1-(1¢,2¢-diaryl-1¢-ethenyl)-3,4-dihy-
droisoquinolines 3 were prepared from known stilbenic
acids13 in two straightforward steps. Treatment of stilben-
ic acid chlorides with a slight excess of 2-(3,4-dimethoxy-
phenyl)ethylamine gave the amides 2, which could be
cyclised using the standard Bischler–Napieralski proce-
dure,14 in the presence of POCl3, to give the 3,4-dihy-
droisoquinolines 3 (Scheme 1, Table 1).
MeO
MeO
MeO
MeO
N
N
H
MeO2C
MeO
jamtine
erysotramidine
HO
O
H
N
Ar1
N
Ar1
MeO
HO
MeO
MeO
ii
i
O
HO
O
Ar2
O
Ar2
2
MeO
1
OMe
HO
lamellarine D
MeO
MeO
MeO
MeO
Br
iii
N
N
R
Figure 1 Alkaloids with pyrrolo[2,1-a]isoquinoline skeleton.
Ar2
Ar2
Ar1
Ar1
4
3
These classes of compounds are traditionally synthesised
by the ring closure of iminium intermediates.4 Since the
discovery of the potent cytotoxic and topoisomerase I in-
hibitory activity of lamellarines, a number of new synthet-
ic strategies have been developed, based on, for example,
intramolecular oxidative biaryl coupling,5 1,3-dipolar cy-
cloaddition of azomethine ylides,6 thermal reactions of 4-
ixovazoline derivatives (obtained by cycloadditions of
3,4-dihydroisoquinoline N-oxides with alkynes),7 in-
Scheme 1 Reagents and conditions: (i) (a) SOCl2, CH2Cl2 (b) (3,4-
dimethoxyphenyl)ethylamine, Et3N, CH2Cl2; (ii) POCl3, toluene,
reflux; (iii) RCH2Br, Et2O, r.t.
Subsequent reaction with ethyl bromoacetate or benzyl
bromide, in anhydrous ether gave the quaternary salts 4.
The dehydrohalogenation of 4 (R = Ph), in an ethanolic
solution at ambient temperature, afforded pyrrolines 5 as
the main product, which could be isolated in moderate to
good yields by simple filtration (Scheme 2). The relative
stereochemistry of this type of cycloadduct was deduced
by NOE studies.
SYNTHESIS 2007, No. 7, pp 1003–1014
x
x
.
x
x
.2
0
0
7
Advanced online publication: 28.02.2007
DOI: 10.1055/s-2007-965959; Art ID: P14906SS
© Georg Thieme Verlag Stuttgart · New York

1004
J. Tóth et al.
PAPER
Table 1 Compounds 2a–h and 3a–h Prepareda
MeO
MeO
MeO
MeO
Br
i
Entry Ar1
Ar2
Isolated Isolated
N
R
N
R
yield
yield
Ar2
Ar1
of 2
of 3
Ar1
Ar2
4
5
1
2a
3a
91%
96%
Scheme 2 Reagents and conditions: (i) Et3N, EtOH, r.t.
OMe
2
2b
95%
3b
98%
MeO
MeO
MeO
MeO
Br
i
N
R
N
R
Ar2
Br
Ar1
Ar1
Ar2
3
4
5
2c
85%
3c
86%
4
6
Scheme 3 Reagents and conditions: (i) Et3N, MnO2, CH2Cl2, r.t.
Cl
2d
82%
3d
90%
In this sequence, the azomethine ylides 7 are produced by
dehydrohalogenation of the isoquinolinium salts15 which
leads, via a 1,5-electrocyclisation, to the pyrrolines 5. In
the presence of manganese dioxide, in a tandem oxidation
process, the pyrrole derivatives 6 were obtained as the
sole product (Scheme 4).
Cl
2e
91%
3e
92%
Cl
MeO
6
7
2f
90%
3f
81%
In summary, we have successfully developed a fast and
efficient protocol for the convenient synthesis of 5,6-dihy-
dropyrrolo[2,1-a]isoquinolines 6, utilising a one-pot, se-
quential electrocyclisation–oxidation process as a key
step. This methodology may find application in the syn-
thesis of the pharmacologically interesting lamellarine de-
rivatives.2
MeO
MeO
Cl
2g
93%
3g
85%
MeO
MeO
O2N
Cl
8
2h
93%
3h
80%
Column chromatography was performed using Merck Kieselgel 60
(70–230 mesh), TLC was performed on aluminium sheets coated
with Kieselgel 60 F254. Plates were stained with anisaldehyde solu-
tion [glacial AcOH (100 mL), H2SO4 (2 mL) and anisaldehyde (1
mL)] and heated at ~150 °C. IR spectra were measured on a Bruker
VECTOR 22 FT-IR instrument. NMR spectra were recorded on a
Bruker Avance DRX-500 spectrometer. Chemical shifts (d) are giv-
en relative to TMS. All solvents were purified according to standard
procedures.
MeO
a Satisfactory microanalyses were obtained for each product: C 0.3,
0.3, N 0.2.
H
When compound 4 (R = CO2Et) was used under the same
conditions, a complex mixture of products were formed
with the main components, pyrrole derivatives 6, obtained
after column chromatography in about 50% yield. In two
cases, the corresponding 5 pyrrolines were also precipitat-
ed and could be isolated, in low yields, by filtration.
Preparation of N-(3,4-Dimethoxyphenethyl)-(E)-2,3-diaryl-2-
propenamides (2); General Procedure
2-(3,4-Dimethoxyphenyl)ethylamine (1.82 g, 10 mmol) was dis-
solved in CH2Cl2 (40 mL) and Et3N (0.71 mL, 1.01 g, 10 mmol) was
added. This mixture was cooled to 0 °C and freshly prepared stilbe-
nic acid chloride (10 mmol; prepared from the corresponding stilbe-
nic acid by the action of thionyl chloride), dissolved in CH2Cl2 (40
mL) was added dropwise. The reaction mixture was stirred at r.t. for
5 h then the organic layer was washed with H2O (2 × 30 mL) and
brine (30 mL) then dried (MgSO4) and evaporated in vacuo to yield
the product. See Table 3 for spectral data.
Reacting the isoquinolinium salts 4 with triethylamine, in
dichloromethane at ambient temperature, in the presence
of manganese dioxide, led to the clean and rapid forma-
tion of 5,6-dihydropyrrolo[2,1-a]isoquinolines 6, which
were isolated in good yields after flash chromatography
(Scheme 3, Table 2).
MeO
MeO
N
N
R
R
4
6
MeO
MeO
Ar2
Ar1
Ar1
Ar2
5
7
Scheme 4
Synthesis 2007, No. 7, 1003–1014 © Thieme Stuttgart · New York

PAPER
Synthesis of Pyrrolo[2,1-a]isoquinolines
1005
Table 2 Compounds 4a–p, 5a–i and 6a–j Prepareda
Entry
1
Starting material
Isolated yield of 4
Rb
Reaction conditionsc Isolated yield of 5
Isolated yield of 6
3a
4a
98%
CO2Et
A
B
A
B
A
B
B
A
B
A
A
B
A
B
A
B
B
B
A
5a
10%
6a
27%
2
3
3a
3a
3b
3b
3b
3c
3c
3d
3d
3e
3e
3e
3f
–
CO2Et
Ph
–
6a
52%
4b
98%
5b
30%
–
4
4c
91%
CO2Et
Ph
–
6b
62%
5
4d
88%
5c
40%
–
6
–
Ph
–
–
6c
60%
7
4e
95%
CO2Et
Ph
6d
71%
8
4f
87%
5d
51%
–
9
4g
94%
CO2Et
Ph
–
6e
66%
10
11
12
13
14
15
16
17
18
19
4h
97%
5e
48%
–
4i
92%
CO2Et
CO2Et
Ph
5f
12%
6f
20%
–
–
6f
71%
4j
96%
5g
50%
–
4k
95%
CO2Et
Ph
–
6g
70%
3f
4l
93%
5h
33%
–
3g
3g
3h
3h
4m
94%
CO2Et
Ph
–
–
–
6h
63%
4n
99%
6i
66%
4o
91%
CO2Et
Ph
6j
57%
4p
5i
–
91%
42%
a Satisfactory microanalyses were obtained for each product: C 0.3, H 0.3, N 0.2.
b For Ar1 and Ar2 refer to Table 1.
c (A) Et3N, EtOH, r.t.; (B) Et3N, MnO2, r.t., CH2Cl2.
Preparation of 6,7-Dimethoxy-1-(1¢,2¢-diaryl-1¢-ethenyl)-3,4-di-
hydroisoquinolines (3); General Procedure
To a well-stirred, externally ice-water cooled solution of the corre-
sponding propenamide 1 (8 mmol) in anhydrous toluene (30 mL)
was added, dropwise, a solution of phosphoryl chloride (4 mL, 6.28
g, 41 mmol) in anhydrous toluene (10 mL). The reaction mixture
was stirred at reflux for 3 h, then the excess of reagent was de-
stroyed by the addition of H2O, with external ice-water cooling. The
residue was stirred for 2 h with an excess of 10% aq NaOH solution
then the aqueous phase was extracted with EtOAc (3 × 20 mL). The
combined organic extracts were washed with brine (30 mL), dried
(MgSO4) and evaporated in vacuo to yield the product. See Table 4
for spectral data.
Synthesis 2007, No. 7, 1003–1014 © Thieme Stuttgart · New York

1006
J. Tóth et al.
PAPER
Preparation of 2-Substituted 1-(1,2-Diarylvinyl)-6,7-dimeth-
oxy-3,4-dihydroisoquinolinium Bromides (4); General Proce-
dure
The corresponding 6,7-dimethoxy-1-(1¢,2¢-diaryl-1¢-ethenyl)-3,4-
dihydroisoquinoline (2 mmol) was dissolved in anhydrous Et2O (30
mL) and either methyl bromoacetate (0.56 mL, 0.82 g, 6 mmol) or
benzyl bromide (0.72 mL, 1.00 g, 6 mmol) was added. The reaction
mixture was stirred at r.t. overnight. The yellow precipitate was fil-
tered off, washed with Et2O (2 × 10 mL) and dried in vacuo to give
the product as a yellow powder. See Table 5 for spectral data.
mL, 1.5 mmol) and the reaction mixture was stirred for 24 h at r.t.
under an argon atmosphere. The precipitated product was filtered
off, washed with EtOH (1 × 5 mL) and dried in vacuo. In several
cases the corresponding 5,6-dihydropyrrolo[2,1-a]isoquinolines (6)
could be isolated from the filtrate after column chromatography on
silica gel (n-hexane–acetone, 3:1). See Table 6 for spectral data.
Preparation of 8,9-Dimethoxy-1,2-diaryl-5,6-dihydropyrro-
lo[2,1-a]isoquinolines (6); General Procedure (B)
To the corresponding 3,4-dihydroisoquinolinium bromide (1.0
mmol) dissolved in CH2Cl2 (10 mL) was added Et3N (0.11 mL, 1.5
mmol) and MnO2 (0.90 g, 10 mmol) and the reaction mixture was
stirred at r.t. for 24 h. The solvent was then removed in vacuo and
the residue was purified by flash column chromatography on silica
gel (n-hexane–acetone, 3:1). See Table 7 for spectral data.
