Site-selective rh-catalyzed c-7 and c-6 dual c-h functionalization of indolines: Synthesis of functionalized pyrrolocarbazoles

Article abstract of DOI:10.1021/acs.joc.9b03180

A site-selective dual C-7 and C-6 C-H functionalization of indolines with azabenzonorbornadienes has been accomplished using Rh-catalysis. The reaction affords a potential route toward pyrrolocarbazoles with broad scope and functional group tolerance.

Full text of DOI:10.1021/acs.joc.9b03180

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Note
Site-Selective Rh-Catalyzed C-7 and C-6 Dual C-H Functionalization
of Indolines: Synthesis of Functionalized Pyrrolocarbazoles
Sonbidya Banerjee, SUNDARAVEL VIVEK KUMAR, and Tharmalingam Punniyamurthy
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.9b03180 • Publication Date (Web): 09 Jan 2020
Downloaded from pubs.acs.org on January 9, 2020
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Site-Selective Rh-Catalyzed C-7 and C-6 Dual C-H Functionalization of Indolines:
Synthesis of Functionalized Pyrrolocarbazoles
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Sonbidya Banerjee, Sundaravel Vivek Kumar and Tharmalingam Punniyamurthy*
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Department of Chemistry, Indian Institute of Technology Guwahati, Guwahati 781039, India
2-pym
N
R'
2-pym
N
H
N
+
Rh
H
N
H
"C-7" C-C bond formation
"C-6" C-N bond formation
R'
H
34 examples
Site-selectivity Substrate scope
Dual C-H functionalization
ABSTRACT: A site-selective dual C-7 and C-6 C-H functionalization of indolines with
azabenzonorbornadienes has been accomplished using Rh-catalysis. The reaction affords a
potential route towards pyrrolocarbazoles with broad scope and functional group tolerance.
Transition-metal-catalyzed direct C-H functionalization revolutionizes the transformation of
simple substrates into complex molecules with structural diversity and atom economy.1,2 Indole
and its analogue are ubiquitous in natural products and pharmaceuticals.3 Particularly, pyrrolo-
/indolocarbazoles represents an appealing class of structural motifs4 that exhibit interesting
medicinal5 and material properties (Figure S1).6 Functionalization of C-27, C-3,7 C-48 and C-
79 C-H bonds of indole/indoline have thus been considerably investigated.10 In contrast, the
C-6 functionalization remains underdeveloped (Scheme S1a).11 The groups of Yu, Baran, Shi
and Frost demonstrated olefination,11a borylation,11b arylation11c and alkylation11d at C6 site,
respectively. Contextually, a dual C-H functionalization of indolines would be valuable as it
can lead to tandem C-C and carbon-heteroatom bond formation for the construction of complex
structural scaffolds. In this line, azabenzonorbornadienes are realized as versatile building
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blocks.12 Herein, we report a dual C-7 and C-6 C-H functionalization of indolines with
azabenzonorbornadienes using a Rh-catalysis to furnish pyrrolocarbazoles (Scheme S1b). The
site-selectivity, substrate scope and functional group diversity are important practical features.
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Scheme 1. Optimization of the Reaction Conditionsa
Bs
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N
2a
2-pym
2-pym
N
N
[Cp*RhCl2]2 (4 mol %)
oxidant (2.5 equiv)
H
additive (1 equiv)
solvent, 110 oC
N
H
N2, 24 h
1a
3a
Bs
Our optimization studies commenced employing 1-(pyrimidin-2-yl)indoline 1a and
azabenzonorbornadiene 2a as the model substrates (Scheme 1, Table S1). Delightfully, the
reaction occurred to furnish pyrrolocarbazole 3a in 48% yield when the substrates reacted using
4 mol % [Cp*RhCl2]2, 2.5 equiv Cu(OAc)2·H2O and 1 equiv K2CO3 for 24 h at 110 C in 1,2-
dichloroethane. Subsequent screening of the additives led to an enhance in the yield to 72%
utilizing Cs2CO3, whereas KOAc, CsOPiv and CsOAc produced moderate results. The reaction
utilizing AgSbF6 inhibited the formation of 3a, indicating cationic Rh(III) catalysis might not
be involved. Further screening of the oxidants revealed that Cu(OAc)2·H2O is the optimal
oxidant. 1,2-Dichloroethane was found to be the solvent of choice. Aerobic condition as well
as decreasing the temperature (100 °C) or the catalyst loading (2.5 mol %) led to drop the yield
to <61% yield. Control experiments confirmed that the combination of the Rh-catalyst, oxidant
and additive is crucial to produce 3a. Moreover, directing groups, 3,4-dihydro-2H-pyrrole I,
pyridinyl II, acetyl III, pivaloyl IV and N,N-dimethylcarbonyl V, were ineffective and the
starting materials were recovered intact (Table S1).
Having optimized the reaction conditions, the scope of the procedure was investigated for
substituted indolines 1 utilizing 2a as a standard substrate (Scheme 2). The substrates having
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substitution at the 4-position of indoline with allyl 1b, bromo 1c, cyano 1d, methoxy 1e and
phenyl 1f, 3-chlorophenyl 1g and 4-biphenyl 1h groups underwent reaction to produce 3b-h in
46-80% yields. In contrast, 5-substituted indolines 1i-k were unsuccessful substrates, which
might be due to steric hindrance near C6-site. However, a spiroindoline 1l gave 3l in 55% yield,
whereas 1-(pyrimidin-2-yl)-1,2-dihydrobenzoindole 1m and N-methyl-N-phenylpyrimidin-2-
amine 1n were found to be incompatible and formation of 3m and 3n was not observed.
Scheme 2. Substrate Scope of Indolines 1 with 2a a,b
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2-pym
2-pym
N
2a
N
H
[Cp*RhCl2]2
Cs2CO3
(CH2Cl)2
R
R
N
H
Bs
3b-n
1b-n
2-pym
H
3b
3c
3d
3e
3f
3g
3h
, X = allyl, 72%
, X = Br, 76%
, X = CN, 46%
, X = OMe, 80%
, X = Ph, 78%
N
X
N
H
Bs
, X = 3-ClC6H4, 67%
, X = 4-PhC6H4, 70%
2-pym
2-pym
N
N
H
H
N
H
N
H
Bs
X
Bs
3i,
trace (X=F)
3j
3k
, n.d. (X= Br)
, n.d (X=Me)
3l
, 55%
2-pym
Me
2-pym
N
N
H
H
N
N
H
H
Bs
3n,
Bs
3m
n.d.
, n.d.
aReaction conditions: 1b-n (0.25 mmol), 2a (0.3
mmol), [Cp*RhCl2]2 (4 mol %), Cu(OAc)2∙H2O
(0.63 mmol), Cs2CO3 (0.25 mmol), (CH2Cl)2 (2
mL), 110 oC, 24 h, N2. bIsolated yield.
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Scheme 3. Substrate Scope of Azabenzonorbornadienes 2 with 1aa,b
R
2-pym
N
N
2-pym
N
H
A
2b-q
7
8
9
[Cp*RhCl2]2
Cs2CO3
(CH2Cl)2
A
N
H
R
3o-ad
1a
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2-pym
H
2-pym
N
N
H
OMe
N
H
N
F
H
Boc
Bs
MeO
F
3p
, 46%
3o
, 71%
2-pym
3q
, X = H, 43%
, X = 3-Me, 51%
, X = 3-CF3, 63%
, X = 4-Cl, 69%
N
3r
H
3s
3t
(CCDC 1948984)
N
H
O S O
3u
3v
3w
3x
3y
, X = 4-I, 67%
, X = 4-Me, 54%
, X = 4-OMe, 58%
, X = 4-NO2, 70%
, X = 4-t-Bu, 55%
X
3q-y
2-pym
H
2-pym
N
N
H
N
H
O S O
Y
N
H
R
3ab,
3ac,
3ad
R = Ms, 71%
R = Cbz, 66%
, R = Boc, 63%
3z
, Y = 2-naphthyl, 52%
3aa
, Y = 2-thienyl, n.d.
aReaction conditions: 1a (0.25 mmol), 2b-q (0.3
mmol), [Cp*RhCl2]2 (4 mol %), Cu(OAc)2∙H2O
(0.63 mmol), Cs2CO3 (0.25 mmol), (CH2Cl)2 (2
o
b
mL), 110 C, 24 h, N2. Isolated yield. n.d. = not
detected.
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Scheme 4. Scope of Carbazoles and Related Frameworks 4 with 1a. a,b
3
4
5
6
7
8
2-pym
Bs
N
[Cp*RhCl2]2 (4 mol %)
Cu(OAc)2 H2O (2.5 equiv)
2-pym
n
N
N
.
n
+
Cs2CO3 (1 equiv)
(CH2Cl)2, 110 oC, 24 h
9
N
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n= 0,1
4a-e
2a
Bs
5
Br
2-pym
H
Bs
2-pym
H
Bs
N
N
N
N
N
2-pym
N
H
Bs
N
H
Bs
5b,
5a'
18%
5a
62%
, 47%
Et
2-pym
H
2-pym
H
N
2-pym
H
N
N
Et
S
N
N
N
H
H
H
Bs
5d
Bs
5e
Bs
, 80%
5c
, 65%
, n.d.
aReaction conditions: 4a-e (0.25 mmol), 2a (0.3 mmol), [Cp*RhCl2]2 (4 mol %),
Cu(OAc)2∙H2O (0.63 mmol), CsOAc (0.25 mmol), (CH2Cl)2 (2 mL), 110 oC, 24 h, N2. bIsolated
yield. n.d. = not detected.
