Synthesis of highly substituted dihydropyrrolophenanthridine derivatives by tandem reaction

Article abstract of DOI:10.1016/j.tet.2011.10.041

The efficient cross-coupling of bromo(iso)quinoline to 1,6-diynes with the Pd-catalyzed system was established. Using unactivated simple diynes with bromo(iso)quinoline in the presence of palladium catalytic system afforded different kinds of rare 7,11-di

Full text of DOI:10.1016/j.tet.2011.10.041

Tetrahedron 68 (2012) 311e318
Contents lists available at SciVerse ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Synthesis of highly substituted dihydropyrrolophenanthridine derivatives by
tandem reaction
*
Yimin Hu , Tao Zhu, Xiaolong Mu, Quansheng Zhao, Tao Yu, Lei Wen, Yulong Zhang, Min Wu, Hao Zhang
Laboratory of Functional Molecular Solids, Ministry of Education, Anhui Key Laboratory of Molecular-Based Materials, School of Chemistry and Materials Science,
Anhui Normal University, Wuhu, Anhui 241000, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 22 May 2011
Received in revised form 27 September 2011
Accepted 11 October 2011
Available online 19 October 2011
The efficient cross-coupling of bromo(iso)quinoline to 1,6-diynes with the Pd-catalyzed system was
established. Using unactivated simple diynes with bromo(iso)quinoline in the presence of palladium
catalytic system afforded different kinds of rare 7,11-diphenyl-9,10-dihydro-8H-pyrrolo[3,4-j]phenan-
thridine derivatives through regioselective CeH functionalization in one step. Different diynes (aep) and
different bromo(iso)quinolines were shown to be very active in the reaction. Thus, the generality of this
process makes the reaction highly valuable in view of the synthetic and medicinal importance of these
pyrrolo[3,4-j]phenanthridine derivatives.
Keywords:
CeH activation
Palladium
Ó 2011 Elsevier Ltd. All rights reserved.
Domino reaction
Pyrrolophenanthridine
Cyclization
1. Introduction
reactive intermediates in the three-step cascade synthesis of 2,3-
dihydro-1H-imidazo[1,2-f]phenanthridinium cations.12 Our group
The pyrrolophenanthridine class of substances displays a variety
of pharmacological properties. This class has been the subject of
considerable interest as potential antitumor, antimicrobial, and an-
tiviral agents.1 A large number of naturally occurring alkaloids that
contain a phenanthridine ring system and have a known scope of
activity are mentioned in the literature.2e4 Lycorine is a phyrrolo-
phenanthridine alkaloid, which displays an antiviral effect against
poliovirus and measles and a high antiretroviral activity as well.5
Therefore, numerous synthetic strategies for the preparation of
these scaffolds have been developed.6e8 Recently, Yu reported the
intermolecular CeH functionalization of pyridine rings at the 3- and
4-positions using a Pd0/PR3/ArBr catalytic system, providing a pow-
erful method for the preparation of structure-related nicotinic and
isonicotinic acids that are of great importance in drug discovery.9,10
Lautens et al. reported a new and general strategy for the synthesis
of hexahydrobenzo[c]phenanthridine alkaloids with the novel and
highly enantioselective palladium(II)-catalyzed ring-opening re-
action of a mesoazabicycle, with an aryl boronic acid asthekeystep.11
Cronin developed facile routes for the synthesis and isolation of bi-
ologically active DNA intercalating framework tetrahydroimidazo
[1,2-f]phenanthridines and pyrrolo[1,2-f]phenanthridine, which are
has also employed a domino strategy13 to devise alternative pro-
cesses for the efficient construction of fused phenanthridine
derivatives.14
2. Results and discussion
In this study, we introduce a diversity-oriented synthesis of
highly substituted dihydropyrrolophenanthridine four-rings con-
densed ring system from 1,6-diynes and bromoquinoline. The
cascade consists of inter-intramolecular Heck reactions and sub-
sequent regioselectively directed arylation by CeH activation of the
quinoline ring at the 2- or 4-positions. Herein, we report on the
palladium-catalyzed novel domino reactions of 1aep with 3-
bromo(iso)quinoline or 3-bromopyridine to provide a direct, effi-
cient, and economic methodology for the construction of phenan-
thridine and quinoline through both CeC bond coupling and CeH
bond activation.
In our previous research on palladium-catalyzed cyclization, we
designed a substance, N,N-bis(3-phenylprop-2-yn-1-yl)-4-methyl-
benzenesulfonamide. A survey of the reaction conditions using 3-
bromoquinoline (2a) and N,N-bis(3-(4-chlorophenyl)prop-2-yn-1-
yl)-4-methylbenzenesulfonamide (1b) was performed as a test ex-
periment (Scheme1, Table 1). In a typical experiment, the reaction of
1b and 2a in N,N-dimethylformamide (DMF) in the presence of cat-
alyst Pd(OAc)2 produced 6-chloro-4-(4-chlorophenyl)-2-tosyl-2,3-
* Corresponding author. Tel.: þ86 553 386 9310; fax: þ86 553 388 3517; e-mail
address: yiminhu@mail.ahnu.edu.cn (Y. Hu).
0040-4020/$ e see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2011.10.041

312
Y. Hu et al. / Tetrahedron 68 (2012) 311e318
F
TsN
N
F
[Pd]
[Pd]
7e
Br
F
TsN
F
+
N
2c
F
1e
TsN
N
8e
(trace)
dihydro-1H-benzo[f]isoindole 9b in 42% yield after 24 h at 140 ꢀC. By
controlling the experimental conditions, we discovered the follow-
ing: (1) The efficiency of domino reaction to produce the product 3b
can be lowering the reaction temperature to 130 ꢀC (Table 1, entry 6);
(2) The additive bases play an important role in the overall efficiency
of this domino reaction by simply varying the bases from tributyl-
amine to silver carbonate (Table 1, entries 6,11e12,16), with the 3b in
84%, 15%, and 5% yield when using tributylamine, potassium car-
bonate, and silver, respectively, under identical conditions; (3)
Among the catalysts investigated (Table 1, entries 12e16), the pal-
ladium(II) acetate/(triphenylphosphine) catalytic system is most ef-
fective (Table 1, entries 6, 13e16). (4) DMF is a better solvent for this
reaction than either toluene or MeCN (Table 1, entries 1e2, 7). As
shown in Table 1, the tetracyclic compound 3b is only isolated in
yields of 11% and 39%, respectively, when toluene was employed as
F
Scheme 1. Synthesis of substituted heterocycle 8e.
a solvent, indicating temperature/solvent effects on the outputs of
the reactions and on the formation of the final products. Thus, the
followingstandard reactionconditions wereusedforcarryingoutthe
following studies: 1,6-diyne (1 equiv) was reacted with 3-
bromoquinoline (1.1 equiv) in the presence of palladium acetate
(2 mol %) and Ph3P (4 mol %), with (n-Bu)3N (1.2 equiv) as an additive
in DMF at 130 ꢀC.