Preparation of 8,9-Dimethoxy-1,2-diaryl-2,3,5,6-tetrahydro-
pyrrolo[2,1-a]isoquinolines (5); General Procedure (A)
To the corresponding 3,4-dihydroisoquinolinium bromide (1.0
mmol) dissolved in anhydrous EtOH (10 mL) was added Et3N (0.11
Table 3 Spectral Data of Compounds 2a–h
Product
IR (KBr; cm–1)
1H NMR [CDCl3/TMS; d (ppm), J (Hz)]
13C NMR [CDCl3/TMS; d (ppm)]
2a
3349, 3062, 2993, 8.13 (1 H, s, H-3), 7.28 (3 H, m, Ar3¢-6¢H, Ph-2¢ and 6¢H),
2961, 2926, 2831, 7.11 (3 H, m, Ph-3¢,4¢ and 5¢H), 6.80 (1 H, d, J = 8.3 Hz,
1651, 1612, 1508, Ar3¢-3¢H), 6.71 (1 H, d, J = 8.2 Hz, Ar-5¢H), 6.62 (1 H, d,
167.0 (q), 158.0 (q), 148.7 (q), 147.3 (q),
136.0 (q), 134.4 (q), 131.7 (CH), 131.1 (q),
129.8 (CH), 129.7 (2 × CH), 129.4 (CH),
1480, 1466, 1437, J = 2 Hz, Ar-2¢H), 6.55 (2 H, m, Ar-6¢H and Ar3¢-4¢H), 6.51 128.8 (2 × CH), 127.8 (CH), 123.9 (q),
1290, 1263, 1240, (1 H, t, J = 8.3 Hz, Ar3¢-5¢H), 5.62 (1 H, t, J = 5.6 Hz, NH), 120.3 (CH), 119.5 (CH), 111.6 (CH), 111.1
1158, 1136, 1115, 3.83 (3 H, s, OMe), 3.81 (3 H, s, OMe), 3.80 (3 H, s, OMe), (CH), 110.2 (CH), 55.7 (CH3), 55.5 (CH3),
1052
3.53 (2 H, m, NCH2), 2.73 (2 H, t, J = 7.0 Hz, ArCH2)
55.1 (CH3), 41.1 (CH2), 34.7 (CH2)
2b
3058, 2999, 2934, 7.72 (1 H, s, H-3), 7.38 (3 H, m, Ph-H), 7.25 (1 H, d, J = 7.9 166.2 (q), 148.8 (q),147.4 (q), 136.8 (q),
2834, 1660, 1616, Hz, Ar3¢-4¢H), 7.09 (2 H, m, Ph-H), 7.05 (1 H, s, Ar3¢-2¢H), 135.7 (q), 135.1 (q), 135.0 (q), 132.7 (CH),
1591, 1505, 1464, 6.96 (1 H, t, J = 7.9 Hz, Ar3¢-5¢H), 6.86 (1 H, d, J = 7.9 Hz, 131.1 (q), 129.4 (CH), 128.5 (2 × CH),
128.4 (CH), 126.9 (q), 126.0 (CH), 121.9
1157, 1141, 1074, J = 2.0 Hz, Ar-2¢H), 6.56 (1 H, dd, J = 2.0, 8.2 Hz, Ar-6¢H), (CH), 120.3 (CH), 111.6 (CH), 111.1 (CH),
1029 5.55 (1 H, t, J = 5.6 Hz, NH), 3.83 (3 H, s, OMe), 3.80 (3 H, 55.7 (CH3), 55.6 (CH3), 41.1 (CH2), 34.6
1418, 1263, 1200, Ar3¢-6¢H), 6.70 (1 H, d, J = 8.2 Hz, Ar-5¢H), 6.60 (1 H, d,
s, OMe), 3.52 (2 H, m, NCH2), 2.71 (2 H, t, J = 7.0 Hz,
(CH2)
ArCH2)
2c
2d
2e
2932, 2921, 2835, 7.79 (1 H, s, H-3), 7.38 (3 H, m, Ar2-H), 7.07 (4 H, m, Ar2- 166.5 (q), 148.7 (q),147.4 (q), 136.1 (q),
1667, 1592, 1513, H and Ar3-H), 6.88 (2 H, m, Ar3-H), 6.71 (1 H, d, J = 8.1 Hz, 135.7 (q), 134.9 (q), 134.2 (q), 130.7 (q),
1454, 1412, 1343, Ar-5¢H), 6.60 (1 H, s, Ar2¢-2¢H), 6.56 (1 H, d, J = 8.1 Hz,
130.5 (2 × CH), 129.5 (2 × CH), 129.4
1310, 1255, 1138, Ar2¢-6¢H), 5.48 (1 H, t, J = 5.6 Hz, NH), 3.86 (3 H, s, OMe), (2 × CH), 129.2 (CH), 126.6 (2 × CH),
1111, 1025
3.82 (3 H, s, OMe), 3.53 (2 H, m, NCH2), 2.72 (2 H, t, J =
120.5 (CH), 120.2 (CH), 111.6 (CH), 111.1
(CH), 55.8 (CH3), 55.7 (CH3), 41.0 (CH2),
34.5 (CH2)
6.6 Hz, ArCH2)
3021, 2935, 2832, 7.94 (1 H, s, H-3),), 7.32 (1 H, d, J = 7.1 Hz, Ar3¢-6¢H), 7.26 166.6 (q), 148.6 (q), 147.6 (q), 135.3 (q),
1652, 1570, 1507, (3 H, m, Ph-H), 7.06 (3 H, m, Ph-H and Ar3¢-4¢H), 6.86 (1 H, 134.3 (q), 134.0 (q), 132.7 (CH), 130.9 (q),
1454, 1359, 1292, t, J = 7.1 Hz, Ar3¢-5¢H), 6.81 (1 H, d, J = 8.1 Hz, Ar-5¢H),
129.6 (2 × CH), 129.4 (CH), 129.3 (CH),
1172, 1165, 1110 6.62 (3 H, m, Ar-2¢, 5¢H and Ar3¢-2¢H), 5.57 (1 H, t, J = 5.6 128.95 (CH), 128.9 (2 × CH), 127.1 (CH),
Hz, NH), 3.85 (3 H, s, OMe), 3.83 (3 H, s, OMe), 3.57 (2 H, 126.8 (q), 125.6 (CH), 120.1 (CH), 111.6
m, NCH2), 2.76 (2 H, t, J = 7.0 Hz, ArCH2)
(CH), 111.1 (CH), 55.7 (CH3), 55.5 (CH3),
41.0 (CH2), 34.3 (CH2)
2936, 2837, 1661, 7.73 (1 H, s, H-3), 7.08 (2 H, d, J = 8.5 Hz, Ar3¢-3¢ and 5¢H), 166.8 (q), 159.3 (q), 148.6 (q), 147.2 (q),
1614, 1513, 1248, 6.98 (2 H, d, J = 8.7 Hz, Ar2¢-2¢ and 6¢H), 6.91 (2 H, d, J = 135.0 (q), 134.4 (q), 133.8 (q), 133.3 (q),
1157, 1091, 1030 8.5 Hz, Ar3¢-2¢ and 6¢H), 6.87 (2 H, d, J = 8.7 Hz, Ar2¢-3¢ and 131.1 (2 × CH), 130.7 (CH), 130.5
5¢H), 6.71 (1 H, d, J = 8.2 Hz, Ar-5¢H), 6.61 (1 H, d, J = 2.0 (2 × CH), 128.2 (q), 128.0 (2 × CH), 126.9
Hz, Ar-2¢H), 6.55 (1 H, dd, J = 2.0, 8.2 Hz, Ar-6¢H), 5.70
(1 H, t, J = 5.6 Hz, NH), 3.83 (3 H, s, OMe), 3.82 (3 H, s,
(q), 120.2 (CH), 114.6 (2 × CH), 111.5
(CH), 111.0 (CH), 55.5 (CH3), 55.4 (CH3),
OMe), 3.80 (3 H, s, OMe), 3.54 (2 H, m, NCH2), 2.72 (2 H, 54.8 (CH3), 40.9 (CH2), 34.5 (CH2)
t, J = 7.0 Hz, ArCH2)
Synthesis 2007, No. 7, 1003–1014 © Thieme Stuttgart · New York

PAPER
Synthesis of Pyrrolo[2,1-a]isoquinolines
13C NMR [CDCl3/TMS; d (ppm)]
1007
Table 3 Spectral Data of Compounds 2a–h (continued)
Product
IR (KBr; cm–1)
1H NMR [CDCl3/TMS; d (ppm), J (Hz)]
2f
3061, 3000, 2935, 7.94 (1 H, s, H-3), 7.31 (1 H, d, J = 6.8 Hz, Ar3¢-6¢H), 7.05 166.9 (q), 159.2 (q), 148.8 (q), 147.4 (q),
2836, 1651, 1573, (1 H, t, J = 6.8 Hz, Ar3¢-4¢H), 6.96 (2 H, d, J = 8.8 Hz, Ar2¢- 136.6 (q), 134.7 (q), 134.0 (q), 132.9 (CH),
1505, 1455, 1361, 2¢ and 6¢H), 6.85 (1 H, t, J = 6.8 Hz, Ar3¢-5¢H), 6.77 (2 H, d, 131.0 (2 × CH), 130.9 (q), 130.5 (CH),
1292, 1175, 1158, J = 8.8 Hz, Ar2¢-3¢ and 5¢H), 6.73 (1 H, d, J = 8.1 Hz, Ar-
129.1 (CH), 128.8 (CH), 126.7 (q), 125.8
1111, 1307
5¢H), 6.70 (1 H, d, J = 6.8 Hz, Ar3¢-2¢H), 6.64 (1 H, d, J = 2.0 (CH), 120.4 (CH), 114.2 (2 × CH), 111.6
Hz, Ar-2¢H), 6.61 (1 H, dd, J = 2.0, 8.1 Hz, Ar-6¢H), 5.70
(1 H, t, J = 4.8 Hz, NH), 3.84 (3 H, s, OMe), 3.82 (3 H, s,
OMe), 3.78 (3 H, s, OMe), 3.56 (2 H, m, NCH2), 2.76 (2 H,
t, J = 7.0 Hz, ArCH2)
(CH), 111.1 (CH), 55.6 (CH3), 55.5 (CH3),
54.9 (CH3), 41.0 (CH2), 34.6 (CH2)
2g
2934, 2820, 1666, 8.00 (2 H, d, J = 8.8 Hz, Ar3¢-3¢ and 5¢H), 7.83 (1 H, s, H-3), 166.2 (q), 149.8 (q), 149.5 (q), 149.0 (q),
1592, 1515, 1464, 7.17 (2 H, d, J = 8.8 Hz, Ar3¢-2¢ and 6¢H), 6.86 (1 H, d, J = 147.7 (q), 146.9 (q), 141.6 (q), 138.0 (q),
1416, 1343, 1258, 8.2 Hz, Ar2¢- 6¢H), 6.61 (1 H, d, J = 8.2 Hz, Ar-5¢H), 6.64
133.9 (CH), 130.8 (q), 130.6 (2 × CH),
(2 H, m Ar2¢-2¢ and 5¢H), 6.54 (2 H, m Ar-2¢ and 6¢H), 5.79 126.7 (q), 123.3 (2 × CH), 121.8 (CH),
(1 H, t, J = 4.4 Hz, NH), 3.94 (3 H, s, OMe), 3.86 (3 H, s, 120.4 (CH), 111.9 (CH), 111.8 (CH), 111.7
OMe), 3.83 (3 H, s, OMe), 3.72 (3 H, s, OMe), 3.57 (2 H, m, (CH), 111.1 (CH), 55.9 (CH3), 55.82 (CH3),
1139, 1025
NCH2), 2.75 (2 H, t, J = 6.8 Hz, ArCH2)
55.80 (CH3), 55.75 (CH3), 41.2 (CH2), 34.6
(CH2)
2h
2934, 2835, 1666, 7.76 (1 H, s, H-3), 7.11 (2 H, d, J = 8.7 Hz, Ar3¢-3¢ and 5¢H), 166.8 (q), 149.6 (q), 149.0 (q), 148.8 (q),
1616, 1515, 1414, 6.94 (2 H, d, J = 8.7 Hz, Ar3¢-2¢ and 6¢H), 6.85 (1 H, d, J = 147.5 (q), 135.3 (q), 134.3 (q), 134.2 (q),
1256, 1139, 1090, 8.2 Hz, Ar2¢-5¢H), 6.70 (1 H, d, J = 8.1 Hz, Ar-5¢H), 6.64
133.3 (q), 131.3 (2 × CH), 130.8 (CH),
1027