The scope of the method was extended for diverse azabenzonorbornadienes 2 with indoline
1a as a standard substrate (Scheme 3). Substrates with 6,7-difluoro 2b and 5,8-dimethoxy 2c
groups in the aryl ring A reacted to give 3o and 3p in 71 and 46% yields, respectively. The
reaction of 2d having 9-phenylsulfonyl substituent afforded 3q in 43% yield. In addition, the
substrates containing 3-methyl 2e and 3-trifluoromethyl 2f groups in the 9-arylsulfonyl ring
reacted to provide 3r and 3s in 51 and 63% yields, respectively. Further, the reaction of the
substrates bearing substitution at the 4-position of the 9-arylsulfonyl ring viz; chloro 2g, iodo
2h, methyl 2i, methoxy 2j, nitro 2k and tert-butyl 2l groups, produced 3t-y in 54-70% yields.
Likewise, 9-naphthylsulfonyl substituted 2m underwent reaction to furnish 3z in 52% yield,
whereas 2n bearing 2-thiophene group was an unsuccessful substrate, which might be due to
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the chelation to the Rh-catalyst. The substrates with 9-mesyl 2o, 9-Cbz 2p and 9-Boc 2q
protecting groups readily reacted to deliver 3ab-ad in 63-71% yields. Notably, the products
were obtained as a single diastereoisomer and stereochemistry was assigned by single-crystal
X-ray of 3t as a representative example (See SI).
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The method was explored with carbazoles and related frameworks (Scheme 4). Thus, 9-
(pyrimidin-2-yl)-9H-carbazole 4a reacted to afford 5a and 5a in 47 and 18% yields,
respectively. The reaction of 3-bromo-9-(pyrimidin-2-yl)-9H-carbazole 4b afforded 5b in 62%
yield. Interestingly, 2,3-diethyl-1-(pyrimidin-2-yl)-1H-indole 4c and 1-(pyrimidin-2-yl)-
1,2,3,4-tetrahydroquinoline 4d conveyed 5c and 5d in 65 and 80% yields, respectively.
However, 10-(pyrimidin-2-yl)-10H-phenothiazine 4e failed to furnish 5e, which might be due
to the chelation of the thioether moiety to the Rh-catalyst.
Scheme 5. Post-Synthetic Modificationsa,b
2-pym
2-pym
H
N
N
a.
i
N
H
NH2
Boc
6
3ad
, 69%
52% (227 mg)
(on 2 mmol scale)
2-pym
2-pym
N
ii
N
b.
H
2-Nap
NH
Bs
, 76%
(CCDC 1951990)
N
H
Bs
5a
7
Reaction conditions: i. 3ad (0.25 mmol), CF3CO2H
(0.75 mmol), CH2Cl2 (2 mL), rt, 1 h; ii. 5a (0. 25
mmol), NaOEt (1.25 mmol), DMSO (3 mL), 110 oC,
2 h.
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The procedure was further examined for the reaction of 1-(pyrimidin-2-yl)indole 1a’ and 1,4-
dihydro-1,4-epoxynaphthalene 2a’ (Scheme S2, See SI). However, they were unsuccessful
substrates and formation of the target products 8 and 9 was not observed.
8
9
Finally, the scale up of the procedure was examined utilizing 1a and 2q as the representative
examples (Scheme 5). The reaction occurred to provide 3ad in 52% yield, which suggests that
the procedure is scalable. The products can be further transformed into diverse scaffolds. For
example, 3ad could be converted to 6 in 69% yield employing trifluoroacetic acid via Boc
deprotection and acid-mediated elimination. Similarly, 5a could be transformed to 7 in 76%
yield using base mediated elimination and the structure was determined using X-ray analysis
(See SI).
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To get insight into the mechanism, an H-D scrambling experiment was performed using 1a in
the presence of D2O as a co-solvent, and 47% D incorporation was observed, while as using
1a and 2a in the presence of D2O produced 20% D incorporation (Scheme S3). These results
suggest that the migratory insertion of alkene is faster than H/D exchange and the initial C-H
activation is reversible. In addition, the kinetic isotope experiments for C(7)-H activation
exhibited kH/kD = 1.32 (one-pot) and [PH]/[PD] = 1.20 (parallel) (Scheme S4a-b). Similarly, the
reaction of C(6)-H activation yielded kH/kD = 1.38 (one-pot) and [PH]/[PD] = 1.12 (parallel)
(Scheme S4c-d). These results confide that the C-H bond cleavage might not be involved in
the rate-determining step.Further, the stoichiometric reaction of [Cp*RhCl2]2 with 1a produced
the rhodacycle A in 57% yield (Scheme S5a), whose structure was determined using the single-
crystal X-ray analysis (CCDC 1948961, See SI). The complex A was catalytically competent
to afford 3a in 61% yield (Scheme S5b), suggesting an involvement of the rhodacycle as the
active species in the catalytic cycle (See SI).
Preliminary mechanistic results and literature12 suggest that 2-pyrimidine directed reversible
fast C(7)-H activation can lead to the formation of the rhodacycle A (Scheme 6). Coordination
of A with 2a can give the Rh-species B, which can lead to the migratory insertion to yield C.
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Concomitant activation of the C(6)-H bond can deliver D, which can undergo -N-elimination
to furnish E that may, in turn, undergo reductive elimination to deliver 3 and RhI species.
Oxidation of RhI using CuII can regenerate the active RhIII species to complete the catalytic
cycle.
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Scheme 6. Proposed Reaction Pathway
CuI
N
[Cp*RhL2]
1
CuII
N
N
L=Cl, OAc
Cp*
Cp*RhI
LH
Rh Cl
3
Rh
R
N
*Cp
A
2
N
2-pym
N
E
R
N
N
N
-N-elimination
R
Cp*
N
Rh
*Cp
N
N
Rh
N
Rh
B
Cp*
N
D
R
N
2-pym
LH
L
C
In summary, we have developed a Rh-catalyzed two-fold C-7 and C-6 functionalization of
indolines with 7-azabenzonorbornadienes to produce pyrrolocarbazoles. The site-selectivity,
substrate scope and functional group diversity are important practical features.
EXPERIMENTAL SECTION
General Information. Cu(OAc)2‧H2O (>98%), Cs2CO3 (99%), [Cp*RhCl2]2, AgOAc
(99.99%) and Ag2CO3 (99%) were purchased from Aldrich and used as received. Silica gel-G
plates (Merck) were used for TLC analysis. Melting point was measured on MPB-540 Büchi
melting point apparatus using open capillary tubes and are uncorrected. NMR spectra were
recorded on Bruker 400 MHz and 600 MHz NMR instruments using TMS as an internal
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standard and CDCl3 as a solvent. Mestrenova software was used for the spectral analysis.
Chemical shifts are given in parts per million (δ-scale) and the coupling constants are given in
Hertz. HRMS was carried out using HA273 Q-Tof ESI-MS instrument. Infrared spectra were
recorded on Perkin Elmer FT-IR instrument. Single crystal X‐ray data were collected on a
Bruker SMART APEX equipped with a CCD area detector using Mo/Kα radiation and the
structure was solved by direct method using SHELXL-16 (Göttingen, Germany).
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1-(Pyrimidin-2-yl)indolines 1a-n were synthesized as per reported procedure.13
1
1-(Pyrimidin-2-yl)indoline 1a.13e Yellow liquid; yield 73% (144 mg); H NMR (400 MHz,
CDCl3) δ 8.37 (d, J = 4.8 Hz, 2H), 8.30 (d, J = 8.1 Hz, 1H), 7.15-7.07 (m, 2H), 6.83 (t, J = 7.4
Hz, 1H), 6.55 (t, J = 4.8 Hz, 1H), 4.12 (t, J = 8.7 Hz, 2H), 3.07 (t, J = 8.7 Hz, 2H); HRMS
(ESI-TOF) m/z: [M+H]+ Calcd for C12H12N3 198.1026; Found 198.1026.
4-Allyl-1-(pyrimidin-2-yl)indoline 1b. Yellow solid, yield 67% (159 mg); mp 92-93 C; 1H
NMR (400 MHz, CDCl3) δ 8.49 (d, J = 4.7 Hz, 2H), 8.29 (dd, J = 8.2, 1.0 Hz, 1H), 7.19 (t, J =
7.8 Hz, 1H), 6.79 (dd, J = 7.6, 0.9 Hz, 1H), 6.68 (t, J = 4.7 Hz, 1H), 6.00-5.90 (m, 1H), 5.09-
5.03(m, 2H), 4.25 (dd, J = 9.2, 8.1 Hz, 2H), 3.35 (dt, J = 6.6, 1.6 Hz, 2H), 3.13 (t, J = 8.7 Hz,
13
2H); C{1H} NMR (101 MHz, CDCl3) δ 159.4, 157.6, 143.7, 136.2, 135.8, 131.0, 127.8,
122.2, 115.9, 113.5, 111.5, 48.9, 37.7, 25.9; HRMS (ESI-TOF) m/z: [M+H]+ Calcd for
C15H16N3 238.1339; Found 238.1339.