To probe the scope of the tandem reaction,
a range of
substituted 3-bromoquinoline and diynes were examined (Table 2).
Various diynes and 3-bromoquinoline or 3-bromoisoquinoline or
Table 1
Optimization of cyclization conditionsa
Entrya
[Pd]/PPh3 (mol %)
Base (equiv)
Solvent
t (h)
Tb (ꢀC)
Yieldc (%)
3b
9b
1
2
3
4
5
6
7
8
Pd(OAc)2/PPh3 (2:4)
Pd(OAc)2/PPh3 (2:4)
Pd(OAc)2/PPh3 (2:4)
Pd(OAc)2/PPh3 (2:4)
Pd(OAc)2/PPh3 (2:4)
Pd(OAc)2/PPh3 (2:4)
Pd(OAc)2/PPh3 (2:4)
Pd(OAc)2/PPh3 (1:2)
Pd(OAc)2/PPh3 (2:4)
Pd(OAc)2/PPh3 (2:4)
Pd(OAc)2/PPh3 (2:4)
Pd(OAc)2/PPh3 (2:4)
Pd(PPh3)4 (2)
(n-Bu)3N
(n-Bu)3N
(n-Bu)3N
(n-Bu)3N
(n-Bu)3N
(n-Bu)3N
(n-Bu)3N
(n-Bu)3N
(n-Bu)3N
(n-Bu)3N
K2CO3
NaHCO3
(n-Bu)3N
(n-Bu)3N
(n-Bu)3N
Ag2CO3
MeCN
Toluene
DMF
DMF
DMF
DMF
Toluene
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
10
10
11
11
16
24
24
24
15
24
24
24
24
24
24
24
100
120
110
120
130
130
130
130
130
140
130
130
130
130
130
130
d
d
11
Trace
25
42
84
39
54
61
14
15
Trace
10
d
Trace
d
7
8
10
11
8
9
42
d
9
10
11
12
13
14
15
16
d
d
PdCl2 (2)
d
Pd(dba)2d (2)
20
5
Trace
d
Pd(OAc)2 (2)
a
All reactions were carried out under argon using 1b (1.0 equiv), 3-bromoquinoline (1.1 equiv), [Pd(OAc)2] (2 mol %), Ph3P, base (2.0 equiv) and solvent (10 mL) at the
indicated temperature.
b
Oil bath temperature.
Isolated yield.
dba: dibenzylidene acetone.
c
d

Table 2
The palladium-catalyzed domino reaction for the formation of fused pyrrolophenanthridinea,b
3a (75%)
3b (84%)
3c (65%)
3d (59%)
3e (86%)
3f (85%)
3g (56%)
3h (33%)
4h (50%)
3i (66%)
3j (31%)
4j (55%)
3k (61%)
3l (29%)
4l (58%)
3m (71%)
3n (62%)
3o (61%)
5p (74%)
6d (41%)
7b (52%)
7d (50%)
8e (Trace)
a
Reaction conditions: aep (1.0 equiv), bromo(iso)quinoline (1.2 equiv), Pd(OAc)2 (2 mol %), PPh3 (4 mol %), (n-Bu)3N (1.2 equiv), DMF 10 mL, 125e130 ꢀC, 24 h.
Isolated yield after flash column chromatography.
b

314
Y. Hu et al. / Tetrahedron 68 (2012) 311e318
3-bromopyridine is compatible with this palladium-catalyzed
domino reaction. Several 7,11-diphenyl-9,10-dihydro-8H-pyrrolo
[3,4-j]phenanthridine compounds were readily isolated in good to
excellent yields, except in the case of 6d, where 3-bromoisoqui-
noline was employed. The para- or ortho- substituted groups on the
benzene ring of 1,6-diynes could be chloro, fluoro, methyl,
methoxyl, and ethoxycarbonyl. Using 3-bromoquinoline with diyne
substrates (b, eef, h, j, l), the reaction yielded 7,11-diphenyl-9,10-
dihydro-8H-pyrrolo[3,4-j]phenanthridine 3b, 3e, 3f, 3hþ4h,
3jþ4j, and 3lþ4l, respectively, in yields higher than 83%. The yield
of compound (3lþ4l) was the highest at 87%. When 3-
bromoquinoline was used in the reaction with a, c,d, g, i, k, and
mep, the desired pyrrolo[3,4-j]phenanthridines were obtained in
good yields ranging from 56% to 75% (3a, 3c, 3d, 3g, 3i, 3k, 3m, 3n,
3o, and 5p). The reaction of 3-bromoquinoline with diyne having
a para-chloro, ortho-methyl, or para-fluoro group (3h, 3j, and 3l)
gave much lower yields of the products than that of 4h, 4j, and 4l.
Compound 6d yield was low (41%), but it is a novel 7,11-diphenyl-
9,10-dihydro-8H-pyrrolo[3,4-b]phenanthridine. Finally, with these
conditions, the generality of the cyclization was studied using 3-
bromopyridine in place of 3-bromoquinoline. Results showed that
the 4,9-diphenyl-2-tosyl-2,3-dihydro-1H-pyrrolo[3,4-g]isoquino-
lines 7b and 7e (Scheme 1) gave moderate yields of 52% and 50%,
respectively. We isolated traces of 8e besides the product 7e when
N,N-bis(3-(4-fluorophenyl)prop-2-yn-1-yl)-4-methylbenzenesulfo
namide and 3-bromopyridine were used in the reaction. The
regioselectivity of the reaction has no clear superiority when either
election-donating or election-withdrawing groups on the aryl ha-
lides. A proposed pathway for this tandem Heck/CeH functionali-
zation reaction is shown in Scheme 1.
Fig. 2. ORTEP polt of 8e showing ellipsiods at the 30% probability level. Selected bond
ꢀ
ꢀ
lengths [A] and angles [ ]: C9eC10 1.487(3), C9eC24 1.336(3), C10eC11 1.402(3),
C11eC12 1.491(3), C12eC14 1.337(3), N1eC8eC9 111.4(2), C8eC9eC10 119.0(2),
C9eC10eC11 123.8(2), C10eC11eC12 124.4(2), C11eC12eC13 118.6(2), N1eC13eC12
111.3(2).
Simplified catalytic cycle mechanisms for selective formation
pyrrolophenanthridines are proposed in Scheme 2. Oxidative ad-
dition of bromoquinoline (2a) would yield aryl-palladium in-
termediate A, which can subsequently undergo carbopalladation
with the diyne moiety (1) to yield intermediate B. Intermediate B
possesses a carbonecarbon double bond that can undergo carbo-
All the resulting fused pyrrolo[3,4-b]phenanthridine com-
pounds were confirmed by various spectroscopic techniques (1H,
13C NMR, and IR spectroscopy, and HRMS). The molecular struc-
tures and relative configurations of 3e (Fig. 1) and 8e (Fig. 2) were
unambiguously confirmed by single-crystal X-ray analysis
(Supplementary data).15
palladation and
s-bond metathesis onto the aryl group to yield
intermediate C. Proton abstraction16 by the base yields pyrrolo-
phenanthridine 3.