(1 H, dd, J = 8.2, 2.0 Hz, Ar2¢-6¢H), 6.63 (1 H, d, J = 2.0 Hz, 128.2 (2 × CH), 127.4 (q), 121.7 (CH),
Ar2¢-2¢H), 6.57 (1 H, d, J = 2.0 Hz, Ar-2¢H), 6.53 (1 H, dd, 120.3 (CH), 112.0 (CH), 111.7 (CH), 111.6
J = 8.1, 2.0 Hz, Ar2¢-2¢H), 5.67 (1 H, t, J = 5.4 Hz, NH), 3.93 (CH), 111.0 (CH), 55.7 (CH3), 55.65
(3 H, s, OMe), 3.85 (3 H, s, OMe), 3.82 (3 H, s, OMe), 3.72 (2 × CH3), 55.6 (CH3), 41.1 (CH2), 34.6
(3 H, s, OMe), 3.55 (2 H, m, NCH2), 2.74 (2 H, t, J = 6.8 Hz, (CH2)
ArCH2)
Table 4 Spectral Data of Compounds 3a–h
Product
IR (KBr; cm–1)
1H NMR [CDCl3/TMS; d (ppm), J (Hz)]
13C NMR [CDCl3/TMS; d (ppm)]
3a
2937, 2834, 1604, 7.49 (2 H, d, J = 7.1 Hz, Ph-2¢ and 6¢H), 7.40 (1 H, s, H-2¢), 167.3 (q), 157.0 (q), 150.6 (q), 147.3 (q),
1568, 1511, 1464, 7.24 (2 H, t, J = 7.1 Hz, Ph-3¢ and 5¢H), 7.16 (2 H, m, Ph-4¢H 141.2 (q), 139.3 (q), 130.9 (q), 129.4 (q),
1318, 1280, 1205, and Ar1¢-6¢H), 7.08 (1 H, t, J = 8.3 Hz, Ar1¢-4¢H), 6.87 (1 H, 128.7 (CH), 128.4 (2 × CH), 128.1 (CH),
1143, 1111, 1029 s, H-8), 6.75 (1 H, d, J = 8.3 Hz, Ar1¢-3¢H), 6.68 (1 H, t, J = 127.4 (CH), 126.7 (2 × CH), 125.9 (CH),
8.3 Hz, Ar1¢-5¢H), 6.61 (1 H, s, H-5), 3.84 (3 H, s, OMe),
122.1 (q), 119.8 (CH), 110.0 (CH), 109.9
3.82 (2 H, m, H-3), 3.77 (3 H, s, OMe), 3.62 (3 H, s, OMe), (CH), 55.8 (CH3), 55.6 (CH3), 55.1 (CH3),
2.70 (2 H, m, H-4) 47.6 (CH2), 25.4 (CH2)
3b
3c
3d
3058, 3002, 2935, 7.49 (3 H, m, Ph), 7.32 (2 H, m, Ph), 7.27 (1 H, d, J = 7.8 Hz, 166.3 (q), 151.0 (q), 147.4 (q), 141.3 (q),
2832, 1605, 1559, Ar1¢-4¢H), 7.23 (2 H, m, Ar1¢-2¢ and 6¢H), 7.07 (1 H, s, H-2¢), 140.0 (q), 138.5 (q), 131.4 (CH), 131.1 (q),
1507, 1464, 1375, 7.03 (1 H, t, J = 7.8 Hz, Ar1¢-5¢H), 6.77 (1 H, s, H-8), 6.69
1318, 1278, 1206, (1 H, s, H-5), 3.86 (2 H, m, H-3), 3.84 (3 H, s, OMe), 3.58
1142, 1075, 1043, (3 H, s, OMe), 2.80 (2 H, t, J = 7.7 Hz, H-4)
1029
130.0 (CH), 129.3 (CH), 128.4 (2 × CH),
128.1 (CH), 127.9 (CH), 127.2 (CH), 126.3
(2 × CH), 121.9 (q), 110.1 (CH), 109.7
(CH), 55.7 (CH3), 55.65 (CH3), 47.6 (CH2),
25.1 (CH2)
2941, 2831, 1600, 8.05 (2 H, d, J = 8.2 Hz, Ar2¢-3¢ and 5¢H), 7.97 (2 H, d, J =
166.1 (q), 151.2 (q), 147.7 (q), 135.1 (q),
1562, 1510, 1409, 8.2 Hz, Ar2¢-2¢ and 6¢H), 7.88 (2 H, m, Ph-H), 7.56 (3 H, m, 133.6 (q), 131.5 (q), 130.6 (q), 130.0 (q),
1363, 1316, 1281, Ph-H), 7.13 (1 H, s, H-2¢), 6.89 (1 H, s, H-8), 6.80 (1 H, s, H- 129.6 (2 × CH), 129.5 (q), 129.3 (2 × CH),
1250, 1208, 1177, 5), 3.85 (3 H, s, OMe), 3.81 (2 H, m, H-3), 3.65 (3 H, s,
1032, 1012 OMe), 2.75 (2 H, t, J = 7.4 Hz, H-4)
128.6 (2 × CH), 126.9 (2 × CH), 125.9 (CH),
124.2 (CH), 121.5 (q), 109.9 (CH), 109.5
(CH), 55.7 (CH3), 55.2 (CH3), 47.3 (CH2),
25.3 (CH2)
3100, 2934, 2810, 7.53 (2 H, d, J = 7.1 Hz, Ar2¢-2¢ and 6¢H), 7.37 (1 H, s, H-2¢), 166.6 (q), 150.6 (q), 147.3 (q), 141.3 (q),
1603, 1569, 1505, 7.33 (2 H, t, J = 7.1 Hz, Ar2¢-3¢ and 5¢H), 7.23 (2 H, m, Ar2¢- 135.1 (q), 131.4 (q), 130.6 (q), 130.1 (q),
1464, 1278, 1141, 6¢H and Ph-4¢H), 7.14 (2 H, m, Ar2¢-4¢ and 5¢H), 6.98 (1 H, 129.2 (CH), 128.9 (CH), 128.5 (CH), 128.4
1030
d, J = 8.8 Hz, Ar2¢-3¢H), 6.84 (1 H, s, H-8), 6.58 (1 H, s, H- (2 × CH), 128.1 (CH), 128.0 (CH), 126.7
5), 3.82 (2 H, m, H-3), 3.81 (3 H, s, OMe), 3.68 (3 H, s,
(2 × CH), 125.8 (CH), 121.7 (q), 109.8
(CH), 109.4 (CH), 55.65 (CH3), 55.6 (CH3),
47.4 (CH2), 25.2 (CH2)
OMe), 2.68 (2 H, t, J = 7.7 Hz, H-4)
Synthesis 2007, No. 7, 1003–1014 © Thieme Stuttgart · New York

1008
J. Tóth et al.
PAPER
Table 4 Spectral Data of Compounds 3a–h (continued)
Product
IR (KBr; cm–1)
1H NMR [CDCl3/TMS; d (ppm), J (Hz)]
13C NMR [CDCl3/TMS; d (ppm)]
3e
2940, 2835, 1603, 7.17 (6 H, m, Ar2¢- and Ar3¢-H), 6.94 (1 H, s, H-2¢), 6.77 (1 H, 168.1 (q), 159.1 (q), 150.4 (q), 146.9 (q),
1567, 1512, 1465, s, H-8), 6.74 (2 H, d, J = 8.5 Hz, Ar1¢-3¢ and 5¢H), 6.67 (1 H, 141.2 (q), 135.2 (q), 132.8 (q), 131.9 (q),
1404, 1353, 1316, s, H-5), 3.87 (3 H, s, OMe), 3.80 (2 H, m, H-3), 3.75 (3 H, s, 131.0 (2 × CH), 130.7 (2 × CH), 130.1 (q),
1285, 1251, 1208, OMe), 3.60 (3 H, s, OMe), 2.71 (2 H, t, J = 7.8 Hz, H-4)
129.9 (CH), 128.1 (2 × CH), 121.2 (q), 114.0
(2 × CH), 111.1 (CH), 110.0 (CH), 55.84
(CH3), 55.77 (CH3), 55.1 (CH3), 47.8 (CH2),
25.8 (CH2)
1174, 1142, 1089,
1036, 1013
3f
3001, 2936, 2834, 7.46 (2 H, d, J = 8.8 Hz, Ar1¢-2¢ and 6¢H), 7.28 (1 H, s, H-2¢), 166.8 (q), 159.5 (q), 150.7 (q), 147.4 (q),
1605, 1567, 1511, 7.25 (1 H, d, J = 7.9 Hz, Ar2¢-6¢H), 7.11 (1 H, d, J = 7.9 Hz, 140.8 (q), 135.3 (q), 132.8 (q), 131.4 (q),
1465, 1441, 1371, Ar2¢-3¢H), 7.00 (2 H, m, Ar2¢-4¢ and 5¢H), 6.87 (2 H, d, J = 8.8 130.7 (q), 130.5 (CH), 129.0 (CH), 128.3
(CH), 128.0 (2 × CH), 125.9 (CH), 124.8
1249, 1207, 1179, 3.86 (2 H, m, H-3), 3.83 (3 H, s, OMe), 3.78 (3 H, s, OMe), (CH), 121.8 (q), 113.9 (2 × CH), 109.9
1144, 1033 3.69 (3 H, s, OMe), 2.74 (1 H, t, J = 7.1 Hz, H-4), 2.69 (1 H, (CH), 109.5 (CH), 55.8 (CH3), 55.7 (CH3),
1349, 1318, 1279, Hz, Ar1¢-3¢ and 5¢H), 6.83 (1 H, s, H-8), 6.59 (1 H, s, H-5),
t, J = 7.1 Hz, H-4)
55.2 (CH3), 47.4 (CH2), 25.3 (CH2)
3g
3h
3002, 2936, 2835, 8.02 (2 H, d, J = 8.8 Hz, Ar2¢-3¢ and 5¢H), 7.34 (2 H, d, J =
166.1 (q), 151.3 (q), 149.6 (q), 148.9 (q),
1592, 1567, 1515, 8.8 Hz, Ar2¢-2¢ and 6¢H), 7.12 (1 H, s, H-2¢), 6.85 (1 H, s, H- 147.6 (q), 146.1 (q), 143.9 (q), 143.3 (q),
1464, 1418, 1341, 8), 6.79 (3 H, m, Ar1¢-H), 6.72 (1 H, s, H-5), 3.90 (3 H, s,
1319, 1268, 1208, OMe), 3.88 (3 H, s, OMe), 3.85 (2 H, m, H-3), 3.84 (3 H, s, (q), 123.3 (2 × CH), 121.2 (q), 119.7 (CH),
1169, 1139, 1110, OMe), 3.63 (3 H, s, OMe), 2.80 (1 H, t, J = 7.7 Hz, H-4),
1081, 1026 2.74 (1 H, t, J = 7.7 Hz, H-4)
131.1 (q), 129.1 (2 × CH), 128.0 (CH), 126.0
111.1 (CH), 110.3 (CH), 109.7 (CH), 109.4
(CH), 55.8 (CH3), 55.7 (CH3), 55.65 (CH3),
55.62 (CH3), 47.8 (CH2), 25.1 (CH2)
2935, 2830, 1604, 7.96 (2 H, d, J = 8.1 Hz, Ar2¢-3¢ and 5¢H), 7.92 (2 H, d, J =
166.5 (q), 151.0 (q), 149.8 (q), 149.1 (q),
1566, 1517, 1465, 8.1 Hz, Ar2¢-2¢ and 6¢H), 7.10 (1 H, s, H-2¢), 6.84 (1 H, s, H- 147.4 (q), 146.2 (q), 142.9 (q), 140.3 (q),
1443, 1372, 1318, 8), 6.82 (1 H, d, J = 7.8 Hz, Ar1¢-5¢H), 6.78 (2 H, m, Ar1¢-H), 130.0 (q), 129.9 (2 × CH), 129.7 (2 × CH),
1272, 1241, 1200, 6.75 (1 H, s, H-5), 3.94 (3 H, s, OMe), 3.89 (3 H, s, OMe), 128.1 (CH), 126.0 (q), 121.0 (q), 119.3
1149, 1030
3.87 (3 H, s, OMe), 3.83 (2 H, m, H-3), 3.62 (3 H, s, OMe), (CH), 111.2 (CH), 110.1 (CH), 109.3 (CH),
2.82 (2 H, t, J = 7.5 Hz, H-4)
109.1 (CH), 55.85 (CH3), 55.8 (CH3), 55.6
(CH3), 55.2 (CH3), 47.7 (CH2), 25.3 (CH2)