4-Bromo-1-(pyrimidin-2-yl)indoline 1c. Brown solid; yield 71% (195 mg); mp 114-115 C;
13e 1H NMR (400 MHz, CDCl3) δ 8.47 (d, J = 4.6 Hz, 2H), 8.33 (dd, J = 6.4, 1.9 Hz, 1H), 7.06
(d, J = 6.7 Hz, 2H), 6.70-6.69 (m, 1H), 4.22 (t, J = 8.6 Hz, 2H), 3.14 (t, J = 8.7 Hz, 2H); HRMS
(ESI-TOF) m/z: [M+H]+ Calcd for C12H11BrN3 276.0131; Found 276.0135.
1-(Pyrimidin-2-yl)indoline-4-carbonitrile 1d.Brown solid; yield 59% (131 mg); mp 174-175
C; 1H NMR (400 MHz, CDCl3) δ 8.57 (d, J = 8.2 Hz, 1H), 8.48 (d, J = 4.8 Hz, 2H), 7.26-7.20
(m, 1H), 7.12 (d, J = 7.6 Hz, 1H), 6.74 (t, J = 4.8 Hz, 1H), 4.28 (t, J = 8.8 Hz, 2H), 3.33 (t, J =
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8.8 Hz, 2H); C{1H} NMR (101 MHz, CDCl3) δ 159.0, 157.7, 144.6, 136.8, 128.4, 124.0,
119.2, 117.6, 112.6, 108.8, 48.6, 26.9; HRMS (ESI-TOF) m/z: [M+H]+ Calcd for C13H11N4
223.0978; Found 223.0988.
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4-Methoxy-1-(pyrimidin-2-yl)indoline 1e.13e Colorless solid; yield 64% (145 mg); mp 200-
201 C; 1H NMR (400 MHz, CDCl3) δ 8.48 (d, J = 4.8 Hz, 2H), 8.06 (d, J = 8.0 Hz, 1H), 7.20
(t, J = 8.4 Hz, 1H), 6.67 (t, J = 4.8 Hz, 1H), 6.54 (d, J = 8.4 Hz, 1H), 4.25 (t, J = 8.4 Hz, 2H),
3.86 (s, 3H), 3.12 (t, J = 8.8 Hz, 2H); 13C{1H} NMR (101 MHz, CDCl3) δ 159.3, 157.5, 155.9,
145.1, 128.7, 119.2, 111.5, 108.8, 104.4, 55.4, 49.4, 24.3; HRMS (ESI-TOF) m/z: [M+H]+
Calcd for C13H14N3O 228.1131; Found 228.1134.
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4-Phenyl-1-(pyrimidin-2-yl)indolines 1f. Yellow solid; yield 73% (199 mg); mp 117-118 C
1H NMR (400 MHz, CDCl3) δ 8.52 (d, J = 4.8 Hz, 2H), 8.47 (d, J = 8.1 Hz, 1H), 7.45 (q, J =
7.9 Hz, 4H), 7.39-7.30 (m, 2H), 7.01 (d, J = 7.6 Hz, 1H), 6.71 (t, J = 4.8 Hz, 1H), 4.25 (t, J =
8.6 Hz, 2H), 3.25 (t, J = 8.6 Hz, 2H); 13C{1H} NMR (101 MHz, CDCl3) δ 159.4, 157.6, 144.1,
140.9, 138.6, 130.0, 128.5, 127.9, 127.2, 122.4, 114.3, 111.6, 49.1, 27.3; HRMS (ESI-TOF)
m/z: [M+H]+ Calcd for C18H16N3 274.1339; Found 274.1349.
1
4-(3-Chlorophenyl)-1-(pyrimidin-2-yl)indoline 1g. Brown liquid; yield 69% (212 mg); H
NMR (600 MHz, CDCl3) δ 8.52 (d, J = 4.7 Hz, 2H), 8.46 (d, J = 8.1 Hz, 1H), 7.44 (s, 1H),
7.38-7.35 (m, 1H), 7.34-7.30 (m, 3H), 6.95 (d, J = 7.6 Hz, 1H), 6.72 (t, J = 4.7 Hz, 1H), 4.25
(t, J = 8.6 Hz, 2H), 3.23 (t, J = 8.6 Hz, 2H);13C{1H} NMR (151 MHz, CDCl3) δ 159.4, 157.6,
144.2, 142.7, 137.2, 134.3, 130.0, 129.8, 128.6, 128.1, 127.3, 126.8, 122.2, 114.8, 111.8, 49.10,
27.2; HRMS (ESI-TOF) m/z: [M+H]+ Calcd for C18H15ClN3 308.0949; Found 308.0959.
4-([1,1'-Biphenyl]-4-yl)-1-(pyrimidin-2-yl)indoline 1h. Colorles solid; yield 71% (248 mg);
mp 157-158 C; 1H NMR (400 MHz, CDCl3) δ 8.53 (d, J = 4.8 Hz, 2H), 8.46 (dd, J = 8.2, 1.0
Hz, 1H), 7.68-7.64 (m, 4H), 7.54 (d, J = 8.3 Hz, 2H), 7.47 (t, J = 7.6 Hz, 2H), 7.39-7.32 (m,
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2H), 7.05 (dd, J = 7.7, 1.0 Hz, 1H), 6.72 (t, J = 4.8 Hz, 1H), 4.27 (dd, J = 9.1, 8.0 Hz, 2H), 3.31
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13
(t, J = 8.5 Hz, 2H); C{1H} NMR (101 MHz, CDCl3) δ 157.6, 144.1, 140.9, 140.1, 139.9,
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138.2, 130.1, 128.98, 128.96, 128.0, 127.5, 127.2, 127.3, 122.5, 114.5, 111.7, 49.2, 27.5;
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HRMS (ESI-TOF) m/z: [M+H]+ Calcd for C24H20N3 350.1652; Found 350.1650.
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5-Fluoro-1-(pyrimidin-2-yl)indoline 1i.13e Yellow solid; yield 63% (135 mg); mp 75-76 C;
1H NMR (400 MHz, CDCl3) δ 8.47 (d, J = 4.8 Hz, 2H), 8.33 (dd, J = 8.6, 4.9 Hz, 1H), 6.93-
6.86 (m, 2H), 6.68 (t, J = 4.8 Hz, 1H), 4.25 (t, J = 8.4 Hz, 2H), 3.18 (t, J = 8.6 Hz, 2H); HRMS
(ESI-TOF) m/z: [M+H]+ Calcd for C12H11FN3 216.0932; Found 216.0932.
5-Bromo-1-(pyrimidin-2-yl)indoline 1j.13e Brown solid; yield 65% (179 mg); mp 109-110 C;
1H NMR (400 MHz, CDCl3) δ 8.26 (d, J = 4.8 Hz, 2H), 8.06 (d, J = 8.6 Hz, 1H), 7.08 (d, J =
8.7 Hz, 1H), 7.02 (s, 1H), 6.48 (t, J = 4.7 Hz, 1H), 3.95 (t, J = 8.7 Hz, 2H), 2.89 (t, J = 8.7 Hz,
2H); HRMS (ESI-TOF) m/z: [M+H]+ Calcd for C12H11BrN3 276.0131; Found 276.0130.
5-Methyl-1-(pyrimidin-2-yl)indoline 1k.13e Brown liquid; yield 67% (141 mg); 1H NMR (400
MHz, CDCl3) δ 8.47 (d, J = 4.8 Hz, 2H), 8.28 (d, J = 8.8 Hz, 1H), 7.03 (d, J = 6.8 Hz, 2H),
6.65 (t, J = 4.8 Hz, 1H), 4.22 (d, J = 8.4 Hz, 2H), 3.16 (t, J = 8.4 Hz, 2H), 2.32 (s, 3H); HRMS
(ESI-TOF) m/z: [M+H]+ Calcd for C13H14N3 212.1182; Found 212.1185.
1'-(Pyrimidin-2-yl)spiro[cyclohexane-1,3'-indoline] 1l.13e Brown liquid; yield 46% (122
mg); 1H NMR (400 MHz, CDCl3) δ 8.41 (d, J = 4.8 Hz, 2H), 8.32 (dd, J = 8.1, 1.0 Hz, 1H),
7.17-7.11 (m, 1H), 7.10-7.06 (m, 1H), 6.90-6.87 (m, 1H), 6.59 (t, J = 4.8 Hz, 1H), 4.00 (s, 2H),
1.66 (d, J = 10.5 Hz, 5H), 1.60-1.53 (m, 3H), 1.44 (dd, J = 9.8, 3.4 Hz, 2H); HRMS (ESI-TOF)
m/z: [M+H]+ Calcd for C17H20N3 266.1652; Found 266.1666.
1-(Pyrimidin-2-yl)-1,2-dihydrobenzo[cd]indole 1m. Brown solid; yield 49% (114 mg); mp
129-130 C; 1H NMR (400 MHz, CDCl3) δ 8.58 (d, J = 4.8 Hz, 2H), 8.06 (d, J = 7.4 Hz, 1H),
7.63 (d, J = 8.2 Hz, 1H), 7.52-7.46 (m, 2H), 7.32 (dd, J = 7.6, 3.2 Hz, 2H), 6.80 (t, J = 4.8 Hz,
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1H), 5.46 (s, 2H); 13C{1H} NMR (101 MHz, CDCl3) δ 159.0, 157.9, 144.0, 136.1, 131.7, 129.6,
127.9, 123.0, 117.2, 116.5, 112.4, 108.5, 55.7; HRMS (ESI-TOF) m/z: [M+H]+ Calcd for
C15H12N3 234.1026; Found 234.1037.