R1
2 or
R
N
Br
TsN
3
2a
N
Pd0L2
nBu3N
R
1 or R2
-[HPdL2Br]
R1
N
A
R2 or
1
BrL2Pd
R
N
L2
Pd
Br
TsN
R2 or R1
TsN
TsN
H
N
R2
R1 or
1
PdL2Br
R2
C
R1 or R2
B
Scheme 2. Proposed catalytic cycle.
3. Conclusions
We developed a tandem sequence method for the preparation of
diversely substituted pyrrolo[3,4-j]phenanthridines from readily
available precursors through multistep CeC bond formation and
CeH activation of quinoline or isoquinoline ring. This series pro-
duced pyrrolo[3,4-j]phenanthridine derivatives in moderate to
very good yields. This methodology will aid in generating more
interesting structures for use in biological studies. Aside from the
Fig. 1. ORTEP polt of 3e showing ellipsiods at the 30% probability level. Selected bond
ꢀ
ꢀ
lengths [A] and angles [ ]: C9eC10 1.396(5), C10eC12 1.384(5), C12eC20 1.417(5),
C21eC22 1.418(5), C9eC22 1.375(5), C9eC10eC11 110.7(3), C11eC10eC12 129.3(3),
C10eC12eC20 117.5(3), C9eC22eC21 118.2(3), C12eC20eC21 122.6(3).

Y. Hu et al. / Tetrahedron 68 (2012) 311e318
315
products, traces of novel pyrido[3,4-d]azepine were also dissoci-
702, 611, 547 cmꢁ1
C34H27N2O2S: 527.1794; found: 527.1778.
;
HRMS (ESI): m/z [MþH]þ calcd for
ated when N,N-bis(3-(4-fluorophenyl)prop-2-yn-1-yl)-4-methyl-
benzenesulfonamide and 3-bromopyridine were used in the
reaction. Further investigations to understand this catalytic trans-
formation, an evaluation of the process with a broader scope of
4.2.2. 7,11-Bis(4-chlorophenyl)-9-tosyl-9,10-dihydro-8H-pyrrolo[3,4-
j]phenanthridine (3b). Yellow powder; 499 mg (84%); Rf¼0.36
(petroleum ether/EtOAc¼4:1); mp 258e259 ꢀC; 1H NMR (300 MHz,
substrates, and synthesis of more complex
are in progress.
p-system heterocycles
CDCl3):
d
¼9.08 (s, 1H; AreH), 8.12 (s, 1H; AreH), 7.70e7.58 (m, 7H;
AreH), 7.31e7.23 (m, 8H; AreH), 4.58 (s, 2H; eCHHe), 4.45 (s, 2H;
eCHHe), 2.41 ppm (s, 3H; CH3e); 13C NMR (75 MHz, CDCl3):
4. Experimental
d
¼151.0, 143.9, 139.9, 138.6, 135.0, 134.8, 134.6, 134.2, 133.2, 132.6,
130.7, 130.4, 130.2, 129.9, 129.5, 129.3, 128.5, 127.5, 126.5, 126.3,
4.1. General experiment
~
54.3, 53.5, 21.5 ppm; FT-IR (KBr): nmax¼2360, 1597, 1492, 1340, 1161,
1012, 767, 673, 592, 545, 526 cmꢁ1; HRMS (ESI): m/z [MþH]þ calcd
All the catalytic reactions were performed under an argon at-
mosphere using the oven-dried Schlenk flask. Chemicals were
purchased from Alfa Aesar and Acros Chemicals. All solvents and
materials were dried, distilled, or recrystallized before use. 1H NMR
(300 MHz) and 13C NMR (75 MHz) spectra were recorded on
a Bruker Avance 300 spectrometer with CDCl3 as the solvent.
for C34H25Cl2N2O2S: 595.1015; found: 595.1007.
4.2.3. 7,11-Di-p-tolyl-9-tosyl-9,10-dihydro-8H-pyrrolo[3,4-j]phenan-
thridine (3c). Yellow powder; 360 mg (65%); Rf¼0.42 (petroleum
ether/EtOAc¼4:1); mp 256e257 ꢀC; 1H NMR (300 MHz, CDCl3):
d
¼9.09 (s,1H; AreH), 8.07 (d, J¼7.7 Hz,1H; AreH), 7.67 (d, J¼8.0 Hz,
Chemical shifts (d) are reported in parts per million by assigning
2H; AreH), 7.56 (t, J¼8.7 Hz, 2H; AreH), 7.37 (t, J¼6.7 Hz, 4H;
AreH), 7.31e7.21 (m, 4H; AreH), 7.16 (d, J¼7.6 Hz, 3H; AreH), 4.60
(s, 2H; eCHHe), 4.49 (s, 2H; eCHHe), 2.54 (s, 3H; CH3e), 2.50 (s,
3H; CH3e), 2.39 ppm (s, 3H; CH3e); 13C NMR (75 MHz, CDCl3):
TMS resonance in the 1H NMR spectra as 0.00 ppm and CDCl3
resonance in the 13C spectra as 77.0 ppm. All coupling constants (J
values) were reported in hertz (Hz). Column chromatography was
performed on silica gel 300e400 mesh. Melting points were de-
termined using a Gallenkamp melting point apparatus and are
uncorrected. The FT-IR spectra were recorded from KBr pellets or
thin film from CHCl3 on the NaCl window in the 4000e400 cmꢁ1
ranges on a Nicolet 5DX spectrometer. All HRMS spectra were re-
cord using EI at 70 eV. X-ray Crystallography diffraction data of ab
d
¼151.7, 145.3, 143.8, 140.0, 138.3, 138.1, 137.5, 136.0, 134.4, 133.4,
133.0, 130.7, 130.0, 129.9, 129.7, 129.4, 128.1, 127.9, 127.5, 126.8,
~
125.9, 54.6, 53.9, 21.6, 21.5, 21.4 ppm; FT-IR (KBr): nmax¼2358, 1597,
1514, 1446, 1346, 1166, 1097, 771, 669, 549 cmꢁ1; HRMS (ESI): m/z
[MþH]þ calcd for C36H31N2O2S: 555.2107; found: 555.2092.
was collected at room temperature with a Bruker SMART Apex CCD
4.2.4. 7,11-Bis(4-methoxyphenyl)-9-tosyl-9,10-dihydro-8H-pyrrolo
[3,4-j]phenanthridine (3d). Yellow powder; 346 mg (59%); Rf¼0.38
(petroleum ether/EtOAc¼4:1); mp 253e254 ꢀC; 1H NMR (300 MHz,
ꢀ
diffractometer with Mo K
monochromator using the
a
radiation (
l
¼0.71073 A) with a graphite
u
-scan mode. Data reductions and ab-
sorption corrections were performed with SAINT and SADABS
software, respectively.17 The structure was solved by direct
methods and refined on F2 by full-matrix least squares using
SHELXTL.18 All non-hydrogen atoms were treated anisotropically.