Table 5 Spectral Data of Compounds 4a–p
Prod- IR (KBr; cm–1)
uct
1H NMR [CDCl3/TMS; d (ppm), J (Hz)]
13C NMR [CDCl3/TMS; d (ppm)]
4a
4b
4c
2937, 2835, 1743, 7.75 (1 H, s, H-2¢), 7.42 (3 H, m, Ph), 7.38 (2 H, m, Ph), 175.3 (q), 164.9 (q), 157.4 (q), 156.8 (q), 148.4
1600, 1549, 1520, 7.27 (1 H, t, J = 7.6 Hz, Ar2¢-4¢H), 7.24 (1 H, d, J = 7.6 Hz, (q), 136.6 (q), 135.7 (q), 135.2 (q), 131.8 (CH),
1485, 1464, 1394, Ar2¢-6¢H), 6.99 (1 H, t, J = 7.6 Hz, Ar2¢-5¢H), 6.98 (1 H, s, 130.3 (CH), 129.52 (2 × CH), 129.49 (CH),
1337, 1294, 1272, H-8), 6.95 (1 H, s, H-5), 6.80 (1 H, d, J = 7.6 Hz, Ar2¢-
129.43 (CH), 126.6 (2 × CH), 122.7 (q), 121.5
1251, 1214, 1169, 3¢H), 5.57 (1 H, d, J = 17.3 Hz, NCH2), 5.13 (1 H, d, J = (CH), 118.3 (q), 113.8 (CH), 110.9 (CH), 110.6
1112, 1020
17.3 Hz, NCH2), 4.62 (1 H, m, H-3), 4.50 (1 H, m, H-3), (CH), 62.1 (CH2), 58.8 (CH2), 56.9 (CH3), 55.8
4.00 (3 H, s, OMe), 3.83 (2 H, q, J = 7.1 Hz, OCH2), 3.80 (CH3), 55.4 (CH2), 52.5 (CH3), 26.0 (CH2), 13.7
(3 H, s, OMe), 3.64 (3 H, s, OMe), 3.63 (1 H, m, H-4),
(CH3)
3.42 (1 H, m, H-4), 1.08 (3 H, t, J = 7.1 Hz, CH3)
2998, 2933, 2833, 7.84 (1 H, s, H-2¢), 7.49 (5 H, m, Ph-H), 7.30 (1 H, t, J = 173.7 (q), 157.1 (q), 157.0 (q), 148.5 (q), 137.2
1604, 1554, 1519, 8.0 Hz, Ar2¢-4¢H), 7.25 (1 H, d, J = 8.0 Hz, Ar2¢-6¢H), 7.19 (q), 134.8 (q), 133.2 (q), 131.5 (q), 130.7 (CH),
1485, 1463, 1396, (3 H, t, J = 7.3 Hz, Bn-H), 7.17 (2 H, d, J = 7.3 Hz, Bn-H), 130.4 (CH), 129.5 (CH), 129.4 (2 × CH), 129.0
1337, 1292, 1276, 7.03 (1 H, t, J = 8.0 Hz, Ar2¢-5¢H), 6.97 (1 H, s, H-8), 6.95 (CH), 128.9 (2 × CH), 128.4 (2 × CH), 126.3
1246, 1211, 1165, (1 H, s, H-5), 6.85 (1 H, d, J = 8.0 Hz, Ar2¢-3¢H), 5.56
1113, 1050, 1029, (1 H, d, J = 14.3 Hz, NCH2), 5,45 (1 H, d, J = 14.3 Hz,
(2 × CH), 122.9 (q), 121.6 (2 × CH), 118.5 (q),
113.6 (CH), 111.1 (CH), 110.8 (CH), 60.2 (CH2),
1007
NCH2), 4.28 (1 H, m, H-3), 4.07 (1 H, m, H-3), 4.00 (3 H, 56.9 (CH3), 55.8 (CH3), 55.4 (CH3), 49.2 (CH2),
s, OMe), 3.78 (3 H, s, OMe), 3.66 (3 H, s, OMe), 3.55
(1 H, m, H-4), 3.36 (1 H, m, H-4)
25.8 (CH2)
2933, 1742, 1600, 7.49 (5 H, m, Ph-H), 7.40 (3 H, m, Ar2¢-H), 7.31 (1 H, d, 174.3 (q), 164.9 (q), 158.1 (q), 148.9 (q), 136.1
1547, 1520, 1465, J = 7.8 Hz, Ar2¢-6¢H), 7.27 (1 H, s, H-2¢), 6.96 (1 H, s, H- (q), 135.5 (q), 135.3 (q), 135.2 (q), 132.9 (CH),
1421, 1392, 1337, 8), 6.89 (1 H, s, H-5), 5.44 (1 H, d, J = 17.5 Hz, NCH2),
132.0 (q), 131.6 (CH), 131.4 (CH), 130.3 (CH),
1294, 1271, 1214, 5.37 (1 H, d, J = 17.5 Hz, NCH2), 4.65 (2 H, m, H-3), 4.03 129.9 (2 × CH), 127.3 (CH), 126.5 (2 × CH),
1168, 1121, 1006 (3 H, s, OMe), 3.86 (2 H, q, J = 6.6 Hz, OCH2), 3.72 (1 H, 122.9 (CH), 117.8 (q), 113.8 (CH), 111.3 (CH),
m, H-4), 3.62 (3 H, s, OMe), 3.54 (1 H, m, H-4), 1.09
(3 H, t, J = 6.6 Hz, CH3)
62.4 (CH2), 59.2 (CH2), 57.1 (CH3), 56.2 (CH3),
52.8 (CH2), 26.1 (CH2), 13.8 (CH3)
Synthesis 2007, No. 7, 1003–1014 © Thieme Stuttgart · New York

PAPER
Synthesis of Pyrrolo[2,1-a]isoquinolines
13C NMR [CDCl3/TMS; d (ppm)]
1009
Table 5 Spectral Data of Compounds 4a–p (continued)
Prod- IR (KBr; cm–1)
uct
1H NMR [CDCl3/TMS; d (ppm), J (Hz)]
4d
3006, 2938, 2830, 7.54 (6 H, m, Ph-H), 7.41 (4 H, m, Ph-H), 7.33 (1 H, s,
172.8 (q), 157.8 (q), 148.9 (q), 136.1 (q), 135.5
1602, 1554, 1518, Ar2¢-2¢H), 7.26 (1 H, t, J = 7.5 Hz, Ar2¢-5¢H), 7.18 (1 H, d, (q), 135.3 (q), 133.8 (q), 132.7 (q), 132.1 (q),
1456, 1407, 1338, J = 7.5 Hz, Ar2¢-4¢H), 7.16 (1 H, d, J = 7.5 Hz, Ar2¢-6¢H), 131.7 (CH), 131.6 (CH), 130.6 (CH), 130.3 (CH),
1293, 1274, 1165, 7.05 (1 H, s, H-2¢), 6.96 (1 H, s, H-8), 6.94 (1 H, s, H-5), 130.2 (2 × CH), 129.7 (2 × CH), 129.3 (CH),
1047
5.61 (1 H, d, J = 14.2 Hz, NCH2), 5.51 (1 H, d, J = 14.2
129.1 (2 × CH), 127.2 (CH), 126.3 (2 × CH),
Hz, NCH2), 4.37 (1 H, m, H-3), 4.27 (1 H, m, H-3), 4.02 123.0 (CH), 117.9 (q), 113.6 (CH), 111.4 (CH),
(3 H, s, OMe), 3.64 (3 H, s, OMe), 3.60 (1 H, m, H-4),
3.48 (1 H, m, H-4)
60.7 (CH2), 57.1 (CH3), 56.2 (CH3), 49.6 (CH2),
26.0 (CH2)
4e
4f
2977, 2935, 1739, 7.61 (1 H, s, H-2¢), 7.44–7.31 (9 H, m, Ar2¢-H and Ph-H), 174.8 (q), 164.7 (q), 158.1 (q), 148.8 (q), 136.1
1602, 1550, 1520, 7.00 (1 H, s, H-8), 6.90 (1 H, s, H-5), 5.63 (1 H, d, J = 17.5 (q), 136.0 (q), 135.7 (q), 131.8 (CH), 130.7 (q),
1495, 1467, 1427, Hz, NCH2), 5.08 (1 H, d, J = 17.5 Hz, NCH2), 4.66 (1 H, 130.2 (2 × CH), 129.9 (CH), 129.6 (2 × CH),
1393, 1338, 1294, m, H-3), 4.53 (1 H, m, H-3), 4.02 (3 H, s, OMe), 3.84
129.55 (2 × CH), 129.0 (q), 126.4 (2 × CH), 117.5
1271, 1241, 1219, (3 H, m, H-4 and OCH2), 3.61 (3 H, s, OMe), 3.45 (1 H, (q), 113.7 (CH), 111.3 (CH), 62.2 (CH2), 59.1
1190, 1171, 1125, m, H-4), 1.06 (3 H, t, J = 7.2 Hz, CH3)
1009
(CH2), 57.0 (CH3), 56.1 (CH3), 52.6 (CH2), 26.0
(CH2), 13.7 (CH3)
3072, 2976, 2911, 7.65 (1 H, s, H-2¢), 7.53 (4 H, s, Ar2¢-H), 7.40 (5 H, s, Ph- 173.1 (q), 157.6 (q), 148.9 (q), 136.9 (q), 136.0
2834, 1602, 1552, H), 7.25 (1 H, t, J = 7.8 Hz, Ph-H), 7.16 (2 H, t, J = 7.8 Hz, (q), 135.3 (q), 135.2 (q), 132.1 (q), 131.0 (q),
1516, 1498, 1467, Ph-H), 6.97 (2 H, s, H-5 and H-8), 6.91 (2 H, d, J = 7.8 Hz, 130.5 (CH), 130.2 (2 × CH), 130.1 (2 × CH),
1454, 1440, 1404, Ph-H), 5.90 (1 H, d, J = 14.0 Hz, NCH2), 5.41 (1 H, d, J = 130.0 (CH), 129.95 (2 × CH), 129.9 (2 × CH),
1392, 1336, 1293, 14.0 Hz, NCH2), 4.52 (1 H, m, H-3), 4.00 (3 H, s, OMe), 129.3 (CH), 129.0 (2 × CH), 126.4 (2 × CH),
1264, 1239, 1214, 3.95 (1 H, m, H-3), 3.76 (1 H, m, H-4), 3.63 (3 H, s,
1193, 1178, 1163, OMe), 3.31 (1 H, m, H-4)
117.8 (q), 113.6 (CH), 111.3 (CH), 60.6 (CH2),
57.0 (CH3), 56.2 (CH3), 49.2 (CH2), 26.1 (CH2)
1086, 1044, 1024,
1006
4g
2999, 2977, 2821, 7.75 (1 H, s, H-2¢), 7.65 (1 H, d, J = 7.3 Hz, Ar2¢-6¢H), 7.47 174.6 (q), 164.9 (q), 148.8 (q), 135.9 (q), 135.8
1743, 1602, 1548, (3 H, m, Ph-H), 7.41 (3 H, m, Ph-H and Ar2¢-4¢H), 7.27
(q), 135.4 (q), 133.1 (q), 132.8 (q), 131.9 (CH),
1520, 1466, 1394, (1 H, d, J = 7.3 Hz, Ar2¢-3¢H), 7.22 (1 H, t, J = 7.3 Hz, Ar2¢- 131.2 (CH), 130.5 (CH), 130.1 (CH), 129.7
1336, 1294, 1216, 5¢H), 6.95 (1 H, s, H-8), 6.86 (1 H, s, H-5), 6.01 (1 H, d, (2 × CH), 129.5 (CH), 129.3 (q), 128.8 (CH),
1023
J = 17.5 Hz, NCH2), 5.04 (1 H, d, J = 17.5 Hz, NCH2),
4.72 (1 H, m, H-3), 4.48 (1 H, m, H-3), 3.98 (3 H, s,
126.8 (2 × CH), 118.3 (q), 113.3 (CH), 110.9
(CH), 62.2 (CH2), 59.7 (CH2), 56.9 (CH3), 56.1
OMe), 3.84 (2 H, q, J = 7.1 Hz, OCH2), 3.80 (1 H, m, H- (CH3), 52.7 (CH2), 26.2 (CH2), 13.7 (CH3)
4), 3.74 (3 H, s, OMe), 3.22 (1 H, m, H-4), 1.06 (3 H, t,