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N-Methyl-N-phenylpyrimidin-2-amine 1n.13d Yellow liquid; yield 86% (159 mg); 1H NMR
(400 MHz, CDCl3) δ 8.34 (d, J = 4.8 Hz, 2H), 7.42 (t, J = 7.8 Hz, 2H), 7.32 (d, J = 7.3 Hz,
2H), 7.27-7.21 (m, 1H), 6.57 (t, J = 4.8 Hz, 1H), 3.53 (s, 3H); HRMS (ESI-TOF) m/z: [M+H]+
Calcd for C11H12N3 186.1026; Found 186.1044.
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9-(Pyrimidin-2-yl)-9H-carbazoles 4a-b and 2,3-diethyl-1-(pyrimidin-2-yl)-1H-indole 4c
prepared as per literature.13f
9-(Pyrimidin-2-yl)-9H-carbazoles 4a. Colorless solid; yield 79% (194 mg); mp 112-113 C;
1H NMR (400 MHz, CDCl3) δ 8.88 (d, J = 8.4 Hz, 2H), 8.81 (d, J = 4.8 Hz, 2H), 8.10 (d, J =
7.7 Hz, 2H), 7.57-7.50 (m, 2H), 7.43-7.37 (m, 2H), 7.07 (t, J = 4.8 Hz, 1H); HRMS (ESI-TOF)
m/z: [M+H]+ Calcd for C16H12N3 246.1026; Found 246.1045.
3-Bromo-9-(pyrimidin-2-yl)-9H-carbazole 4b. Colorless solid; yield 74% (239 mg); mp 157-
158 C; 1H NMR (400 MHz, CDCl3) δ 8.87 (d, J = 3.6 Hz, 1H), 8.83 (d, J = 4.4 Hz, 2H), 8.77
(d, J = 8.8 Hz, 1H), 8.17 (d, J = 2.4 Hz, 1H), 8.02 (d, J = 7.6 Hz, 1H), 7.57 (dd, J = 8.8, 2.0
Hz, 1H), 7.55-7.51 (m, 1H), 7.40-7.36 (m, 1H), 7.14 (t, J = 4.8 Hz, 1H); HRMS (ESI-TOF)
m/z: [M+H]+ Calcd for C16H11BrN3 324.0131; Found 324.0151.
2,3-Diethyl-1-(pyrimidin-2-yl)-1H-indole 4c. Yellow liquid; yield 69% (173 mg); 1H NMR
(600 MHz, CDCl3) δ 8.79 (d, J = 4.8 Hz, 2H), 8.22 (d, J = 7.6 Hz, 1H), 7.55 (d, J = 7.9 Hz,
1H), 7.23-7.19 (m, 2H), 7.12 (t, J = 4.8 Hz, 1H), 3.19 (q, J = 7.4 Hz, 2H), 2.79 (q, J = 7.6 Hz,
2H), 1.28 (t, J = 7.6 Hz, 3H), 1.11 (t, J = 7.4 Hz, 3H); HRMS (ESI-TOF) m/z: [M+H]+ Calcd
for C16H18N3 252.1495; Found 252.1513.
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1-(Pyrimidin-2-yl)-1,2,3,4-tetrahydroquinoline was prepared as per literature.13e
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1-(Pyrimidin-2-yl)-1,2,3,4-tetrahydroquinoline 4d. Yellow liquid; yield 87% (184 mg); 1H
NMR (400 MHz, CDCl3) δ 8.41 (d, J = 4.7 Hz, 2H), 7.76 (d, J = 8.2 Hz, 1H), 7.16 (dd, J =
17.1, 7.8 Hz, 2H), 7.04-6.98 (m, 1H), 6.66 (t, J = 4.7 Hz, 1H), 4.07-4.01 (m, 2H), 2.80 (t, J =
6.6 Hz, 2H), 2.02 (p, J = 6.5 Hz, 2H); HRMS (ESI-TOF) m/z: [M+H]+ Calcd for C13H16N3
212.1182; Found 212.1201.
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10-(Pyrimidin-2-yl)-10H-phenothiazine 4e. Phenothiazine (1.5 mmol, 298.5 mg), 2-
bromopyrimidine (2.25 mmol, 355.5 mg), PCy3 (7 mol %, 21.8 mg), NaOtBu (3.75 mmol,
360.4 mg) and Pd2(dba)3 (5 mol %, 68.7 mg) were stirred in toluene (10 ml) at 110 °C in a
preheated oil-bath for 24 h. The reaction mixture was cooled to room temperature and the
solvent was evaporated. The residue was purified on silica gel column chromatography using
1:9 ethyl acetate and hexane to give the title compound. Green solid; yield 59% (163 mg); mp
211-212 C; 1H NMR (400 MHz, CDCl3) 8.38 (d, J = 4.7 Hz, 2H), 7.76 (dd, J = 8.1, 1.4 Hz,
2H), 7.44 (dd, J = 7.8, 1.5 Hz, 2H), 7.36 (td, J = 7.7, 1.5 Hz, 2H), 7.21 (td, J = 7.6, 1.4 Hz, 2H),
6.77 (t, J = 4.7 Hz, 1H; 13C{1H} NMR (101 MHz, CDCl3) δ 160.3, 157.9, 140.1, 133.5, 128.7,
128.2, 126.6, 126.2, 113.9; HRMS (ESI-TOF) m/z: [M+H]+ Calcd for C16H12N3S 278.0746;
Found 278.0750.
1-(3,4-Dihydro-2H-pyrrol-5-yl)indoline,13b 1-(pyridin-2-yl)indoline,13a 1-(indolin-1-yl)ethan-
1-one,13b
1-(indolin-1-yl)-2,2-dimethylpropan-1-one13d
and
N,N-dimethylindoline-1-
carboxamide were prepared as per literature and the data were accordance with literature.
1-(3,4-Dihydro-2H-pyrrol-5-yl)indoline I. Brown solid; yield 85% (158 mg); mp 186-187
1
C; H NMR (400 MHz, CDCl3) δ 7.54 (d, J = 7.9 Hz, 1H), 7.17-7.07 (m, 2H), 6.84 (t, J = 7.4
Hz, 1H), 4.05 (t, J = 8.7 Hz, 2H), 3.81 (t, J = 7.1 Hz, 2H), 3.12 (t, J = 8.7 Hz, 2H), 2.82 (t, J =
8.1 Hz, 2H), 2.08-1.99 (m, 2H); 13C{1H} NMR (101 MHz, CDCl3) δ 164.2, 144.8, 131.5, 127.4,
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125.0, 121.0, 112.8, 56.7, 49.9, 33.4, 27.8, 23.5; HRMS (ESI-TOF) m/z: [M+H]+ Calcd for
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C12H15N2 187.1230; Found 187.1246.
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1-(Pyridin-2-yl)indoline II. Brown liquid; yield 79% (157 mg); H NMR (400 MHz, CDCl3)
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δ 8.43 (d, J = 2.4 Hz, 1H), 8.33-8.29 (m, 1H), 7.62-7.58 (m, 1H), 7.25 (dd, J = 15.9, 7.4 Hz,
2H), 6.98-6.90 (m, 1H), 6.84-6.79 (m, 1H), 6.78-6.74 (m, 1H), 4.04-3.98 (m, 2H), 3.21 (t, J =
8.5 Hz, 2H); HRMS (ESI-TOF) m/z: [M+H]+ Calcd for C13H13N2 197.1073; Found 197.1093.
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1-(Indolin-1-yl)ethan-1-one III. Brown solid; yield 73% (118 mg); mp 102-103 C; 1H NMR
(400 MHz, CDCl3) δ 8.20 (d, J = 8.0 Hz, 1H), 7.18 (dd, J = 10.6, 7.7 Hz, 2H), 7.00 (t, J = 7.4
Hz, 1H), 4.03 (t, J = 8.5 Hz, 2H), 3.18 (t, J = 8.5 Hz, 2H), 2.21 (s, 3H); HRMS (ESI-TOF) m/z:
[M+H]+ Calcd for C10H12NO 162.0913; Found 162.0934.
1-(Indolin-1-yl)-2,2-dimethylpropan-1-one IV. Brown liquid; yield 75% (152 mg); 1H NMR
(400 MHz, CDCl3) δ 8.17-8.12 (m, 1H), 7.08 (t, J = 6.9 Hz, 2H), 6.91 (t, J = 7.4 Hz, 1H), 4.11
(t, J = 8.2 Hz, 2H), 3.02 (t, J = 8.1 Hz, 2H), 1.28 (s, 9H); HRMS (ESI-TOF) m/z: [M+H]+ Calcd
for C13H18NO 204.1383; Found 204.1400.
N,N-Dimethylindoline-1-carboxamide V. Brown liquid; yield 72% (133 mg); 1H NMR (400
MHz, CDCl3) δ 7.14 -7.03 (m, 2H), 6.89 (d, J = 7.9 Hz, 1H), 6.81 (t, J = 7.4 Hz, 1H), 3.83 (t,
J = 8.2 Hz, 2H), 2.95 (t, J = 8.1 Hz, 2H), 2.87 (s, 6H); HRMS (ESI-TOF) m/z: [M+H]+ Calcd
for C11H15N2O 191.1179; Found 191.1198.