The positions of hydrogen atoms were generated geometrically. 1,6-
Diynes aep were prepared by published procedures.19
CDCl3):
d
¼9.05 (s, 1H; AreH), 8.08 (s, 1H; AreH), 7.69e7.59 (m, 4H;
AreH), 7.31e7.22 (m, 5H; AreH), 7.21e7.07 (m, 6H; AreH), 4.61 (s,
2H; eCHHe), 4.50 (s, 2H; eCHHe), 3.96 (d, J¼9.7 Hz, 6H; CH3Oe),
2.39 ppm (s, 3H; CH3e); 13C NMR (75 MHz, CDCl3):
d
¼159.5, 151.5,
149.8, 145.4, 143.7, 140.3, 136.8, 136.0, 134.5, 133.5, 132.5, 130.7,
130.0, 129.8, 129.3, 128.2, 128.0, 127.5, 126.7, 126.1, 115.5, 114.4, 55.4,
~
54.6, 53.9, 21.5 ppm; FT-IR (KBr): nmax¼2835, 1608, 1514, 1340, 1161,
4.2. Synthesis
1103, 1031, 767, 669, 546 cmꢁ1; HRMS (ESI): m/z [MþH]þ calcd for
C36H31N2O4S: 587.2005; found: 587.2002.
Typical procedure for the palladium-catalyzed domino reaction
of the 1,6-diynes with bromo(iso)quinoline: diyne 1aep (1.0 equiv),
3-bromoquinoline (1.2 equiv), Pd(OAc)2 (2 mol %), and PPh3
(4 mol %) were added to the degassed solution of (n-Bu)3N
(1.2 equiv) in DMF (5 mL) and the mixture was stirred at room
temperature for 40 min then heated at 125e130 ꢀC for 24 h. The
reaction mixture was cooled, quenched with water, and extracted
with EtOAc (3ꢂ5 mL). The combined organic layers were washed
with hydrochloric acid (5%), aqueous sodium carbonate (5%), and
saturated aqueous sodium chloride solution. After separation, the
organic layer was dried over anhydrous MgSO4 and concentrated
under reduced pressure. The residue was purified by flash chro-
matography (6:1 petroleum ether/EtOAc) to give the corresponding
product 3.
4.2.5. 7,11-Bis(4-fluorophenyl)-9-tosyl-9,10-dihydro-8H-pyrrolo[3,4-
j]phenanthridine (3e). Yellow powder; 483 mg (86%); Rf¼0.42 (pe-
troleum ether/EtOAc¼4:1); mp 246e247 ꢀC; 1H NMR (300 MHz,
CDCl3):
d
¼9.11 (s, 1H; AreH), 8.07 (d, J¼8.5 Hz, 1H; AreH),
7.71e7.47 (m, 4H; AreH), 7.29e7.21 (m, 6H; AreH), 7.20e7.16 (m,
5H; AreH), 4.58 (d, J¼11.8 Hz, 2H; eCHHe), 4.48 (d, J¼11.5 Hz, 2H;
eCHHe), 2.38 ppm (d, J¼17.0 Hz, 3H; CH3e); 13C NMR (75 MHz,
CDCl3):
d
¼164.5, 164.4, 161.2, 161.1, 151.2, 143.9, 140.2, 136.3, 136.2,
135.2, 134.7, 133.5, 132.8, 131.8, 131.3, 131.2, 130.3, 130.0, 129.9,
128.5, 127.5, 126.5, 126.2, 117.4, 117.1, 116.4, 116.1, 54.4, 53.6,
~
21.5 ppm; FT-IR (KBr): nmax¼2854, 1604, 1512, 1348, 1157, 1095, 815,
667, 548 cmꢁ1; HRMS (ESI): m/z [MþH]þ calcd for C34H25F2N2O2S:
563.1606; found: 563.1587.
4.2.1. 7,11-Diphenyl-9-tosyl-9,10-dihydro-8H-pyrrolo[3,4-j]phenan-
thridine (3a). Yellow powder; 395 mg (75%); Rf¼0.38 (petroleum
ether/EtOAc¼4:1); mp 253e254 ꢀC; 1H NMR (300 MHz, CDCl3):
4.2.6. 7,11-Di-o-tolyl-9-tosyl-9,10-dihydro-8H-pyrrolo[3,4-j]phenan-
thridine (3f). Yellow powder; 471 mg (85%); Rf¼0.48 (petroleum
ether/EtOAc¼4:1); mp 186e187 ꢀC; 1H NMR (300 MHz, CDCl3):
d
¼9.08 (s, 1H; AreH), 8.08 (d, J¼6.9 Hz, 1H; AreH), 7.69e7.57 (m,
d
¼8.90 (s, 1H; AreH), 8.10 (d, J¼7.8 Hz, 1H; AreH), 7.68 (d, J¼7.3 Hz,
5H; AreH), 7.56e7.47 (m, 5H; AreH), 7.31 (m, 6H; AreH), 7.14 (s,
1H; AreH), 4.62 (s, 2H; eCHHe), 4.51 (s, 2H; eCHHe), 2.40 ppm (s,
2H; AreH), 7.58e7.38 (m, 8H; AreH), 7.30 (d, J¼7.4 Hz, 2H; AreH),
7.20 (t, J¼8.5 Hz, 3H; AreH), 4.65e4.31 (m, 4H; eCHHe), 2.39 (s,
3H; CH3e), 1.98 (s, 3H; CH3e), 1.90 ppm (s, 3H; CH3e); 13C NMR
3H; CH3e); 13C NMR (75 MHz, CDCl3):
d
¼151.5, 143.8, 145.2, 140.4,
139.8, 136.0, 135.9, 134.4, 133.6, 133.3, 130.0, 129.8, 129.4, 128.9,
128.5, 128.4, 128.2, 128.1, 127.5, 126.7, 125.9, 59.6, 53.7, 21.5 ppm;
(75 MHz, CDCl3):
130.3, 129.9, 129.3, 129.2, 128.9, 128.4, 128.0, 127.9, 127.7, 127.5,
126.7, 126.5, 125.4, 125.3, 54.6, 53.8, 21.5, 19.9, 19.5 ppm; FT-IR
d
¼151.6, 145.3, 143.9, 139.8, 135.5, 131.4, 130.6,
~
FT-IR (KBr): nmax¼3055, 1597, 1448, 1400, 1346, 1317, 1157, 1095,

316
Y. Hu et al. / Tetrahedron 68 (2012) 311e318
(KBr): nmax¼2918, 1595, 1446, 1344, 1165, 1097, 818, 667, 550 cmꢁ1
;
1095, 771, 705, 671, 590, 549 cmꢁ1; HRMS (ESI): m/z [MþH]þ calcd
~
HRMS (ESI): m/z [MþH]þ calcd for C36H31N2O2S: 555.2107; found:
for C35H29N2O2S: 541.1950.; found: 541.1926.