J = 7.1 Hz, CH3)
4h
2993, 2812, 1604, 7.76 (1 H, s, H-2¢), 7.56 (3 H, m, Ph-H), 7.52 (2 H, m, Ph- 172.9 (q), 157.3 (q), 148.7 (q), 137.3 (q),134.9
1551, 1520, 1496, H), 7.25 (6 H, m, Ar2¢-H and Ph-H), 7.16 (1 H, t, J = 7.6 (q), 133.0 (q), 132.0 (q), 131.1 (CH), 130.4 (q),
1462, 1394, 1338, Hz, Ar2¢-4¢H), 7.13 (1 H, s, H-8), 6.94 (2 H, d, J = 7.5 Hz, 130.1 (2 × CH), 129.9 (CH), 129.8 (2 × CH),
1295, 1213, 1167, Ph-H), 6.87 (1 H, s, H-5), 6.24 (1 H, d, J = 14.2 Hz,
1045, 1006 NCH2), 5.40 (1 H, d, J = 14.2 Hz, NCH2), 4.63 (1 H, m,
129.7 (q), 129.6 (CH), 129.3 (CH), 129.2 (CH),
129.15 (CH), 128.9 (2 × CH), 128.6 (CH), 126.7
H-3), 4.32 (1 H, m, H-3), 3.97 (3 H, s, OMe), 3.76 (3 H, s, (2 × CH), 118.4 (q), 113.2 (CH), 110.9 (CH), 60.6
OMe), 3.69 (1 H, m, H-4), 3.10 (1 H, m, H-4)
(CH2), 59.9 (CH3), 56.1 (CH3), 49.1 (CH2), 26.1
(CH2)
4i
4j
2970, 2949, 2840, 7.46 (1 H, s, H-2¢), 7.32 (6 H, m, Ar1¢-and Ar2¢-H), 6.99
1748, 1605, 1551, (1 H, s, H-8), 6.95 (2 H, d, J = 8.9 Hz, Ar1¢-3¢ and 5¢H),
1508, 1403, 1337, 6.89 (1 H, s, H-5), 5.56 (1 H, d, J = 17.5 Hz, NCH2), 5.21 130.5 (q), 130.0 (2 × CH), 129.6 (2 × CH), 128.1
1296, 1280, 1210, (1 H, d, J = 17.5 Hz, NCH2), 4.61 (2 H, m, H-3), 4.02 (q), 128.0 (2 × CH), 117.7 (q), 115.1 (2 × CH),
1200, 1189, 1032, (3 H, s, OMe), 3.80 (2 H, q, J = 7.3 Hz, OCH2), 3.77 (3 H, 113.8 (CH), 111.2 (CH), 62.2 (CH2), 59.2 (CH2),
175.0 (q), 165.0 (q), 160.9 (q), 157.9 (q),148.8
(q), 135.9 (q), 135.7 (q), 133.8 (CH), 132.1 (q),
1018
s, OMe), 3.62 (3 H, s, OMe), 3.48 (2 H, m, H-4), 1.08
57.0 (CH3), 56.2 (CH3), 55.5 (CH2), 52.7 (CH3),
26.2 (CH2), 15.2 (CH2), 13.8 (CH3)
(3 H, t, J = 7.3 Hz, CH3)
2935, 2840, 1605, 7.56 (1 H, s, H-2¢), 7.52 (2 H, d, J = 8.9 Hz, Ar1¢-2¢ and
173.2 (q), 160.9 (q), 148.8 (q), 135.5 (q), 135.0
1549, 1506, 1462, 6¢H), 7.36 (2 H, d, J = 8.6 Hz, Ar2¢-3¢ and 5¢H), 7.31 (2 H, (q), 132.4 (q), 132.2 (q), 130.7 (q), 130.6 (q),
1394, 1334, 1289, d, J = 8.6 Hz, Ar2¢-2¢ and 6¢H), 7.26 (1 H, t, J = 7.4 Hz, Ph- 130.0 (2 × CH), 129.8 (2 × CH), 129.7 (2 × CH),
1214, 1161, 1097, 4¢H), 7.17 (2 H, t, J = 7.4 Hz, Ph-3¢ and 5¢H), 7.04 (2 H, d, 129.2 (CH), 128.9 (2 × CH), 128.8 (q), 127.8
1028, 1007
J = 8.9 Hz, Ar1¢-3¢ and 5¢H), 7.00 (1 H, s, H-8), 6.88 (1 H, (2 × CH), 117.9 (q), 115.4 (2 × CH), 113.6 (CH),
s, H-5), 6.94 (2 H, d, J = 7.4 Hz, Ph-2¢ and 6¢H), 5.70 (1 H, 111.3 (CH), 60.5 (CH2), 57.0 (CH3), 56.2 (CH3),
d, J = 14.2 Hz, NCH2), 5.47 (1 H, d, J = 14.2 Hz, NCH2), 55.5 (CH3), 49.2 (CH2), 26.0 (CH2)
4.34 (1 H, m, H-3), 4.11 (1 H, m, H-3), 4.00 (3 H, s,
OMe), 3.85 (3 H, s, OMe), 3.63 (3 H, s, OMe), 3.62 (1 H,
m, H-4), 3.41 (1 H, m, H-4)
Synthesis 2007, No. 7, 1003–1014 © Thieme Stuttgart · New York

1010
J. Tóth et al.
PAPER
Table 5 Spectral Data of Compounds 4a–p (continued)
Prod- IR (KBr; cm–1)
uct
1H NMR [CDCl3/TMS; d (ppm), J (Hz)]
13C NMR [CDCl3/TMS; d (ppm)]
4k
3000, 2835, 1753, 7.63 (1 H, s, H-2¢), 7.54 (1 H, d, J = 7.7 Hz, Ar2¢-6¢H), 7.42 174.8 (q), 165.0 (q), 161.0 (q), 157.7 (q), 148.7
1604, 1464, 1394, (1 H, t, J = 7.7 Hz, Ar2¢-5¢H), 7.37 (2 H, d, J = 8.8 Hz, Ar1¢- (q), 135.7 (q), 133.1 (q), 133.0 (q), 132.4 (q),
1339, 1296, 1255, 2¢ and 6¢H), 7.26 (1 H, d, J = 7.7 Hz, Ar2¢-3¢H), 7.19 (1 H, 132.1 (q), 130.9 (q), 130.1 (q), 129.4 (q), 128.5
1214, 1187, 1170, t, J = 7.7 Hz, Ar2¢-4¢H), 6.97 (2 H, d, J = 8.8 Hz, Ar1¢-3¢
(CH), 128.2 (2 × CH), 128.1 (CH), 118.3 (q),
and 5¢H), 6.94 (1 H, s, H-7), 6.87 (1 H, s, H-5), 5.88 (2 H, 113.3 (CH), 110.9 (CH), 62.2 (CH2), 59.4 (CH2),
1032
d, J = 17.5 Hz, CH2CO), 5.12 (2 H, d, J = 17.5 Hz,
CH2CO), 4.63 (1 H, m, H-3), 4.50 (1 H, m, H-3), 3.99
(3 H, s, OMe), 3.87 (2 H, q, J = 7.2 Hz, OCH2), 3.84 (6 H,
s, 2 × OMe), 3.73 (3 H, s, OMe), 3.72 (1 H, m, H-4), 3.29
(1 H, m, H-4), 1.09 (3 H, t, J = 7.2 Hz, CH3)
56.9 (CH3), 56.1 (CH3), 55.4 (CH3), 52.6 (CH2),
26.1 (CH2), 13.7 (CH3)
4l
2933, 2835, 1603, 7.56 (1 H, d, J = 7.0 Hz, Ar2¢-6¢H), 7.47 (2 H, d, J = 8.8
1550, 1512, 1455, Hz, Ar1¢-2¢ and 6¢H), 7.18–7.35 (6 H, m, Ph-H and Ar2¢-
161.2 (q), 157.3 (q), 148.9 (q), 135.2 (q), 135.1
(q), 133.3 (q), 133.1 (q), 132.7 (q), 132.5 (q),
1392, 1339, 1294, H), 7.17 (2 H, d, J = 8.8 Hz, Ar1¢-3¢ and 5¢H), 7.02 (1 H, s, 132.2 (CH), 130.6 (CH), 130.4 (q), 130.3 (CH),
1268, 1216, 1181, H-2¢), 6.99 (2 H, d, J = 8.4 Hz, Ph-H), 6.86 (1 H, s, H-5), 129.9 (2 × CH), 129.6 (CH), 129.4 (CH), 129.2
1163, 1026, 1003 6.85 (1 H, s, H-7), 6.09 (1 H, d, J = 14.2 Hz, PhCH2), 5.45 (CH), 129.1 (2 × CH), 129.0 (CH), 128.8 (CH),
(1 H, d, J = 14.2 Hz, PhCH2), 4.50 (2 H, m, H-3), 3.96
(3 H, s, OMe), 3.88 (3 H, s, OMe), 3.74 (3 H, s, OMe),
3.66 (1 H, m, H-4), 3.16 (1 H, m, H-4)
128.2 (2 × CH), 127.3 (q), 115.5 (2 × CH), 115.2
(CH), 113.3 (CH), 110.9 (CH), 60.6 (CH2), 56.9
(CH3), 56.2 (CH3), 55.6 (CH3), 49.3 (CH2), 26.1
(CH2)
4m
2937, 2780, 1743, 8.19 (2 H, d, J = 8.8 Hz, Ar2¢-3¢ and 5¢H), 7.78 (1 H, s, H- 174.4 (q), 172.0 (q), 158.3 (q), 151.2 (q), 150.1
1597, 1517, 1466, 2¢), 7.68 (2 H, d, J = 8.8 Hz, Ar2¢-2¢ and 6¢H), 7.03 (1 H, s, (q), 148.9 (q), 147.6 (q), 140.9 (q), 139.8 (q),
1341, 1268, 1140, Ar1¢-2¢H), 6.92 (2 H, m, Ar1¢-5¢ and 6¢H), 6.89 (1 H, s, H- 132.8 (q), 129.9 (2 × CH), 127.0 (q), 124.4
1024
8), 6.83 (1 H, s, H-5), 5.72 (1 H, d, J = 17.7 Hz, NCH2),
5.01 (1 H, d, J = 17.7 Hz, NCH2), 4.67 (1 H, m, H-3), 4.56 113.5 (CH), 111.7 (CH), 111.2 (CH), 108.9 (CH),
(1 H, m, H-3), 4.00 (3 H, s, OMe), 3.98 (3 H, s, OMe), 62.4 (CH2), 59.5 (CH2), 56.6 (CH3), 56.4 (CH3),
3.91 (3 H, s, OMe), 3.87 (2 H, q, J = 7.0 Hz, OCH2), 3.63 56.3 (CH3), 55.9 (CH3), 52.8 (CH2), 26.2 (CH2),
(2 × CH), 120.5 (q), 117.6 (CH), 113.6 (CH),
(3 H, s, OMe), 3.49 (1 H, m, H-4), 3.37 (1 H, m, H-4),
13.7 (CH3)
1.06 (3 H, t, J = 7.0 Hz, CH3)
4n
2937, 2850, 1602, 8.19 (2 H, d, J = 8.8 Hz, Ar2¢-3¢ and 5¢H), 7.83 (1 H, s, H- 172.6 (q), 157.8 (q), 151.5 (q), 150.5 (q), 149.0
1555, 1520, 1468, 2¢), 7.67 (2 H, d, J = 8.8 Hz, Ar2¢-2¢ and 6¢H), 7.28 (3 H, (q), 147.5 (q), 140.0 (q), 135.2 (q), 133.7 (q),
1393, 1344, 1297, m, Ph-H), 7.17 (2 H, t, J = 7.8 Hz, Ph-H), 7.01 (1 H, d, J = 131.9 (q), 130.4 (q), 130.0 (2 × CH), 129.7
1264, 1220, 1154, 8.3 Hz, Ar1¢-6¢H), 6.99 (1 H, s, Ar1¢-2¢H), 6.97 (1 H, d, J = (2 × CH), 129.5 (CH), 129.1 (2 × CH), 128.3 (q),
1017
8.3 Hz, Ar1¢-5¢H), 6.92 (1 H, s, H-8), 6.90 (1 H, s, H-5),
5.99 (1 H, d, J = 14.0 Hz, NCH2), 5.37 (1 H, d, J = 14.0
124.7 (2 × CH), 120.5 (CH), 117.8 (CH), 113.5
(CH), 111.9 (CH), 111.2 (CH), 109.0 (CH), 60.7