7-Azabenzonorbornadienes 2a-q prepared as per literature.12g
9-((4-Bromophenyl)sulfonyl)-1,4-dihydro-1,4-epiminonaphthalene 2a. Brown solid; yield
1
80% (289 mg); mp 157-158 C; H NMR (400 MHz, CDCl3) δ 7.40 (m, 4H), 7.01 (dd, J = 5.2,
13
3.0 Hz, 2H), 6.86 (s, 2H), 6.80 (dd, J = 5.2, 3.0 Hz, 2H), 5.44 (t, J = 1.5 Hz, 2H); C{1H}
NMR (101 MHz, CDCl3) δ 147.0, 142.7, 137.2, 132.0, 129.8, 127.6, 125.3, 121.5, 67.8; HRMS
(ESI-TOF) m/z: [M+H]+ Calcd for C16H13BrNO2S 361.9845; Found 361.9865.
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9-((4-Bromophenyl)sulfonyl)-6,7-difluoro-1,4-dihydro-1,4-epiminonaphthalene
2b.
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Brown solid; yield 75% (240 mg); mp 178-179 C; 1H NMR (400 MHz, CDCl3) δ 7.51 (d, J =
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8.6 Hz, 2H), 7.45 (d, J = 8.7 Hz, 2H), 6.93-6.85 (m, 4H), 5.42 (t, J = 1.3 Hz, 2H); C{1H}
8
9
NMR (101 MHz, CDCl3) δ 147.4 (dd, J = 249.9, 14.9 Hz), 143.5 (t, J = 4.9 Hz), 142.8, 137.1,
132.19, 129.9, 128.2, 112.2 (t, J = 9.1 Hz), 112.0 (t, J = 9.2 Hz), 67.5; HRMS (ESI-TOF) m/z:
[M+H]+ Calcd for C16H11BrF2NO2S 397.9656; Found 397.9655.
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tert-Butyl-5,8-dimethoxy-1,4-dihydro-1,4-epiminonaphthalene-9-carboxylate 2c. Brown
1
solid; yield 59% (201 mg); mp 129-130 C; H NMR (400 MHz, CDCl3) δ 7.00-6.97 (m, 2H),
6.51 (s, 2H), 5.71-5.69 (m, 2H), 3.76 (s, 6H), 1.37 (s, 9H); 13C{1H} NMR (101 MHz, CDCl3)
δ154.9, 148.1, 147.9, 143.5, 142.2, 136.8, 111.3, 80.4, 64.3, 63.7, 56.4, 28.1; HRMS (ESI-
TOF) m/z: [M+H]+ Calcd for C17H22NO4 304.1543; Found 304.1558.
9-Phenylsulfonyl-1,4-dihydro-1,4-epiminonaphthalene 2d. Brown solid; yield 69% (196
mg); mp 146-147 C; 1H NMR (400 MHz, CDCl3) δ 7.57 (dd, J = 8.4, 1.3 Hz, 2H), 7.42-7.38
(m, 1H), 7.32-7.26 (m, 2H), 7.02 (dd, J = 5.2, 3.0 Hz, 2H), 6.80 (t, J = 1.6 Hz, 2H), 6.76 (dd, J
= 5.2, 3.0 Hz, 2H), 5.46 (t, J = 1.6 Hz, 2H); 13C{1H} NMR (101 MHz, CDCl3) δ 147.2, 142.5,
138.2, 132.5, 128.8, 128.3, 125.2, 121.3, 67.8; HRMS (ESI-TOF) m/z: [M+H]+ Calcd for
C16H14NO2S 284.0740; Found 284.0753.
9-(m-Tolylsulfonyl)-1,4-dihydro-1,4-epiminonaphthalene 2e. Colorless solid; yield 72%
(214 mg); mp 129-130 C; 1H NMR (400 MHz, CDCl3) δ 7.41 (td, J = 4.7, 4.2, 2.0 Hz, 1H),
7.30 (s, 1H), 7.20-7.16 (m, 2H), 7.00 (dd, J = 5.2, 3.0 Hz, 2H), 6.83 (t, J = 1.6 Hz, 2H), 6.75
(dd, J = 5.1, 3.0 Hz, 2H), 5.45 (s, 2H), 2.28 (s, 3H); 13C{1H} NMR (101 MHz, CDCl3) δ 147.2,
142.6, 138.9, 137.8, 133.3, 128.8, 128.7, 125.5, 125.1, 121.3, 67.8, 21.2; HRMS (ESI-TOF)
m/z: [M+H]+ Calcd for C17H16NO2S 298.0896; Found 298.0909.
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9-((3-(Trifluoromethyl)phenyl)sulfonyl)-1,4-dihydro-1,4-epiminonaphthalene
2f.
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Colorless solid; yield 76% (267 mg); mp 115-116 C; 1H NMR (400 MHz, CDCl3) δ 7.73-7.71
(m, 2H), 7.60 (d, J = 7.8 Hz, 1H), 7.41-7.37 (m, 1H), 6.96 (dd, J = 5.1, 3.0 Hz, 2H), 6.93 (t, J
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= 1.7 Hz, 2H), 6.69 (dd, J = 5.2, 3.0 Hz, 2H), 5.47 (t, J = 1.7 Hz, 2H); C{1H} NMR (101
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MHz, CDCl3) δ 146.6, 143.0, 138.9, 131.8 (q, JC-F = 33.3 Hz), 131.59, 131.58, 129.5, 129.0 (q,
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JC-F = 3.6 Hz), 127.3 (q, JC-F = 273.7 Hz), 125.5 (q, JC-F = 4.2 Hz), 125.48, 121.6, 67.8; F
NMR (377 MHz, CDCl3) δ -62.9; HRMS (ESI-TOF) m/z: [M+H]+ Calcd for C17H13F3NO2S
352.0614; Found 352.0624.
9-((4-Chlorophenyl)sulfonyl)-1,4-dihydro-1,4-epiminonaphthalene 2g. Colorless solid;
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yield 84% (266 mg); mp 147-148 C; H NMR (400 MHz, CDCl3) δ 7.47 (d, J = 8.6 Hz, 2H),
7.24 (d, J = 8.6 Hz, 2H), 7.01 (dd, J = 5.1, 3.0 Hz, 2H), 6.86 (t, J = 1.6 Hz, 2H), 6.79 (dd, J =
5.2, 3.0 Hz, 2H), 5.44 (t, J = 1.6 Hz, 2H); 13C{1H} NMR (101 MHz, CDCl3) δ 147.0, 142.7,
139.1, 136.7, 129.8, 129.0, 125.3, 121.5, 67.8; HRMS (ESI-TOF) m/z: [M+H]+ Calcd for
C16H13ClNO2S 318.0350; Found 318.0365.
9-((4-Iodophenyl)sulfonyl)-1,4-dihydro-1,4-epiminonaphthalene 2h. Brown solid; yield
77% (314 mg); mp 168-169 C; 1H NMR (400 MHz, CDCl3) δ 7.62 (d, J = 8.5 Hz, 2H), 7.24
(d, J = 8.5 Hz, 2H), 7.01 (dd, J = 5.2, 2.8 Hz, 2H), 6.86 (t, J = 1.5 Hz, 2H), 6.80 (dd, J = 5.2,
3.0 Hz, 2H), 5.43 (t, J = 1.6 Hz, 2H); 13C{1H} NMR (101 MHz, CDCl3) 147.0, 142.7, 138.0,
137.8, 129.7, 125.3, 121.5, 100.1, 67.8; HRMS (ESI-TOF) m/z: [M+H]+ Calcd for
C16H13INO2S 409.9706; Found 409.9713.
9-Tosyl-1,4-dihydro-1,4-epiminonaphthalene 2i. Colorless solid; yield 73% (217 mg); mp
172-173 C; 1H NMR (400 MHz, CDCl3) δ 7.46 (d, J = 8.3 Hz, 2H), 7.09 (d, J = 8.1 Hz, 2H),
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7.03 (dd, J = 5.1, 3.0 Hz, 2H), 6.81-6.75 (m, 4H), 5.44 (s, 2H), 2.34 (s, 3H); C{1H} NMR
(101 MHz, CDCl3) δ 147.4, 143.4, 142.5, 135.4, 129.5, 128.4, 125.2, 121.3, 67.9, 21.6; HRMS
(ESI-TOF) m/z: [M+H]+ Calcd for C17H16NO2S 298.0896; Found 298.0910.
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9-((4-Methoxyphenyl)sulfonyl)-1,4-dihydro-1,4-epiminonaphthalene 2j. Colorless solid;
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yield 61% (191 mg); mp 127-128 C; H NMR (400 MHz, CDCl3) δ 7.51-7.47 (m, 2H), 7.03
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(dd, J = 5.1, 3.0 Hz, 2H), 6.80-6.75 (m, 6H), 5.42 (t, J = 1.6 Hz, 2H), 3.81 (s, 3H); C{1H}
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NMR (101 MHz, CDCl3) δ 163.0, 147.4, 142.5, 130.4, 129.9, 125.2, 121.3, 114.1, 67.8, 55.7;
HRMS (ESI-TOF) m/z: [M+H]+ Calcd for C17H16NO3S 314.0845; Found 314.0856.