555.2058.
4.2.12. 7-Phenyl-11-(o-tolyl)-9-tosyl-9,10-dihydro-8H-pyrrolo[3,4-j]
phenanthridine (4j). Yellow powder; 297 mg (55%); Rf¼0.43 (pe-
troleum ether/EtOAc¼4:1); mp 251e252 ꢀC; 1H NMR (300 MHz,
4.2.7. Diethyl 4,40-(9-tosyl-9,10-dihydro-8H-pyrrolo[3,4-j]phenan-
thridine-7,11-diyl)dibenzoate (3g). Yellow powder; 375 mg (56%);
Rf¼0.38 (petroleum ether/EtOAc¼4:1); mp 217e218 ꢀC; 1H NMR
CDCl3):
d
¼9.11 (s, 1H; AreH), 8.09 (d, J¼7.7 Hz, 1H; AreH), 7.68 (d,
(300 MHz, CDCl3):
d¼9.03 (s, 1H; AreH), 8.29 (d, J¼6.5 Hz, 4H;
J¼7.8 Hz, 2H; AreH), 7.57 (d, J¼6.5 Hz, 4H; AreH), 7.50e7.27 (m,
8H; AreH), 7.16 (d, J¼6.1 Hz, 2H; AreH), 4.71e4.30 (m, 4H;
eCHHe), 2.40 (s, 3H; CH3e), 1.92 (s, 3H; CH3e); 13C NMR (75 MHz,
AreH), 8.11 (d, J¼7.3 Hz, 1H; AreH), 7.67e7.49 (m, 6H; AreH),
7.48e7.27 (m, 5H; AreH), 7.17 (d, J¼6.8 Hz, 1H; AreH), 4.56e4.46
(m, 8H; eCHHe), 2.40 (s, 3H; CH3e), 1.49 ppm (d, J¼5.9 Hz, 6H;
CDCl3):
d
¼151.8, 145.1, 143.8, 139.7, 139.6, 136.1, 136.0, 135.3, 133.6,
eOCH2CH3); 13C NMR (75 MHz, CDCl3):
d
¼166.2, 150.9, 145.5, 145.0,
131.4, 130.2, 130.0, 129.5, 129.0, 128.9, 128.5, 128.4, 128.0, 127.7,
127.5, 126.7, 125.4, 124.5, 54.5, 53.9, 21.5, 19.6 ppm; FT-IR (KBr):
144.0, 140.6, 139.7, 135.4, 134.5, 133.4, 133.1, 131.3, 130.9, 130.7,
130.3, 130.0, 129.6, 128.6, 128.4, 127.5, 126.6, 126.4, 123.7, 118.5, 61.4,
nmax¼3051, 1595, 1167, 1095, 667, 613, 546 cmꢁ1; HRMS (ESI): m/z
~
~
54.3, 53.5, 21.5, 14.4 ppm; FT-IR (KBr): nmax¼2978, 1722, 1709, 1274,
[MþH]þ calcd for C35H29N2O2S: 541.1950; found: 541.1931.
1161, 763, 705, 665 cmꢁ1; HRMS (ESI): m/z [MþH]þ calcd for
C40H35N2O6S: 671.2217; found: 671.2189.
4.2.13. 7-(4-Methoxyphenyl)-11-phenyl-9-tosyl-9,10-dihydro-8H-
pyrrolo[3,4-j]phenanthridine (3k). Yellow powder; 339 mg (61%);
Rf¼0.39 (petroleum ether/EtOAc¼4:1); mp 231e232 ꢀC; 1H NMR
4.2.8. 7-(4-Chlorophenyl)-11-phenyl-9-tosyl-9,10-dihydro-8H-pyr-
rolo[3,4-j]phenanthridine (3h). Yellow powder; 169 mg (33%);
Rf¼0.42 (petroleum ether/EtOAc¼4:1); mp 265e266 ꢀC; 1H NMR
(300 MHz, CDCl3):
d
¼9.13 (s, 1H; AreH), 8.08 (d, J¼7.6 Hz, 1H;
AreH), 7.68 (d, J¼7.4 Hz, 2H; AreH), 7.58 (s, 4H; AreH), 7.48 (d,
J¼8.4 Hz, 1H; AreH), 7.29 (s, 6H; AreH), 7.20e7.08 (m, 3H; AreH),
4.63 (s, 2H; eCHHe), 4.50 (s, 2H; eCHHe), 3.95 (s, 3H; CH3Oe),
(300 MHz, CDCl3):
d
¼9.07 (s, 1H; AreH), 8.07 (d, J¼7.8 Hz, 1H;
AreH), 7.78 (d, J¼7.2 Hz, 2H; AreH), 7.58e7.45 (m, 11H; AreH),
7.36e7.26 (m, 4H; AreH), 7.13 (t, J¼7.4 Hz, 1H; AreH), 4.63 (s, 2H;
eCHHe), 4.52 ppm (s, 2H; eCHHe); 13C NMR (75 MHz, CDCl3):
2.40 (s, 3H; CH3e); 13C NMR (75 MHz, CDCl3):
d
¼159.7, 151.7, 145.4,
143.8, 140.5, 139.8, 135.9, 134.7, 133.5, 133.4, 130.7, 130.0, 129.9,
129.5, 129.3, 128.9, 128.4, 128.2, 128.1, 127.5, 126.8, 125.9, 115.5,
d
¼151.6, 145.4, 140.5, 139.7, 136.5, 136.0, 133.7, 132.9, 129.5, 129.3,
~
129.0, 128.6, 128.5, 128.2, 127.5, 126.8, 126.0, 54.6, 53.8 ppm; FT-IR
114.4, 55.5, 54.6, 53.9, 21.5 ppm; FT-IR (KBr): nmax¼3028,1612,1514,
~
(KBr): nmax¼2310, 1445, 1348, 1168, 1099, 763, 619, 594,
1344, 1157, 1095, 810, 594 cmꢁ1; HRMS (ESI): m/z [MþH]þ calcd for
573 cmꢁ1
;
HRMS (ESI): m/z [MþH]þ calcd for C33H25N2O2S:
C35H29N2O3S: 557.1899; found: 557.1883.
513.1637; found: 513.1622.