Hz, NCH2), 4.58 (1 H, m, H-3), 4.02 (3 H, s, OMe), 3.98 (CH2), 57.0 (CH3), 56.8 (CH3), 56.3 (CH3), 56.2
(3 H, s, OMe), 3.95 (3 H, s, OMe), 3.92 (1 H, m, H-3),
3.80 (1 H, m, H-4), 3.63 (3 H, s, OMe), 3.27 (1 H, m, H-4)
(CH3), 49.3 (CH2), 26.2 (CH2)
4o
2938, 2815, 1740, 7.57 (1 H, s, H-2¢), 7.34 (4 H, s, Ar2¢-H), 6.96 (2 H, m,
174.9 (q), 165.1 (q), 157.9 (q), 150.7 (q), 149.8
1601, 1551, 1518, Ar1¢-5¢ and 6¢H), 6.92 (1 H, d, J = 2.0 Hz, Ar1¢-2¢H), 6.90 (q), 148.8 (q), 135.9 (q), 135.8 (q), 134.3 (q),
1465, 1391, 1339, (2 H, s, H-5 and H-8), 5.62 (1 H, d, J = 17.5 Hz, NCH2), 132.1 (q), 130.6 (CH), 130.2 (2 × CH), 129.6
1269, 1219, 1021 5.14 (1 H, d, J = 17.5 Hz, NCH2), 4.65 (1 H, m, H-3), 4.61 (2 × CH), 128.3 (q), 120.1 (CH), 117.8 (q), 113.8
(1 H, m, H-3), 4.02 (3 H, s, OMe), 3.96 (3 H, s, OMe),
(CH), 111.8 (CH), 111.1 (CH), 108.8 (CH), 62.2
3.89 (3 H, s, OMe), 3.86 (2 H, q, J = 7.1 Hz, OCH2), 3.77 (CH2), 59.2 (CH2), 57.0 (CH3), 56.4 (CH3), 56.2
(1 H, m, H-4), 3.63 (3 H, s, OMe), 3.45 (1 H, m, H-4),
1.08 (3 H, t, J = 7.1 Hz, CH3)
(CH3), 56.0 (CH3), 52.7 (CH2), 26.2 (CH2), 13.7
(CH3)
4p
2951, 2939, 2820, 7.73 (1 H, s, H-2¢), 7.35 (4 H, s, Ar2¢-H), 7.26 (1 H, t, J = 173.2 (q), 157.5 (q), 150.8 (q), 150.1 (q), 148.8
1604, 1556, 1513, 7.4 Hz, Ph-4¢H), 7.21 (1 H, s, H-8), 7.18 (2 H, t, J = 7.4
(q), 135.3 (q), 134.8 (q), 132.6 (q), 132.4 (q),
1467, 1392, 1339, Hz, Ph-3¢ and 5¢H), 6.98 (6 H, m, Ar1¢-H, H-5, Ph-2¢ and 130.6 (q), 130.5 (q), 130.0 (2 × CH), 129.9
1296, 1263, 1220, 6¢H), 5.66 (1 H, d, J = 14.2 Hz, NCH2), 4.39 (1 H, d, J = (2 × CH), 129.7 (2 × CH), 129.2 (CH), 129.0
1153, 1103, 1016 14.2 Hz, NCH2), 4.36 (1 H, m, H-3), 4.07 (1 H, m, H-3), (CH), 128.9 (2 × CH), 120.0 (CH), 117.9 (q),
4.00 (6 H, s, 2 × OMe), 3.92 (3 H, s, OMe), 3.64 (3 H, s, 113.5 (CH), 111.8 (CH), 111.2 (CH), 108.6 (CH),
OMe), 3.62 (1 H, m, H-4), 3.39 (1 H, m, H-4);
60.4 (CH2), 56.9 (CH3), 56.6 (CH3), 56.2 (CH3),
56.0 (CH3), 49.1 (CH2), 26.0 (CH2)
Synthesis 2007, No. 7, 1003–1014 © Thieme Stuttgart · New York

PAPER
Synthesis of Pyrrolo[2,1-a]isoquinolines
13C NMR [CDCl3/TMS; d(ppm)]
1011
Table 6 Spectral Data of Compounds 5a–i
Product IR (KBr; cm–1)
1H NMR [CDCl3/TMS; d (ppm), J (Hz)]
5a
2933, 2782, 1745, 7.32 (1 H, d, J = 7.5 Hz, Ar2¢-6¢H), 7.19 (5 H, m, Ph-H), 172.7 (q), 157.7 (q), 148.6 (q), 146.5 (q), 139.3 (q),
1608, 1515, 1491, 7.12 (1 H, t, J = 7.5 Hz, Ar2¢-4¢H), 6.85 (1 H, t, J = 7.5 137.8 (q), 130.1 (q), 130.0 (2 × CH), 129.8 (CH),
1464, 1387, 1347, Hz, Ar2¢-5¢H), 6.80 (1 H, s, H-10), 6.75 (1 H, t, J = 7.5 128.2 (q), 128.1 (2 × CH), 128.0 (CH), 127.7 (CH),
1246, 1222, 1162, Hz, Ar2¢-3¢H), 6.60 (1 H, s, H-7), 5.04 (1 H, d, J = 9.9
126.1 (CH), 121.0 (q), 120.5 (CH), 112.4 (q), 110.6
1112, 1035
Hz, H-3), 4.22 (2 H, m, OCH2), 3.90 (1 H, d, J = 9.9 Hz, (CH), 109.5 (CH), 73.4 (CH), 60.8 (CH2), 55.7
H-2), 3.84 (3 H, s, OMe), 3.70 (3 H, s, OMe), 3.35 (1 H, (CH3), 55.3 (CH3), 54.9 (CH3), 47.6 (CH), 29.9
m, H-5), 3.26 (3 H, s, OMe), 3.22 (1 H, m, H-5), 3.01
(1 H, m, H-6), 2.85 (1 H, m, H-6), 1.24 (3 H, t, J = 7.1
Hz, OCH2CH3)
(CH2), 14.2 (CH3)
5b
5c
5d
3060, 2940, 2810, 7.37 (2 H, d, J = 7.0 Hz, Ph-H), 7.25 (6 H, m, Ph-H),
158.0 (q), 148.6 (q), 146.6 (q), 142.2 (q), 138.6 (q),
1608, 1515, 1491, 7.16 (2 H, t, J = 7.0 Hz, Ph-H), 7.08 (1 H, d, J = 8.0 Hz, 130.0 (2 × CH), 129.9 (q), 128.3 (q), 128.1 (CH),
1462, 1451, 1422, Ar2¢-6¢H), 7.04 (1 H, t, J = 8.0 Hz, Ar2¢-4¢H), 6.94 (1 H, 128.07 (2 × CH), 128.05 (2 × CH), 127.4 (2 × CH),
1385, 1342, 1267, s, H-10), 6.86 (1 H, t, J = 8.0 Hz, Ar2¢-5¢H), 6.67 (1 H, 127.3 (q), 127.2 (CH), 127.1 (CH), 126.7 (q), 125.8
1243, 1218, 1159, d, J = 8.0 Hz, Ar2¢-3¢H), 6.62 (1 H, s, H-7), 4.82 (1 H, d, (CH), 121.4 (q), 120.5 (CH), 112.8 (q), 111.0 (CH),
1094, 1022
J = 9.8 Hz, H-2), 4.19 (1 H, d, J = 9.8 Hz, H-3), 3.85
(3 H, s, OMe), 3.37 (3 H, s, OMe), 3.29 (3 H, s, OMe), 55.3 (CH3), 55.0 (CH3), 54.8 (CH), 46.6 (CH2),
3.11 (2 H, m, H-5), 2.84 (2 H, m, H-6) 30.0 (CH2)
110.7 (CH), 109.5 (CH), 76.5 (CH), 55.8 (CH3),
2994, 2951, 2934, 7.35 (1 H, s, Ar2¢-2¢H), 7.29 (6 H, m, Ph-H), 7.19 (4 H, 148.8 (q), 146.7 (q), 144.8 (q), 141.1 (q), 141.0 (q),
2905, 2833, 1621, m, Ph-H), 7.08 (1 H, t, J = 6.8 Hz, Ar2¢-5¢H), 7.03 (2 H, 138.1 (q), 132.1 (q), 130.2 (CH), 129.6 (CH), 129.5
1567, 1513, 1464, m, Ar2¢-4¢ and 6¢H), 6.86 (1 H, s, H-10), 6.62 (1 H, s, H- (CH), 128.41 (2 × CH), 128.39 (2 × CH), 128.3 (q),
1439, 1422, 1384, 7), 4.18 and 4.14 (2 H, 2 × d, J = 11.3 Hz, H-2 and H-3), 128.0 (CH), 127.5 (CH), 127.33 (2 × CH), 127.31
1350, 1339, 1311, 3.85 (3 H, s, OMe), 3.27 (3 H, s, OMe), 3.18 (1 H, m, H- (2 × CH), 126.29 (CH), 122.1 (q), 120.8 (q), 110.6
1267, 1239, 1220, 5), 3.07 (1 H, m, H-5), 2.87 (1 H, m, H-6), 2.80 (1 H, m, (CH), 109.4 (CH), 63.5 (CH), 55.7 (CH3), 55.0
1204, 1182, 1154, H-6)
1067
(CH3), 46.7 (CH2), 29.9 (CH2)
2998, 2955, 2925, 7.29 (5 H, m, Ph-H), 7.19 (5 H, m, Ph-H), 7.14 (2 H, d, 148.8 (q), 146.7 (q), 141.1 (q), 141.0 (q), 140.7 (q),
2823, 1607, 1515, J = 8.1 Hz, Ar2-3 and 5¢H), 7.08 (2 H, d, J = 8.1 Hz, Ar2- 138.2 (q), 132.0 (q), 130.5 (2 × CH), 130.2
1490, 1459, 1439, 2 and 6¢H), 6.87 (1 H, s, H-10), 6.62 (1 H, s, H-7), 4.20 (2 × CH), 128.4 (2 × CH), 128.3 (2 × CH), 128.25
1421, 1410, 1384, (1 H, d, J = 11.5 Hz, H-3), 4.09 (1 H, d, J = 11.5 Hz, H- (q), 128.2 (2 × CH), 127.5 (CH), 127.4 (2 × CH),
1358, 1339, 1308, 2), 3.85 (3 H, s, OMe), 3.27 (3 H, s, OMe), 3.18 (1 H, m, 126.3 (q), 120.9 (q), 112.1 (q), 110.6 (CH), 109.4
1266, 1231, 1221, H-5), 3.08 (1 H, m, H-5), 2.86 (1 H, m, H-6), 2.80 (1 H, (CH), 78.7 (CH), 63.3 (CH), 55.8 (CH3), 55.0
1191, 1152, 1096, m, H-6)
1063, 1039, 1020,
1012
(CH3), 46.9 (CH2), 29.8 (CH2)
5ea
3155, 2910, 2850, 7.81 (1 H, s, H-10), 7.72 (2 H, d, J = 7.2 Hz, Ph-H), 7.50 175.9 (q), 157.0 (q), 147.5 (q), 137.1 (q), 135.6 (q),
1604, 1559, 1524, (3 H, m, Ph-H), 7.33 (1 H, s, H-7), 7.31 (1 H, d, J = 7.2 135.0 (q), 134.2 (CH), 130.2 (CH), 130.2 (q), 129.7
1453, 1388, 1289, Hz, Ar2¢-6¢H), 7.26 (5 H, m, Ph-H), 7.07 (1 H, t, J = 7.2 (4 × CH), 129.65 (4 × CH), 129.2 (CH), 129.0
1222, 1172, 1048 Hz, Ar2¢-5¢H), 6.88 (1 H, t, J = 7.2 Hz, Ar2¢-4¢H), 6.83
(CH), 128.8 (CH), 128.7 (q), 126.5 (q), 125.2 (CH),
(1 H, d, J = 7.2 Hz, Ar2¢-3¢H), 6.19 (1 H, d, J = 10.2 Hz, 113.8 (q), 112.8 (CH), 112.1 (CH), 72.8 (CH), 60.0
H-2), 5.13 (1 H, d, J = 10.2 Hz, H-3), 4.13 (1 H, m, H- (CH), 56.7 (CH3), 55.8 (CH3), 44.5 (CH2), 25.5
5), 3.93 (3 H, s, OMe), 3.65 (2 H, m, H-5), 3.32 (3 H, s, (CH2)
OMe), 3.31 (1 H, m, H-6), 3.26 (2 H, m, H-6)
5f