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9-((4-Nitrophenyl)sulfonyl)-1,4-dihydro-1,4-epiminonaphthalene 2k. Brown solid; yield
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90% (296 mg); mp 205-206 C; H NMR (400 MHz, CDCl3) δ 8.07 (d, J = 8.8 Hz, 2H), 7.70
(d, J = 8.8 Hz, 2H), 7.00 (dd, J = 5.0, 3.0 Hz, 2H), 6.93 (s, 2H), 6.73 (dd, J = 5.1, 3.0 Hz, 2H),
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5.49 (s, 2H); C{1H} NMR (101 MHz, CDCl3) δ 146.8, 144.0, 142.9, 130.7, 129.6, 125.5,
123.8, 121.7, 67.9; HRMS (ESI-TOF) m/z: [M+H]+ Calcd for C16H13N2O4S 329.0591; Found
329.0600.
9-((4-(tert-Butyl)phenyl)sulfonyl)-1,4-dihydro-1,4-epiminonaphthalene 2l. Colorless solid;
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yield 68% (230 mg); mp 158-159 C; H NMR (400 MHz, CDCl3) δ 7.47 (d, J = 8.6 Hz, 2H),
7.27 (d, J = 8.7 Hz, 2H), 6.99 (dd, J = 5.1, 3.0 Hz, 2H), 6.90 (t, J = 1.7 Hz, 2H), 6.73 (dd, J =
5.2, 3.0 Hz, 2H), 5.45 (s, 2H), 1.30 (s, 9H); 13C{1H} NMR (101 MHz, CDCl3) 156.2, 147.2,
142.9, 134.8, 128.2, 125.7, 125.1, 121.4, 67.8, 35.1, 31.2; HRMS (ESI-TOF) m/z: [M+H]+
Calcd for C20H22NO2S 340.1366; Found 340.1373.
9-(Naphthalen-2-ylsulfonyl)-1,4-dihydro-1,4-epiminonaphthalene 2m. Brown solid; yield

1
65% (216 mg); mp 173-174 C; H NMR (400 MHz, CDCl3) δ 8.15 (s, 1H), 7.84-7.80 (m,
2H), 7.74 (d, J = 8.7 Hz, 1H), 7.58-7.53 (m, 3H), 6.98 (dd, J = 5.1, 3.1 Hz, 2H), 6.78 (t, J = 1.6
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Hz, 2H), 6.60 (dd, J = 5.2, 3.0 Hz, 2H), 5.52 (t, J = 1.3 Hz, 2H); C{1H} NMR (101 MHz,
CDCl3) δ 147.2, 142.5, 135.2, 134.7, 132.2, 129.8, 129.2, 128.9, 128.8, 127.9, 127.4, 125.0,
123.5, 121.2, 67.9; HRMS (ESI-TOF) m/z: [M+H]+ Calcd for C20H16NO2S 334.0896; Found
334.0911.
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9-(Thiophen-2-ylsulfonyl)-1,4-dihydro-1,4-epiminonaphthalene 2n. Brown solid; yield
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77% (222 mg); mp 173-174 C; H NMR (400 MHz, CDCl3) δ 7.45 (d, J = 6.2 Hz, 1H), 7.22
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(dd, J = 3.7, 1.2 Hz, 1H), 7.09 (dd, J = 5.1, 3.0 Hz, 2H), 6.88 (dd, J = 5.0, 3.8 Hz, 1H), 6.84
(dd, J = 5.2, 3.0 Hz, 2H), 6.77 (t, J = 1.6 Hz, 2H), 5.48 (s, 2H); 13C{1H} NMR (101 MHz,
CDCl3) δ 147.0, 141.6, 138.7, 133.5, 133.0, 127.9, 125.4, 121.4, 68.0; HRMS (ESI-TOF) m/z:
[M+H]+ Calcd for C14H12NO2S2 290.0304; Found 290.0313.
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9-(Methylsulfonyl)-1,4-dihydro-1,4-epiminonaphthalene 2o. Colorless solid; yield 63%
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(139 mg); mp 101-102 C; H NMR (400 MHz, CDCl3) δ 7.29 (dd, J = 5.1, 3.0 Hz, 2H), 7.07
(t, J = 1.6 Hz, 2H), 7.02 (dd, J = 5.2, 3.0 Hz, 2H), 5.47 (t, J = 1.6 Hz, 2H), 2.35 (s, 3H); 13C{1H}
NMR (101 MHz, CDCl3) δ 147.5, 143.2, 125.9, 121.7, 67.7, 39.2; HRMS (ESI-TOF) m/z:
[M+H]+ Calcd for C11H12NO2S 222.0583; Found 222.0595.
Benzyl-1,4-dihydro-1,4-epiminonaphthalene-9-carboxylate 2p. Colorless solid; yield 52%
(144 mg); mp 84-85 C; 1H NMR (400 MHz, CDCl3) δ 7.25-7.15 (m, 7H), 6.89 (dd, J = 5.2,
3.0 Hz, 4H), 5.51 (s, 2H), 4.99 (s, 2H); 13C{1H} NMR (101 MHz, CDCl3) δ 155.4, 148.2, 143.6,
142.7, 136.4, 128.6, 128.2, 127.9, 125.3, 121.3, 121.0, 67.3, 66.4; HRMS (ESI-TOF) m/z:
[M+H]+ Calcd for C18H16NO2 278.1176; Found 278.1174.
tert-Butyl-1,4-dihydro-1,4-epiminonaphthalene-9-carboxylate 2q. Yellow liquid; yield
62% (903 mg); 1H NMR (400 MHz, CDCl3) δ 7.19 (d, 2H), 6.90-6.86 (m, 4H), 5.41 (s, 2H),
1.30 (s, 9H); 13C{1H} NMR (101 MHz, CDCl3) δ 155.2, 148.4, 125.0, 80.7, 28.3; HRMS (ESI-
TOF) m/z: [M+H]+ Calcd for C15H18NO2 244.1332; Found 244.1344.
General Procedure for Synthesis of Pyrrolocarbazoles. 1-(Pyrimidin-2-yl)indoline 1 (0.25
mmol, 1 equiv), 9-((aryl)sulfonyl)-1,4-dihydro-1,4-epiminonaphthalene 2 (0.3 mmol, 1.2
equiv), [Cp*RhCl2]2 (4 mol %, 0.01 mmol, 6.2 mg), Cu(OAc)2·H2O (0.625 mmol, 2.5 equiv,
124.4 mg) and Cs2CO3 (0.25 mmol, 1 equiv, 81.5 mg) were stirred at 110 oC in a preheated oil
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bath for 24 h in (CH2Cl)2 (2 mL, 0.13 M) under nitrogen atmosphere. Progress of the reaction
was monitored using TLC with ethyl acetate and hexane as the eluent. The reaction mixture
was cooled to room temperature, diluted with CH2Cl2 (20 mL) and passed through a short pad
of celite. Evaporation of the solvent gave a residue that was purified on silica gel column
chromatography using n-hexane and ethyl acetate as an eluent to afford analytically pure
functionalized pyrrolocarbazoles.
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6-((4-Bromophenyl)sulfonyl)-1-(pyrimidin-2-yl)-1,2,3,6,6a,12a-hexahydrobenzo[a]
pyrrolo-[2,3-g]carbazole 3a. Brown solid; yield 72% (100 mg); mp 213-214 °C; Rf = 0.28
(1:9 ethyl acetate/hexane); 1H NMR (400 MHz, CDCl3) δ 8.28 (d, J = 4.8 Hz, 2H), 7.92 (d, J
= 7.6 Hz, 1H), 7.57-7.55 (m, 2H), 7.47-7.45 (m, 2H), 7.31 (d, J = 8.0 Hz, 1H), 7.28-7.24 (m,
1H), 7.13 (t, J = 7.6 Hz, 1H), 7.07 (d, J = 8.0 Hz, 1H), 6.84 (d, J = 7.2 Hz, 1H), 6.72 (t, J = 4.8
Hz, 1H), 6.09 (d, J = 10.0 Hz, 1H), 5.57 (d, J = 10.0 Hz, 1H), 5.09 (dd, J = 10.0, 5.6 Hz, 1H),
4.67-4.61 (m, 1H), 4.03 (q, J = 10.0 Hz, 1H), 3.66 (dd, J = 10.4, 6.0 Hz, 1H), 3.29-3.20 (m,
1H), 2.88-2.80 (m, 1H); 13C{1H} NMR (101 MHz, CDCl3) δ 160.6, 157.9, 140.9, 140.0, 136.5,
133.0, 132.5, 131.8, 131.6, 129.0, 128.6, 128.5, 128.2, 127.9, 127.2, 126.6, 126.4, 123.4, 123.0,
116.2, 112.7, 63.6, 51.8, 42.0, 29.0; FT-IR (KBr) 3128, 1630, 1576, 1550, 1400, 1166, 1088,
1014 cm-1; HRMS (ESI-TOF) m/z: [M+H]+ Calcd for C28H22BrN4O2S 557.0641; Found
557.0661.