4.2.14. 7-(4-Fluorophenyl)-11-phenyl-9-tosyl-9,10-dihydro-8H-pyr-
rolo[3,4-j]phenanthridine (3l). Yellow powder; 158 mg (29%);
Rf¼0.42 (petroleum ether/EtOAc¼4:1); mp 262e263 ꢀC; 1H NMR
4.2.9. 11-(4-Chlorophenyl)-7-phenyl-9-tosyl-9,10-dihydro-8H-pyr-
rolo[3,4-j]phenanthridine (4h). Yellow powder; 280 mg (50%);
Rf¼0.38 (petroleum ether/EtOAc¼4:1); mp 266e267 ꢀC; 1H NMR
(300 MHz, CDCl3):
d
¼9.05 (s, 1H; AreH), 8.09 (s, 1H; AreH),
(300 MHz, CDCl3):
d
¼9.07 (s, 1H; AreH), 8.09 (d, J¼7.6 Hz, 1H;
7.69e7.50 (m, 7H; AreH), 7.31 (s, 8H; AreH), 7.15 (s,1H; AreH), 4.60
(s, 2H; eCHHe), 4.50 (s, 2H; eCHHe), 2.40 ppm (s, 3H; CH3e); 13
NMR (75 MHz, CDCl3):
AreH), 7.68 (d, J¼7.6 Hz, 2H; AreH), 7.60e7.51 (m, 7H; AreH),
7.33e7.12 (m, 7H; AreH), 4.60 (s, 2H; eCHHe), 4.47 (s, 2H;
eCHHe), 2.40 ppm (s, 3H; CH3e); 13C NMR (75 MHz, CDCl3):
C
d
¼164.5, 161.2, 151.1, 145.4, 143.9, 140.4,
140.0, 135.0,134.7,134.0,131.3,131.2,131.0,130.1,130.0,128.5, 128.4,
d
¼151.5, 145.4, 144.0, 140.0, 139.0, 136.5135.9, 134.6, 132.3, 130.4,
127.5, 126.8, 126.1, 125.7, 124.0, 116.3, 116.0, 54.5, 53.7, 21.5 ppm; FT-
IR (KBr): nmax¼3055, 1512, 1346, 1159, 813, 592, 547, 530 cmꢁ1
;
~
130.3, 129.9, 128.7, 128.5, 127.6, 126.6, 126.2, 54.4, 53.7, 21.6 ppm;
FT-IR (KBr): nmax¼2954, 1595, 1490, 1157, 1093, 831, 765, 588,
HRMS (ESI): m/z [MþH]þ calcd for C34H26FN2O2S: 545.1699; found:
~
523 cmꢁ1; HRMS (ESI): m/z [MþH]þ calcd for C34H26ClN2O2S:
545.1685.
561.1404; found: 561.1377.
4.2.15. 11-(4-Fluorophenyl)-7-phenyl-9-tosyl-9,10-dihydro-8H-pyr-
rolo[3,4-j]phenanthridine (4l). Yellow powder; 315 mg (58%);
Rf¼0.40 (petroleum ether/EtOAc¼4:1); mp 264e265 ꢀC; 1H NMR
4.2.10. 11-Phenyl-7-(p-tolyl)-9-tosyl-9,10-dihydro-8H-pyrrolo[3,4-j]
phenanthridine (3i). Yellow powder; 356 mg (66%); Rf¼0.46 (pe-
troleum ether/EtOAc¼4:1); mp 271e272 ꢀC; 1H NMR (300 MHz,
(300 MHz, CDCl3):
d
¼9.08 (s, 1H; AreH), 8.10 (s, 1H; AreH),
CDCl3):
d
¼9.12 (s, 1H; AreH), 8.09 (s, 1H; AreH), 7.69e7.50 (m, 7H;
7.69e7.51 (m, 5H; AreH), 7.50e7.34 (m, 6H; AreH), 7.33e7.20 (m,
5H; AreH), 4.62 (s, 2H; eCHHe), 4.50 (s, 2H; eCHHe), 2.40 ppm (s,
AreH), 7.39e7.13 (m, 9H; AreH), 4.62 (s, 2H; eCHHe), 4.51 (s, 2H;
eCHHe), 2.52 (s, 3H; CH3e), 2.40 (s, 3H; CH3e); 13C NMR (75 MHz,
3H; CH3e); 13C NMR (75 MHz, CDCl3):
d
¼164.4, 161.1, 151.5, 145.5,
CDCl3):
d
¼151.7, 145.4, 143.8, 140.5, 139.9, 138.4, 136.4, 134.6, 133.5,
143.9,140.1,136.4,136.0,134.6,133.7,132.6,131.0,130.3,130.1,129.9,
129.5, 129.0, 128.6, 128.4, 127.5, 126.6, 126.1, 117.4, 117.1, 54.5, 53.8,
133.0, 130.4, 130.9, 130.1, 129.9, 129.7, 129.4, 128.4, 128.2, 127.6,
~
~
126.9, 126.0, 54.6, 53.9, 21.5, 21.4 ppm; FT-IR (KBr): nmax¼2866,
21.5 ppm; FT-IR (KBr): nmax¼3061, 1595, 1508, 1346, 1157, 769, 590,
1597, 1157, 1095, 759, 594, 522 cmꢁ1; HRMS (ESI): m/z [MþH]þ
548, 530 cmꢁ1; HRMS (ESI): m/z [MþH]þ calcd for C34H26FN2O2S:
calcd for C35H29N2O2S: 541.1950; found: 541.1944.
545.1699; found: 545.1678.
4.2.11. 11-Phenyl-7-(o-tolyl)-9-tosyl-9,10-dihydro-8H-pyrrolo[3,4-j]
phenanthridine (3j). Yellow powder; 167 mg (31%); Rf¼0.45 (pe-
troleum ether/EtOAc¼4:1); mp 157e158 ꢀC; 1H NMR (300 MHz,
4.2.16. 7-(4-Fluorophenyl)-11-(o-tolyl)-9-tosyl-9,10-dihydro-8H-
pyrrolo[3,4-j]phenanthridine (3m). Yellow powder; 396 mg (71%);
Rf¼0.45 (petroleum ether/EtOAc¼4:1); mp 234e235 ꢀC; 1H NMR
CDCl3):
d
¼8.87 (s, 1H; AreH), 8.08 (d, J¼7.9 Hz, 1H; AreH), 7.68 (d,
(300 MHz, CDCl3):
d
¼9.07 (s, 1H; AreH), 8.10 (d, J¼7.8 Hz, 1H;
J¼7.9 Hz, 2H; AreH), 7.59 (s, 3H; AreH), 7.54e7.27 (m, 9H; AreH),
7.15 (t, J¼9.2 Hz, 2H; AreH), 4.60e4.40 (m, 4H; eCHHe), 2.40 (s,
AreH), 7.68 (d, J¼7.7 Hz, 2H; AreH), 7.59e7.47 (m, 6H; AreH),
7.46e7.30 (m, 5H; AreH), 7.17 (t, J¼7.9 Hz, 2H; AreH), 4.69e4.30
(m, 4H; eCHHe), 2.40 (s, 3H; CH3e), 1.91 (s, 3H; CH3e); 13C NMR
3H; CH3e), 1.99 (s, 3H; CH3e); 13C NMR (75 MHz, CDCl3):
d
¼151.4,
145.5, 143.8, 140.5, 140.0, 136.2, 135.4, 134.5, 133.7, 130.6, 130.2,
130.1, 129.8, 129.3, 128.9, 128.4, 128.2, 127.5, 126.8, 126.6, 126.0,
(75 MHz, CDCl3):
134.9, 134.8, 133.6, 133.5, 131.4, 131.3, 130.2, 129.9, 128.9, 128.5,
127.9, 127.7, 127.5, 126.8, 125.4, 116.3, 116.0, 54.5, 53.7, 21.5,
d
¼164.4, 161.1, 151.4, 143.9, 139.7, 139.6, 135.2,
~
124.3, 54.6, 53.7, 21.5, 19.9 ppm; FT-IR (KBr): nmax¼3057, 1344, 1157,

Y. Hu et al. / Tetrahedron 68 (2012) 311e318
317
~
19.6 ppm; FT-IR (KBr): nmax¼3064, 1510, 1348, 1095, 815, 742, 665,
549 cmꢁ1; HRMS (ESI): m/z [MþH]þ calcd for C35H28FN2O2S:
559.1856; found: 559.1834.