2997, 2957, 2834, 7.21 (4 H, s, Ar2¢-H), 7.04 (2 H, d, J =8.6 Hz, Ar2¢-2¢ and 172.0 (q), 158.2 (q), 148.8 (q), 146.6 (q), 140.8 (q),
1738, 1683, 1605, 6¢H), 6.77 (1 H, s, H-10), 6.75 (2 H, d, J = 8.6 Hz, Ar2¢- 139.8 (q), 132.2 (q), 132.0 (q), 131.3 (2 × CH),
1507, 1489, 1465, 3¢ and 5¢H), 6.60 (1 H, s, H-7), 4.49 (1 H, d, J = 10.5 Hz, 130.2 (2 × CH), 128.4 (2 × CH), 128.1 (q), 127.2
1442, 1422, 1387, H-3), 4.23 (2 H, m, OCH2), 3.84 (3 H, s, OMe), 3.76
(q), 120.6 (q), 113.9 (2 × CH), 110.5 (CH), 109.3
1267, 1243, 1220, (1 H, d, J = 10.5 Hz, H-2), 3.71 (3 H, s, OMe), 3.43
(CH), 74.6 (CH), 61.1 (CH2), 57.1 (CH2), 55.7
1174, 1105, 1081, (1 H, m, H-5), 3.29 (3 H, s, OMe), 3.25 (1 H, m, H-5), (CH3), 55.1 (CH3), 55.0 (CH3), 48.0 (CH), 29.8
1066, 1012
2.96 (1 H, m, H-6), 2.85 (1 H, m, H-6), 1.25 (3 H, t, J = (CH2), 14.2 (CH3)
7.2 Hz, OCH2CH3)
5g
3107, 2950, 2812, 7.55 (1 H, s, H-10), 7.39 (5 H, m, Ph-H), 6.98 (2 H, d, 179.2 (q), 159.6 (q), 157.0 (q), 148.3 (q), 134.1 (q),
1608, 1561, 1515, J = 8.8 Hz, Ar1-2¢ and 6¢H), 6.96 (2 H, d, J = 8.4 Hz,
133.5 (q), 133.2 (q), 130.5 (2 × CH), 130.2 (q),
1496, 1460, 1387, Ar2-3¢ and 5¢H), 6.87 (2 H, d, J = 8.4 Hz, Ar2-2 and 6¢H), 130.1 (2 × CH), 129.8 (3 × CH), 128.6 (q), 128.1
1336, 1289, 1251, 6.77 (1 H, s, H-7), 6.75 (2 H, d, J = 8.8 Hz, Ar1-3¢ and (2 × CH), 126.3 (2 × CH), 115.6 (q), 114.1
1223, 1173, 1092, 5¢H), 5.46 (1 H, d, J = 10.6 Hz, H-3), 5.31 (1 H, d, J = (2 × CH), 113.8 (CH), 110.6 (CH), 86.4 (q), 73.6
1049
10.6 Hz, H-2), 3.93 (3 H, s, OMe), 3.88 (1 H, m, H-5), (CH), 63.5 (CH), 56.5 (CH3),56.0 (CH3), 55.2
3.79 (1 H, m, H-5), 3.72 (3 H, s, OMe), 3.58 (3 H, s,
OMe), 3.58 (1 H, m, H-6), 3.07 (1 H, m, H-6)
(CH3), 44.1 (CH2), 26.3 (CH2)
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PAPER
Table 6 Spectral Data of Compounds 5a–i (continued)
Product IR (KBr; cm–1) 1H NMR [CDCl3/TMS; d (ppm), J (Hz)]
13C NMR [CDCl3/TMS; d(ppm)]
5h
3161, 2941, 2837, 7.53 (1 H, d, J = 7.4 Hz, Ar2¢-6¢H), 7.24 (2 H, d, J = 8.9 158.1 (q), 148.8 (q), 146.7 (q), 141.9 (q), 137.7 (q),
1627, 1605, 1553, Hz, Ar1¢-2¢ and 6¢H), 7.16 (2 H, m, Ph-2¢ and 6¢H), 7.12 136.5 (q), 134.2 (q), 131.8 (q), 131.5 (CH), 131.0
(2 × CH), 128.9 (q), 128.7 (CH), 128.4 (2 × CH),
1332, 1290, 1250, 5¢H), 6.89 (2 H, m, Ar2¢-3¢ and 4¢H), 6.78 (2 H, d, J = 8.9 127.4 (CH), 127.3 (2 × CH), 126.8 (CH), 125.9
1221, 1176, 1037, Hz, Ar1¢-3¢ and 5¢H), 6.66 (1 H, s, H-7), 4.98 (1 H, d,
(CH), 121.0 (q), 114.0 (q), 113.8 (2 × CH), 110.7
1516, 1462, 1387, (1 H, s, H-10), 7.07 (4 H, m, Ph-3¢, 4¢, 5¢H and Ar2¢-
1023
J = 10.0 Hz, H-2), 4.70 (1 H, d, J = 10.0 Hz, H-3), 3.88 (CH), 109.5 (CH), 73.6 (CH), 55.8 (CH3), 55.2
(3 H, s, OMe), 3.73 (3 H, s, OMe), 3.39 (3 H, s, OMe), (2 × CH3), 54.3 (CH), 46.1 (CH2), 30.2 (CH2)
3.20 (1 H, ddd, J = 14.0, 10.4, 5.4 Hz, H-6), 3.09 (1 H,
ddd, J = 11.0, 5.4, 3.0 Hz, H-5), 2.75 (1 H, ddd, J = 14.0,
11.0, 3.0 Hz, H-6), 2.64 (1 H, ddd, J = 11.0, 10.4, 3.0
Hz, H-5)
5i
2934, 2833, 2677, 7.58 (1 H, s, H-7), 7.39 (3 H, m, Ph-H), 7.02 (2 H, d,
178.9 (q), 157.1 (q), 149.5 (q), 149.1 (q), 148.2 (q),
1627, 1602, 1556, J = 8.6 Hz, Ar2-3 and 5¢H), 6.90 (2 H, d, J = 8.6 Hz, Ar2- 134.1 (q), 133.6 (q), 133.0 (q), 130.5 (q), 130.1
1513, 1494, 1462, 2 and 6¢H), 6.83 (1 H, s, H-10), 6.72 (1 H, d, J = 8.3 Hz, (6 × CH), 129.8 (CH), 129.5 (q), 128.9 (q), 128.1
1387, 1358, 1311, Ar1-5¢H), 6.60 (1 H, d, J = 2.1 Hz, Ar1-3¢H), 6.40 (2 H, (2 × CH), 116.3 (CH), 115.6 (q), 113.8 (CH), 110.7
1291, 1269, 1179, dd, J = 8.3 and 2.1 Hz, Ar1-6¢H), 5.41 (1 H, d, J = 10.6 (CH), 110.1 (CH), 109.6 (CH), 73.2 (CH), 63.5
1167, 1016
Hz, H-2), 5.33 (1 H, d, J = 10.6 Hz, H-3), 3.95 (3 H, s, (CH), 56.5 (CH3), 56.0 (CH3), 55.8 (CH3), 55.7
OMe), 3.79 (3 H, s, OMe), 3.62 (3 H, s, OMe), 3.55
(3 H, s, OMe), 3.75 (2 H, m, H-5), 3.15 (2 H, m, H-6)
(CH3), 44.1 (CH2), 26.3 (CH2)
a Both 1H NMR and 13C NMR recorded in DMSO-d6.
Table 7 Spectral Data of Compounds 6a–j
Product IR (KBr; cm–1)
1H NMR [CDCl3/TMS; d (ppm), J (Hz)]
13C NMR [CDCl3/TMS; d (ppm)]
6a
3073, 2989, 2930, 7.18 (6 H, m, Ph-H and Ar2¢-4¢H), 7.00 (1 H, d, J = 161.9 (q), 157.2 (q), 147.8 (q), 147.1 (q), 135.9 (q),
2832, 1682, 1602, 8.1 Hz, Ar2¢-6¢H), 6.78 (1 H, t, J = 8.1 Hz, Ar2¢-5¢H), 132.0 (CH), 130.9 (q), 130.7 (2 × CH), 128.6 (q),
1545, 1510, 1484, 6.73 (1 H, d, J = 8.1 Hz, Ar2¢-3¢H), 6.71 (1 H, s, H- 127.9 (2 × CH), 127.8 (CH), 126.3 (CH), 125.7
1465, 1433, 1415, 10), 6.54 (1 H, s, H-7), 4.64 (2 H, t, J = 6.6 Hz, H-5), (CH), 125.0 (q), 121.9 (q), 121.0 (q), 119.6 (CH),
1398, 1383, 1343, 4.02 (2 H, q, J = 7.2 Hz, OCH2), 3.86 (3 H, s, OMe), 118.9 (q), 110.6 (q), 110.1 (CH), 108.7 (CH), 59.5
1263, 1241, 1197, 3.58 (3 H, s, OMe), 3.27 (3 H, s, OMe), 3.06 (2 H, t, (CH2), 55.8 (CH3), 55.3 (CH3), 55.0 (CH3), 42.7
1174, 1136, 1097, J = 6.6 Hz, H-6), 0.89 (3 H, t, J = 7.2 Hz, CH2CH3) (CH2), 29.0 (CH2), 13.6 (CH3)
1064
6b
6c
2993, 2956, 2831, 7.38 (1 H, s, Ar2¢-2¢H), 7.26 (3 H, m Ph-H), 7.17
161.6 (q), 148.1 (q), 147.2 (q), 137.8 (q), 135.1 (q),
1682, 1597, 1542, (3 H, m, Ph-H and Ar2¢-4¢H), 7.01 (1 H, t, J = 7.6 Hz, 133.9 (CH), 131.2 (2 × CH), 131.1 (q), 129.1 (CH),
1509, 1481, 1393, Ar2¢-5¢H), 6.99 (1 H, d, J = 7.6 Hz, Ar2¢-6¢H), 4.66
1339, 1265, 1242, (2 H, t, J = 6.7 Hz, H-5), 4.08 (2 H, q, J = 7.1 Hz,
1214, 1203, 1178, OCH2), 3.87 (3 H, s, OMe), 3.26 (3 H, s, OMe), 3.06 118.3 (q), 110.6 (CH), 108.6 (CH), 59.8 (CH2), 55.9
129.0 (CH), 128.5 (CH), 128.3 (2 × CH), 126.8
(CH), 125.9 (2 × q), 121.7 (q), 120.9 (q), 120.6 (q),
1141, 1089
(2 H, t, J = 6.7 Hz, H-6), 0.98 (3 H, t, J = 7.1 Hz,
CH2CH3)
(CH3), 55.0 (CH3), 42.8 (CH2), 29.0 (CH2), 13.6
(CH3)
3047, 2998, 2937, 7.26 (10 H, m, Ph-H), 7.15 (1 H, d, J = 7.8 Hz, Ar2¢- 147.3 (q), 146.9 (q), 137.5 (q), 136.0 (q), 133.4 (q),
2837, 1593, 1546, 4¢H), 7.02 (1 H, s, Ar2¢-2¢H), 6.87 (1 H, t, J = 7.8 Hz, 131.4 (q), 131.2 (2 × CH), 131.0 (2 × CH), 130.1
1509, 1494, 1482, Ar2¢-5¢H), 6.81 (1 H, d, J = 7.8 Hz, Ar2¢-6¢H), 6.70
(q),129.9 (q),129.2 (CH), 128.9 (CH), 128.4
1464, 1441, 1406, (1 H, s, H-10), 6.54 (1 H, s, H-7), 4.03 (2 H, t, J = 6.5 (2 × CH), 128.2 (2 × CH), 128.0 (CH), 127.4 (CH),
1371, 1337, 1299, Hz, H-5), 3.85 (3 H, s, OMe), 3.32 (3 H, s, OMe),
1260, 1225, 1208, 2.96 (2 H, t, J = 6.5 Hz, H-6)
1165, 1110, 1070,
126.4 (CH), 125.8 (q), 124.7 (CH), 122.1 (q), 121.4
(q), 119.8 (q), 110.8 (CH), 108.0 (CH), 55.8 (CH3),
55.0 (CH3), 42.4 (CH2), 28.5 (CH2)
1040, 1024
6d
2974, 2837, 2879, 7.25 (3 H, m, Ph-H), 7.14 (4 H, m, Ph-H, Ar2¢-3¢ and 161.7 (q), 148.1 (q), 147.2 (q), 135.3 (q), 134.2 (q),