4-Allyl-6-((4-bromophenyl)sulfonyl)-1-(pyrimidin-2-yl)-1,2,3,6,6a,12a-hexahydrobenzo
[a]-pyrrolo[2,3-g]carbazole 3b. Colorless solid; yield 72% (107 mg); mp 168-169 °C; Rf =
0.29 (1:9 ethyl acetate/hexane); 1H NMR (400 MHz, CDCl3) δ 8.28 (d, J = 4.8 Hz, 2H), 7.92
(d, J = 8.0 Hz, 1H), 7.57 (d, J = 8.8 Hz, 2H), 7.48 (d, J = 8.4 Hz, 2H), 7.28-7.24 (m, 1H), 7.18
(s, 1H), 7.13 (t, J = 7.6 Hz, 1H), 6.84 (d, J = 7.2 Hz, 1H), 6.72 (t, J = 4.8 Hz, 1H), 6.08 (d, J =
10.0 Hz, 1H), 5.95-5.85 (m, 1H), 5.57 (d, J = 10.0 Hz, 1H), 5.10-5.03 (m, 3H), 4.67-4.61 (m,
1H), 4.02 (q, J = 10.4 Hz, 1H), 3.66 (dd, J = 10.0, 6.0 Hz, 1H), 3.31 (d, J = 6.4 Hz, 2H), 3.18-
3.09 (m, 1H), 2.84-2.77 (m, 1H); 13C{1H} NMR (151 MHz, CDCl3) δ 160.7, 157.8, 141.2,
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139.7, 136.7, 135.8, 135.0, 132.4, 131.8, 131.7, 131.5, 129.0, 128.6, 128.5, 128.1, 127.9, 127.1,
126.6, 124.3, 123.2, 116.5, 116.4, 112.6, 63.7, 51.5, 41.9, 37.9, 27.6; FT-IR (KBr) 3130, 1631,
1575, 1400, 1167, 1085, 1066 cm-1. HRMS (ESI-TOF) m/z: [M+H]+ Calcd for C31H26BrN4O2S
597.0954; Found 597.0950.
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4-Bromo-6-((4-bromophenyl)sulfonyl)-1-(pyrimidin-2-yl)-1,2,3,6,6a,12a-hexahydro-
benzo-[a]pyrrolo[2,3-g]carbazole 3c. Brown solid; yield 76% (120 mg); mp 237-238 °C; Rf
= 0.28 (1:9 ethyl acetate/hexane); 1H NMR (400 MHz, CDCl3) δ 8.31 (d, J = 4.4 Hz, 2H), 7.89
(d, J = 7.6 Hz, 1H), 7.60 (d, J = 8.4 Hz, 2H), 7.52 (d, J = 8.4 Hz, 2H), 7.47 (s, 1H), 7.28-7.25
(m, 1H), 7.13 (t, J = 7.2 Hz, 1H), 6.84 (d, J = 7.6 Hz, 1H), 6.77 (t, J = 4.8 Hz, 1H), 6.09 (d, J
= 10.0 Hz, 1H), 5.57 (d, J = 10.0 Hz, 1H), 5.02 (dd, J = 9.6, 5.6 Hz, 1H), 4.61 (t, J = 10.0 Hz,
1H), 4.13-4.03 (m, 1H), 3.59 (dd, J = 10.0, 6.0 Hz, 1H), 3.22-3.13 (m, 1H), 2.88 (dd, J = 16.4,
8.4 Hz, 1H); 13C{1H} NMR (101 MHz, CDCl3) δ 160.4, 157.8, 142.2, 140.5, 136.4, 133.2,
132.5, 131.6, 131.2, 128.9, 128.6, 128.5, 128.3, 128.1, 127.5, 126.7, 125.4, 122.4, 118.7, 117.3,
113.2, 63.8, 50.9, 41.7, 30.5; FT-IR (KBr) 3132, 1736, 1574, 1452, 1401, 1360, 1285, 1231,
1168, 1086 cm-1; HRMS (ESI-TOF) m/z: [M+H]+ Calcd for C28H24Br2N4O2S 634.9746; Found
634.9746.
6-((4-Bromophenyl)sulfonyl)-1-(pyrimidin-2-yl)-1,2,3,6,6a,12a-hexahydrobenzo[a]-
pyrrolo-[2,3-g]carbazole-4-carbonitrile 3d. Yellow solid; yield 46% (67 mg); mp 214-215
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°C; Rf = 0.26 (1:9 ethyl acetate/hexane); H NMR (400 MHz, CDCl3) δ 8.32 (d, J = 4.8 Hz,
2H), 7.88 (d, J = 7.6 Hz, 1H), 7.62-7.60 (m, 2H), 7.53 (s, 1H), 7.50-7.48 (m, 2H), 7.31-7.27
(m, 1H), 7.19-7.15 (m, 1H), 6.87 (d, J = 7.6 Hz, 1H), 6.82 (t, J = 4.8 Hz, 1H), 6.13 (d, J = 10.0
Hz, 1H), 5.61 (d, J = 10.4 Hz, 1H), 5.00 (dd, J = 9.6, 5.6 Hz, 1H), 4.73-4.67 (m, 1H), 4.13 (q,
J = 10.0 Hz, 1H), 3.74-3.70 (m, 1H), 3.43-3.34 (m, 1H), 3.12-3.05 (m, 1H); 13C{1H} NMR
(101 MHz, CDCl3) δ 160.3, 158.0, 142.1, 141.2, 137.9, 136.3, 132.7, 131.5, 130.9, 130.8,
128.94, 128.90, 128.62, 128.57, 128.4, 128.3, 126.9, 121.3, 118.1, 116.9, 113.7, 107.8, 63.7,
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51.5, 42.3, 28.7. FT-IR (KBr) 3129, 2225, 1574, 1400, 1288, 1168, 1067 cm-1; HRMS (ESI-
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TOF) m/z: [M+H]+ Calcd for C29H21BrN5O2S 582.0594; Found 582.0589.
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6-((4-Bromophenyl)sulfonyl)-4-methoxy-1-(pyrimidin-2-yl)-1,2,3,6,6a,12a-hexahydro-
benzo-[a]pyrrolo[2,3-g]carbazole 3e. Colorless solid; yield 80% (117 mg); mp 229-230 °C;
Rf = 0.25 (1:9 ethyl acetate/hexane); 1H NMR (400 MHz, CDCl3) δ 8.28 (d, J = 4.8 Hz, 2H),
7.92 (d, J = 8.0 Hz, 1H), 7.58 (d, J = 8.8 Hz, 2H), 7.49-7.47 (m, 2H), 7.29-7.25 (m, 1H), 7.13
(t, J = 7.6 Hz, 1H), 6.94 (s, 1H), 6.84 (d, J = 7.2 Hz, 1H), 6.71 (t, J = 4.8 Hz, 1H), 6.07 (d, J =
10.0 Hz, 1H), 5.55 (d, J = 10.0 Hz, 1H), 5.07 (dd, J = 9.6, 5.6 Hz, 1H), 4.64-4.58 m, 1H), 4.03
(q, J = 10.8 Hz, 1H), 3.86 (s, 3H), 3.59 (dd, J = 10.0, 6.0 Hz, 1H), 3.13-3.04 (m, 1H), 2.87-
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2.80 (m, 1H); C{1H} NMR (101 MHz, CDCl3) δ 160.7, 157.8, 155.1, 142.1, 140.5, 136.5,
132.4, 131.8, 131.7, 129.0, 128.6, 128.4, 128.1, 127.9, 126.9, 126.6, 123.6, 119.8, 119.0, 112.6,
100.1, 64.0, 55.9, 51.9, 41.5, 26.0; FT-IR (KBr) 3125, 3011, 1630, 1575, 1400, 1169 cm-1;
HRMS (ESI-TOF) m/z: [M+H]+ Calcd for C29H24BrN4O3S 587.0747; Found 587.0751.
6-((4-Bromophenyl)sulfonyl)-4-phenyl-1-(pyrimidin-2-yl)-1,2,3,6,6a,12a-hexahydro-
benzo-[a]pyrrolo[2,3-g]carbazole 3f. Colorless solid; yield 78% (123 mg); mp 245-246 °C;
Rf = 0.28 (1:9 ethyl acetate/hexane); 1H NMR (400 MHz, CDCl3) δ 8.32 (d, J = 4.8 Hz, 2H),
7.98 (d, J = 8.0 Hz, 1H), 7.62 (d, J = 8.4 Hz, 2H), 7.54 (d, J = 8.4 Hz, 2H), 7.41 (q, J = 6.4 Hz,
5H), 7.35-7.28 (m, 2H), 7.16 (t, J = 7.2 Hz, 1H), 6.88 (d, J = 7.2 Hz, 1H), 6.75 (t, J = 4.8 Hz,
1H), 6.13 (d, J = 10.0 Hz, 1H), 5.63 (d, J = 10.0 Hz, 1H), 5.12 (dd, J = 9.6, 5.6 Hz, 1H), 4.68
(t, J = 9.6 Hz, 1H), 3.99 (q, J = 9.2 Hz, 1H), 3.72 (dd, J = 10.0, 6.0 Hz, 1H), 3.43-3.34 (m, 1H),
2.80 (dd, J = 15.6, 7.6 Hz, 1H); 13C{1H} NMR (101 MHz, CDCl3) δ 160.6, 157.9, 141.4, 140.1,
140.0, 137.7, 136.6, 132.5, 131.7, 131.6, 130.8, 129.0, 128.7, 128.5, 128.2, 127.9, 127.5, 127.3,
126.6, 125.3, 122.9, 116.7, 112.6, 63.7, 51.7, 41.9, 29.1; FT-IR (KBr) 3130, 1616, 1574, 1550,
1400, 1168, 1085 cm-1; HRMS (ESI-TOF) m/z: [M+H]+ Calcd for C34H26BrN4O2S 633.0954;
Found 633.0959.