2.37 ppm (s, 3H; CH3e); 13C NMR (75 MHz, CDCl3):
d
¼154.9, 148.7,
143.2, 137.5, 137.3, 137.0, 135.8, 135.3, 134.6, 134.0, 133.8, 133.6,
132.8, 132.6, 130.7, 130.4, 129.5, 128.7, 128.6, 127.6, 127.0, 122.7, 49.7,
~
47.1, 21.5 ppm; FT-IR (KBr): nmax¼3030, 1489, 1334, 1157, 1095, 767,
4.2.17. 11-(4-Fluorophenyl)-7-(4-methoxyphenyl)-9-tosyl-9,10-
dihydro-8H-pyrrolo[3,4-j]phenanthridine (3n). Yellow powder;
356 mg (62%); Rf¼0.42 (petroleum ether/EtOAc¼4:1); mp
673, 530, 509 cmꢁ1
C30H23Cl2N2O2S: 545.0858; found: 545.0850.
;
HRMS (ESI): m/z [MþH]þ calcd for
236e237 ꢀC; 1H NMR (300 MHz, CDCl3):
d¼9.13 (s, 1H; AreH), 8.09
4.2.22. 4,9-Bis(4-fluorophenyl)-2-tosyl-2,3-dihydro-1H-pyrrolo[3,4-
g]isoquinoline (7d). Yellow powder; 256 mg (50%); Rf¼0.36 (pe-
troleum ether/EtOAc¼3:1); mp 189e190 ꢀC; 1H NMR (300 MHz,
(d, J¼7.9 Hz, 1H; AreH), 7.69 (d, J¼7.7 Hz, 2H; AreH), 7.58 (t,
J¼7.3 Hz, 1H; AreH), 7.48 (d, J¼8.5 Hz, 1H; AreH), 7.29 (s, 8H;
AreH), 7.20e7.08 (m, 3H; AreH), 4.63 (s, 2H; eCHHe), 4.49 (s, 2H;
eCHHe), 3.95 (s, 3H; CH3Oe), 2.40 (s, 3H; CH3e); 13C NMR
CDCl3):
d
¼8.50 (s, 1H; AreH), 7.49 (d, J¼7.1 Hz, 1H; AreH),
7.42e7.26 (m, 8H; AreH), 7.16e7.07 (m, 4H; AreH), 6.63 (s, 1H;
(75 MHz, CDCl3):
d
¼164.3, 161.0, 159.8, 151.6, 145.4, 143.9, 140.1,
AreH), 4.48 (s, 4H; eCHHe), 2.36 ppm (s, 3H; CH3e); 13C NMR
136.4, 136.3, 136.2, 134.8, 132.3, 131.0, 130.7, 130.2, 130.1, 130.0,
129.9, 128.3, 127.9, 127.6, 126.6, 126.0, 125.9, 123.9, 117.4, 117.1, 114.5,
(75 MHz, CDCl3):
137.0, 136.8, 136.6, 132.8, 132.6, 131.7, 131.6, 131.2, 131.1, 130.9, 130.8,
129.9, 129.5, 127.6, 126.9, 122.5, 115.6, 115.5, 115.4, 115.3, 49.7, 47.1,
d
¼163.8, 163.7, 160.5, 160.4, 155.0, 148.6, 143.1,
~
55.5, 54.5, 53.8, 21.5 ppm; FT-IR (KBr): nmax¼3047, 1608, 1398,1248,
1097, 812, 667, 588 cmꢁ1; HRMS (ESI): m/z [MþH]þ calcd for
21.5 ppm; FT-IR (KBr): nmax¼3034,1599,1506,1338,1157,1093, 935,
~
C35H28FN2O3S: 575.1805; found: 575.1786.
661, 547, 526 cmꢁ1
;
HRMS (ESI): m/z [MþH]þ calcd for
C30H23F2N2O2S: 513.1449; found: 513.1427.
4.2.18. 7-(4-Chlorophenyl)-11-(4-fluorophenyl)-9-tosyl-9,10-
dihydro-8H-pyrrolo[3,4-j]phenanthridine (3o). Yellow powder;
353 mg (61%); Rf¼0.38 (petroleum ether/EtOAc¼4:1); mp
4.2.23. 6-Chloro-4-(4-chlorophenyl)-2-tosyl-2,3-dihydro-1H-benzo
[f]isoindole (9b). Yellow powder; 47 mg (10%); Rf¼0.49 (petroleum
ether/EtOAc¼3:1); mp 197e198 ꢀC; 1H NMR (300 MHz, CDCl3):
268e269 ꢀC; 1H NMR (300 MHz, CDCl3):
d¼9.04 (s, 1H; AreH), 8.11
(s, 1H; AreH), 7.69 (d, J¼7.5 Hz, 2H; AreH), 7.57 (d, J¼7.2 Hz, 2H;
AreH), 7.49e7.37 (m, 6H; AreH), 7.36e7.19 (m, 5H; AreH), 4.59 (s,
2H; eCHHe), 4.48 (s, 2H; eCHHe), 2.41 ppm (s, 3H; CH3e); 13C
d
¼7.75 (d, J¼7.5 Hz, 2H; AreH), 7.63e7.47 (m, 4H; AreH), 7.42e7.34
(m, 3H; AreH), 7.32 (d, J¼7.8 Hz, 2H; AreH), 7.19 (d, J¼7.8 Hz, 2H;
AreH), 4.78 (s, 2H; eCHHe), 4.44 (s, 2H; eCHHe), 2.40 ppm (s, 3H;
NMR (75 MHz, CDCl3):
136.2, 135.1, 134.9, 134.4, 133.6, 130.8, 130.0, 129.9, 128.5, 127.5,
d
¼164.4, 161.1, 151.3, 143.9, 140.5, 139.8,
CH3e); 13C NMR (75 MHz, CDCl3):
d
¼143.9,138.1,135.2,134.8,134.7,
134.4, 132.4,131.7,130.7,130.5, 130.0, 129.9, 129.6,129.5, 129.3128.9,
127.6, 127.5, 127.1, 124.3, 120.9, 118.7, 53.3, 52.9, 21.5 ppm; FT-IR
~
126.3, 117.5, 117.1, 54.4, 53.6, 21.5 ppm; FT-IR (KBr): nmax¼3064,
1597, 1508, 1346, 1014, 813, 667, 549 cmꢁ1; HRMS (ESI): m/z
(KBr): nmax¼2860, 1599, 1492, 1344, 1159, 1095, 667, 605,
~
[MþH]þ calcd for C34H25ClFN2O2S: 579.1310; found: 579.1286.