2831, 1688, 1606, 5¢H), 7.06 (2H, d, J = 8.4 Hz, Ar2¢-2¢ and 6¢H), 6.72 132.1 (q), 132.0 (2 × CH), 131.9 (q), 131.6 (q),
1547, 1512, 1490, (1 H, s, H-10), 6.47 (1 H, s, H-7), 4.65 (2 H, t, J = 6.6 131.2 (2 × CH), 128.3 (2 × CH), 127.2 (2 × CH),
1461, 1414, 1404, Hz, H-5), 4.06 (2 H, q, J = 7.1 Hz, OCH2), 3.87 (3 H, 126.7 (CH), 125.9 (q), 121.7 (q), 120.6 (q), 118.3
1384, 1263, 1240, s, OMe), 3.25 (3 H, s, OMe), 3.06 (2 H, t, J = 6.6 Hz, (q), 110.6 (CH), 108.7 (CH), 59.8 (CH2), 55.9 (CH3),
1220, 1212, 1200, H-6), 0.97 (3 H, t, J = 7.1 Hz, CH2CH3)
1176, 1139, 1111,
55.0 (CH3), 42.9 (CH2), 29.1 (CH2), 13.7 (CH3)
1091, 1059, 1016
Synthesis 2007, No. 7, 1003–1014 © Thieme Stuttgart · New York

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Synthesis of Pyrrolo[2,1-a]isoquinolines
13C NMR [CDCl3/TMS; d (ppm)]
1013
Table 7 Spectral Data of Compounds 6a–j (continued)
Product IR (KBr; cm–1)
1H NMR [CDCl3/TMS; d (ppm), J (Hz)]
6e
2980, 2900, 2870, 7.31 (1 H, d, J = 7.7 Hz, Ar2¢-6¢H), 7.21 (4 H, m, Ph- 161.5 (q), 148.0 (q), 147.2 (q), 135.5 (q), 135.3 (q),
1681, 1603, 1544, H and Ar2¢-H), 7.15 (1 H, m, Ar2¢-H), 7.10 (1 H, m, 134.7 (q), 131.9 (CH), 131.2 (q), 130.8 (2 × CH),
1511, 1485, 1461, Ar2¢-H), 7.05 (2 H, m, Ph-H), 6.72 (1 H, s, H-10),
129.8 (q), 128.4 (2 × CH), 128.1 (CH), 127.8 (CH),
1417, 1400, 1343, 6.52 (1 H, s, H-7), 4.86 (1 H, m, H-5), 4.51 (1 H, m, 126.6 (CH), 125.8 (q), 125.6 (CH), 121.7 (q), 120.8
1253, 1216, 1179, H-5), 4.05 (1 H, m, OCH2), 3.96 (1 H, m, OCH2),
1139, 1115, 1068 3.86 (3 H, s, OMe), 3.27 (3 H, s, OMe), 3.12 (1 H,
(q), 118.6 (q), 110.7 (CH), 108.6 (CH), 59.6 (CH2),
55.9 (CH3), 55.0 (CH3), 42.8 (CH2), 29.0 (CH2), 13.4
m, H-6), 3.05 (1 H, m, H-6), 0.85 (3 H, t, J = 7.2 Hz, (CH3)
CH2CH3)
6f
2994, 2935, 2842, 7.16 (2 H, d, J = 7.9 Hz, Ar1¢-3¢ and 5¢H), 7.06 (2 H, 161.8 (q), 158.4 (q), 148.1 (q), 147.2 (q), 134.3 (q),
1684, 1612, 1542, d, J = 8.1 Hz, Ar2¢-3¢ and 5¢H), 7.04 (2 H, d, J = 8.1 132.2 (2 × CH), 132.0 (2 × CH), 131.7 (q), 131.3
1521, 1488, 1421, Hz, Ar2¢-2¢ and 6¢H), 6.79 (2 H, d, J = 8.4 Hz, Ar1¢-2¢ (q), 127.3 (q), 127.2 (2 × CH), 125.9 (q), 121.3
1398, 1333, 1285, and 6¢H), 6.72 (1 H, s, H-10), 6.55 (1 H, s, H-7), 4.63 (q),120.8 (q), 118.2 (q), 113.8 (2 × CH), 110.6 (CH),
1264, 1248, 1221, (2 H, t, J = 6.8 Hz, H-5), 4.07 (2 H, q, J = 6.5 Hz,
108.6 (CH), 59.8 (CH2), 55.9 (CH3), 55.2 (CH3),
1198, 1175, 1143, OCH2), 3.87 (3 H, s, OMe), 3.76 (3 H, s, OMe), 3.21 55.1 (CH3), 42.8 (CH2), 29.1 (CH2), 13.7 (CH3)
1066, 1030
(3 H, s, OMe), 3.05 (2 H, t, J = 6.8 Hz, H-6), 0.98
(3 H, t, J = 6.5 Hz, CH2CH3)
6g
2987, 2932, 2903, 7.30 (1 H, d, J = 7.9 Hz, Ar2¢-6¢H), 7.09 (5 H, m,
161.6 (q), 158.4 (q), 148.0 (q), 147.2 (q), 135.7 (q),
2866, 2830, 1675, Ar2¢-3¢, 4¢, 5¢H, Ar1¢-2¢ and 6¢H), 6.76 (2 H, d, J = 8.2 134.7 (q), 132.0 (CH), 131.8 (2 × CH), 131.2 (q),
1547, 1519, 1487, Hz, Ar1¢-3¢ and 5¢H), 6.72 (1 H, s, H-10), 6.59 (1 H, 130.0 (q), 128.4 (CH), 127.7 (CH), 127.4 (q), 125.8
1460, 1437, 1416, s, H-7), 4.84 (1 H, br m, Hz, H-5), 4.52 (1 H, br m, (q), 125.7 (CH), 121.3 (q), 120.9 (q), 118.5 (q),
1398, 1289, 1249, Hz, H-5), 4.05 (1 H, br m, OCH2), 3.97 (1 H, br m, 113.6 (2 × CH), 110.7 (CH), 108.6 (CH), 59.6
1216, 1198, 1178, OCH2), 3.88 (3 H, s, OMe), 3.73 (3 H, s, OMe), 3.33 (CH2), 55.9 (CH3), 55.15 (CH3), 55.1 (CH3), 42.8
1140, 1114
(3 H, s, OMe), 3.07 (2 H, br m, H-6), 0.85 (3 H, br (CH2), 29.0 (CH2), 13.4 (CH3)
m, CH2CH3)
6h
2939, 2840, 1694, 8.07 (2 H, d, J = 8.4 Hz, Ar2¢-3¢ and 5¢H), 7.31 (2 H, 161.3 (q), 148.8 (q), 148.4 (q), 148.1 (q), 147.3 (q),
1594, 1547, 1513, d, J = 8.4 Hz, Ar2¢-2¢ and 6¢H), 6.76 (1 H, d, J = 8.1 146.3 (q), 143.5 (q), 131.5 (2 × CH), 131.5 (q),
1497, 1442, 1396, Hz, Ar1¢-6¢H), 6.74 (1 H, s, Ar1¢-2¢H), 6.69 (1 H, d,
130.6 (q), 127.0 (q), 126.0 (q), 123.4 (CH), 122.3
1340, 1238, 1213, J = 8.1 Hz, Ar1¢-5¢H), 6.63 (1 H, s, H-10), 6.62 (1 H, (2 × CH), 121.3 (q), 120.4 (q), 114.1 (CH), 111.2
1181, 1136, 1067, s, H-7), 4.67 (2 H, t, J = 5.9 Hz, H-5), 4.08 (2 H, q, (CH), 110.7 (CH), 108.6 (CH), 60.0 (CH2), 55.9
1020
J = 7.0 Hz, OCH2), 3.89 (3 H, s, OMe), 3.83 (3 H, s, (CH3), 55.8 (2 × CH3), 55.2 (CH3), 42.9 (CH2), 29.0
OMe), 3.63 (3 H, s, OMe), 3.34 (3 H, s, OMe), 3.08 (CH2), 13.7 (CH3)
(2 H, t, J = 5.9 Hz, H-6), 0.96 (3 H, t, J = 7.0 Hz,
CH2CH3)
6i
2940, 2835, 1592, 7.88 (2 H, d, J = 9.0 Hz, Ar2¢-3¢ and 5¢H), 7.37 (3 H, 149.0 (q), 147.9 (q), 147.4 (q), 147.2 (q), 145.1 (q),
1552, 1514, 1497, m Ph-H), 7.22 (2 H, m Ph-H), 7.01 (2 H, d, J = 9.0 143.0 (q), 131.1 (q), 131.0 (2 × CH), 130.8
1459, 1443, 1341, Hz, Ar2¢-2¢ and 6¢H), 6.85 (1 H, d, J = 8.2 Hz, Ar1¢- (2 × CH), 128.5 (2 × CH), 128.1 (q), 127.9 (CH),
1264, 1250, 1229, 6¢H), 6.75 (2 H, m, Ar1¢-2¢ and 5¢H), 6.73 (1 H, s, H- 126.3 (q), 124.8 (q), 123.4 (CH), 122.9 (2 × CH),
1210, 1164, 1137, 10), 6.66 (1 H, s, H-7), 4.04 (2 H, t, J = 6.7 Hz, H-5), 121.8 (q), 120.9 (q), 119.4 (q), 114.2 (CH), 111.4
1114, 1023
3.89 (3 H, s, OMe), 3.88 (3 H, s, OMe), 3.67 (3 H, s, (CH), 110.9 (CH), 108.1 (CH), 55.92 (CH3), 55.89
OMe), 3.40 (3 H, s, OMe), 2.98 (2 H, t, J = 6.7 Hz, (2 × CH3), 55.3 (CH3), 42.3 (CH2), 29.5 (CH2)
H-6)
6j
2938, 2834, 1690, 7.18 (2 H, d, J = 8.7 Hz, Ar2¢-3¢ and 5¢H), 7.07 (2 H, 161.7 (q), 148.6 (q), 148.1 (q), 147.8 (q), 147.2 (q),
1582, 1547, 1520, d, J = 8.7 Hz, Ar2¢-2¢ and 6¢H), 6.76 (1 H, d, J = 8.3 134.4 (q), 132.1 (q), 132.0 (2 × CH), 131.7 (q),
1493, 1464, 1403, Hz, Ar1¢-5¢H), 6.73 (1 H, s, H-10), 6.72 (1 H, dd, J = 131.1 (q), 127.5 (q), 127.2 (2 × CH), 126.0 (q),
1382, 1318, 1299, 2.1, 8.3 Hz, Ar1¢-6¢H), 6.65 (1 H, s, H-7), 6.59 (1 H, 123.5 (CH), 121.3 (q), 120.7 (q), 118.3 (q), 114.3
1262, 1251, 1238, d, J = 2.1 Hz, Ar1¢-2¢H), 4.64 (2 H, t, J = 6.5 Hz, H- (CH), 111.0 (CH), 110.7 (CH), 108.7 (CH), 59.8
1213, 1173, 1135, 5), 4.07 (2 H, q, J = 7.1 Hz, OCH2), 3.88 (3 H, s,
(CH2), 55.9 (CH3), 55.8 (CH3), 55.75 (CH3), 55.2
1088, 1060, 1025
OMe), 3.84 (3 H, s, OMe), 3.63 (3 H, s, OMe), 3.34 (CH3), 42.8 (CH2), 29.1 (CH2), 13.7 (CH3)
(3 H, s, OMe), 3.06 (2 H, t, J = 6.5 Hz, H-6), 0.98
(3 H, t, J = 7.1 Hz, CH2CH3)
Acknowledgment
References
This work was financially supported by the National Fund for
Science and Research, Hungary (OTKA Project No. T 046196). A
grant from the EGIS Pharmaceuticals provided to J.T. is gratefully
appreciated.
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Synthesis 2007, No. 7, 1003–1014 © Thieme Stuttgart · New York