551 cmꢁ1; HRMS (ESI): m/z [MþH]þ calcd for C25H20Cl2NO2S:
468.0593; found: 468.0586.
4.2.19. 7,11-Diphenyl-9-(phenylsulfonyl)-9,10-dihydro-8H-pyrrolo
[3,4-j]phenanthridine (5p). Yellow powder; 379 mg (74%); Rf¼0.42
(petroleum ether/EtOAc¼4:1); mp 265e266 ꢀC; 1H NMR (300 MHz,
Acknowledgements
CDCl3):
d¼9.07 (s, 1H; AreH), 8.07 (d, J¼7.8 Hz, 1H; AreH), 7.78 (d,
The authors thank the National Science Foundation of China
(21072003, 20872002) for financial support. The authors are
grateful to Prof. J. Hu, Dr. Y. Wei for their assistance in running NMR
spectra and X-ray diffraction analyses.
J¼7.2 Hz, 2H; AreH), 7.58e7.52 (m, 5H; AreH), 7.51e7.45 (m, 6H;
AreH), 7.36e7.26 (m, 4H; AreH), 7.13 (t, J¼7.4 Hz, 1H; AreH), 4.63
(s, 2H; eCHHe), 4.52 ppm (s, 2H; eCHHe); 13C NMR (75 MHz,
CDCl3):
d
¼151.6, 145.4, 140.5, 139.7, 136.5, 136.0, 133.7, 132.9, 129.5,
129.3, 129.0, 128.6, 128.5, 128.2, 127.5, 126.8, 126.0, 54.6, 53.8 ppm;
Supplementary data
~
FT-IR (KBr): nmax¼2310, 1445, 1348, 1168, 1099, 763, 619, 594,
573 cmꢁ1
;
HRMS (ESI): m/z [MþH]þ calcd for C33H25N2O2S:
CCDC 809656 (3e) and CCDC 809657 (8e) contain the supple-
mentary crystallographic data for this paper. These data can be
obtained free of charge from The Cambridge Crystallographic Data
Centre via www.ccdc.cam.ac.uk/data_request/cif. Copies of 1H
NMR, 13C NMR spectra of all compounds are provided. Supple-
mentary data related to this article can be found online at
doi:10.1016/j.tet.2011.10.041. These data include MOL files and
InChiKeys of the most important compounds described in this
article.
513.1637; found: 513.1622.
4.2.20. 7,11-Bis(4-methoxyphenyl)-9-tosyl-9,10-dihydro-8H-pyrrolo
[3,4-b]phenanthridine (6d). White powder; 240 mg (41%); Rf¼0.45
(petroleum ether/EtOAc¼6:1); mp 200e201 ꢀC; 1H NMR (300 MHz,
CDCl3):
d
¼9.80 (s, 1H; AreH), 7.74 (q, J¼8.0 Hz, 3H; AreH), 7.47 (t,
J¼7.5 Hz,1H; AreH), 7.33e7.18 (m, 6H; AreH), 6.98 (d, J¼8.1 Hz, 2H;
AreH), 6.83 (d, J¼8.1 Hz, 2H; AreH), 6.70 (d, J¼6.5 Hz, 2H; AreH),
4.78 (s, 2H; eCHHe), 4.60e4.43 (m, 2H; eCHHe), 3.87 (s, 3H;
CH3Oe), 3.75 (s, 3H; CH3Oe), 2.43 ppm (s, 3H; CH3e); 13C NMR
References and notes
(75 MHz, CDCl3):
135.7,135.2,134.4, 133.5,133.2, 131.7,131.1,130.9,130.4,129.8,129.3,
129.2, 127.7, 127.6, 127.4, 114.3, 113.9, 113.7, 55.4, 54.0, 53.8,
d
¼191.4, 159.4, 158.7, 144.3, 143.7, 137.4, 136.7,
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~
21.5 ppm; FT-IR (KBr): nmax¼2839,1691,1597,1519,1346,1167,1097,
827, 673, 549 cmꢁ1
;
HRMS (ESI): m/z [MþH]þ calcd for
C36H31N2O4S: 587.2005; found: 587.1999.
€
4.2.21. 4,9-Bis(4-chlorophenyl)-2-tosyl-2,3-dihydro-1H-pyrrolo[3,4-
g]isoquinoline (7b). Yellow powder; 272 mg (50%); Rf¼0.45 (pe-
troleum ether/EtOAc¼3:1); mp 202e203 ꢀC; 1H NMR (300 MHz,
CDCl3):
d
¼8.51 (s, 1H; AreH), 7.50 (d, J¼7.5 Hz, 1H; AreH),
€
7.42e7.27 (m, 8H; AreH), 7.20 (d, J¼7.7 Hz, 2H; AreH), 7.10 (d,
J¼7.6 Hz, 2H; AreH), 6.62 (s, 1H; AreH), 4.48 (s, 4H; eCHHe),
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2375e2380; (b) Renu, O.; Lapointe, D.; Fagnou, K. Org. Lett. 2009, 11,
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15. Crystal structure determination: C35H25Cl3F2N2O2S 3e, M¼681.98, triclinic,
3
ꢀ
ꢀ
space group Pꢁ1, a¼11.301(5), b¼11.524(5), c¼12.526(5) A, U¼1567.9(11) A ,
T¼293 K, Z¼2, 5555 reflections measured, 13,622 unique (Rint¼0.022), which
were used in all calculations. The final wR(F2) was 0.1238 (all data). Crystal
structure determination: C30H26F2N2O2S 8e, M¼2519.0(3), triclinic, space group
€
8. (a) Harayama, T.; Hori, A.; Abe, H.; Takeuchi, Y. Tetrahedron 2004, 60,
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3
ꢀ
ꢀ
Pꢁ1, a¼12.6080(2), b¼18.4828(12), c¼12.3061(8) A, U¼2519.0(3) A , T¼293 K,
Z¼4, 5787 reflections measured, 21,530 unique (Rint¼0.025), which were used
in all calculations. The final wR(F2) was 0.0762 (all data).
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(USA), 2003.
18. (a) Sheldrick, G. M. SHELXL97, Program for Crystal Structure Refinement; Uni-
€
versity of Gottingen: Germany, 1997; (b) Sheldrick, G. M. SHELXS97, Program for
€
Crystal Structure Refinement; University of Gottingen: Germany, 1997; (c)
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