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hydrobenzo[a]pyrrolo[2,3-g]carbazole 3g. Colorless solid; yield 67% (112 mg); mp 252-253
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°C; Rf = 0.27 (1:9 ethyl acetate/hexane); H NMR (400 MHz, CDCl3) δ 8.21 (d, J = 4.8 Hz,
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2H), 7.85 (d, J = 8.0 Hz, 1H), 7.52-7.50 (m, 2H), 7.43-7.40 (m, 2H), 7.31 (s, 1H), 7.26-7.18
(m, 5H), 7.07 (t, J = 7.6 Hz, 1H), 6.78 (d, J = 6.8 Hz, 1H), 6.65 (t, J = 4.8 Hz, 1H), 6.03 (d, J
= 10.0 Hz, 1H), 5.51 (d, J = 10.0 Hz, 1H), 4.99 (dd, J = 9.8, 5.6 Hz, 1H), 4.61-4.55 (m, 1H),
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3.93-3.85 (m, 1H), 3.61-3.57 (m, 1H), 3.32-3.23 (m, 1H), 2.72-2.65 (m, 1H); C{1H} NMR
(151 MHz, CDCl3) δ 160.6, 157.9, 141.8, 141.7, 140.4, 136.7, 136.3, 134.5, 132.5, 131.8,
131.6, 130.8, 129.0, 128.7, 128.6, 128.3, 128.2, 128.0, 127.6, 127.4, 126.8, 126.7, 125.9, 122.7,
116.5, 112.8, 63.8, 51.7, 41.9, 29.0; FT-IR (KBr) 3129, 1634, 1574, 1400, 1167, 1087 cm-1;
HRMS (ESI-TOF) m/z: [M+H]+ Calcd for C34H25BrClN4O2S 667.0565; Found 667.0562.
4-([1,1'-Biphenyl]-4-yl)-6-((4-bromophenyl)sulfonyl)-1-(pyrimidin-2-yl)-1,2,3,6,6a,12a-
hexahydrobenzo[a]pyrrolo[2,3-g]carbazole 3h. Colorless solid; yield 70% (124 mg); mp
241-242 °C; Rf = 0.28 (1:9 ethyl acetate/hexane); 1H NMR (400 MHz, CDCl3) δ 8.32 (d, J =
4.8 Hz, 2H), 7.98 (d, J = 7.6 Hz, 1H), 7.65-7.60 (m, 6H), 7.54-7.44 (m, 7H), 7.36 (t, J = 7.2
Hz, 1H), 7.33-7.29 (m, 1H), 7.17 (t, J = 7.6 Hz, 1H), 6.88 (d, J = 7.2 Hz, 1H), 6.75 (t, J = 4.8
Hz, 1H), 6.14 (d, J = 10.0 Hz, 1H), 5.63 (d, J = 10.4 Hz, 1H), 5.12 (dd, J = 9.6, 5.6 Hz, 1H),
4.70 (t, J = 9.6 Hz, 1H), 4.00 (q, J = 9.2 Hz, 1H), 3.72 (dd, J = 10.0, 6.0 Hz, 1H), 3.48-3.40 (m,
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1H), 2.87 (q, J = 8.0, 7.8 Hz, 1H); C{1H} NMR (101 MHz, CDCl3) δ 160.7, 157.9, 141.5,
140.8, 140.3, 140.3, 139.0, 137.3, 136.7, 132.5, 131.8, 131.7, 130.8, 129.01, 128.95, 128.7,
128.6, 128.2, 128.0, 127.5, 127.3, 127.24, 127.20, 126.7, 125.4, 122.9, 116.6, 112.7, 63.8, 51.8,
41.9, 29.3; FT-IR (KBr) 3128, 1633, 1569, 1550, 1400, 1168, 1072 cm-1; HRMS (ESI-TOF)
m/z: [M+H]+ Calcd for C40H30BrN4O2S 709.1267; Found 709.1288.
6-((4-Bromophenyl)sulfonyl)-1-(pyrimidin-2-yl)-1,6,6a,12a-tetrahydro-2H-spiro[benzo-
[a]-pyrrolo[2,3-g]carbazole-3,1'-cyclohexane] 3l. Colorless solid; yield 55% (86 mg) mp
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243-244 °C; Rf = 0.27 (1:9 ethyl acetate/hexane); 1H NMR (400 MHz, CDCl3) δ 8.29 (d, J =
4.8 Hz, 2H), 7.92 (d, J = 7.6 Hz, 1H), 7.52 (d, J = 8.4 Hz, 2H), 7.42 (d, J = 8.8 Hz, 2H), 7.34
(d, J = 8.0 Hz, 1H), 7.29-7.25 (m, 1H), 7.14 (t, J = 7.6 Hz, 1H), 7.00 (d, J = 7.6 Hz, 1H), 6.85
(d, J = 6.8 Hz, 1H), 6.72 (t, J = 4.8 Hz, 1H), 6.09 (d, J = 9.6 Hz, 1H), 5.56 (d, J = 10.0 Hz, 1H),
5.08 (dd, J = 10.0, 5.6 Hz, 1H), 4.68 (d, J = 11.2 Hz, 1H), 3.70-3.63 (m, 2H), 1.81-1.74 (m,
3H), 1.64 (t, J = 11.6 Hz, 2H), 1.46 (t, J = 11.2 Hz, 2H), 1.35-1.26 (m, 3H); 13C{1H} NMR
(101 MHz, CDCl3) δ 160.9, 157.9, 142.5, 141.0, 139.1, 136.4, 132.3, 131.8, 131.7, 129.0,
128.7, 128.5, 128.2, 127.9, 127.1, 126.6, 126.3, 123.1, 121.2, 116.4, 112.6, 63.5, 61.5, 45.3,
42.0, 37.1, 36.0, 25.7, 23.5, 23.0; FT-IR (KBr) 3128, 1631, 1576, 1548, 1400, 1167, 1088,
1068, 1019 cm-1; HRMS (ESI-TOF) m/z: [M+H]+ Calcd for C33H30BrN4O2S 625.1267; Found
625.1282.
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6-((4-Bromophenyl)sulfonyl)-8,9-difluoro-1-(pyrimidin-2-yl)-1,2,3,6,6a,12a-hexahydro-
benzo[a]pyrrolo[2,3-g]carbazole 3o. Colorless solid; yield 71% (105 mg); mp 253-254 °C;
Rf = 0.24 (1:9 ethyl acetate/hexane); 1H NMR (600 MHz, CDCl3) δ 8.28 (d, J = 4.8 Hz, 2H),
7.74 (dd, J = 10.8, 8.4 Hz, 1H), 7.57 (d, J = 8.4 Hz, 2H), 7.45 (d, J = 8.4 Hz, 2H), 7.31 (d, J =
7.8 Hz, 1H), 7.10 (d, J = 7.8 Hz, 1H), 6.74 (t, J = 4.8 Hz, 1H), 6.64 (dd, J = 10.8, 7.8 Hz, 1H),
5.97 (d, J = 10.2 Hz, 1H), 5.46 (d, J = 10.2 Hz, 1H), 5.12 (dd, J = 9.6, 5.4 Hz, 1H), 4.67-4.63
(m, 1H), 4.05 (q, J = 11.4 Hz, 1H), 3.64 (dd, J = 10.2, 6.0 Hz, 1H), 3.29-3.23 (m, 1H), 2.87
(dd, J = 15.6, 8.4 Hz, 1H); 13C{1H} NMR (151 MHz, CDCl3) δ 160.5, 157.9, 150.8 (dd, J =
12.6, 10.0 Hz), 149.2 (dd, J = 21.0, 9.4 Hz), 140.5, 140.0, 136.1, 133.2, 132.5, 128.9, 128.7
(dd, J = 6.3, 3.6 Hz), 128.5 (t, J = 4.1 Hz), 128.1, 125.7, 125.3, 123.9, 123.7, 118.0 (d, J = 19.1
Hz), 116.1, 115.0 (d, J = 17.8 Hz), 112.8, 62.9, 51.7, 41.5, 28.9; 19F NMR (377 MHz, CDCl3)
δ -137.2, -137.3, -139.5, -139.6; FT-IR (KBr) 3130, 1576, 1548, 1400, 1310, 1167, 1085 cm-1;
HRMS (ESI-TOF) m/z: [M+H]+ Calcd for C28H20BrF2N4O2S 593.0453; Found 593.0453.
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tert-Butyl-7,10-dimethoxy-1-(pyrimidin-2-yl)-2,3,6a,12a-tetrahydrobenzo[a]pyrrolo[2,3-
g]carbazole-6(1H)-carboxylate 3p. Thick liquid; yield 46% (57 mg); Rf = 0.23 (1:9 ethyl
acetate/hexane); 1H NMR (400 MHz, CDCl3) δ 8.42 (d, J = 4.8 Hz, 2H), 7.41 (d, J = 8.0 Hz,
1H), 7.04 (d, J = 8.0 Hz, 1H), 6.77 (d, J = 8.8 Hz, 1H), 6.72 (d, J = 9.2 Hz, 2H), 6.66 (t, J = 4.8
Hz, 1H), 5.71 (d, J = 7.6 Hz, 1H), 5.52 (dd, J = 10.0, 3.2 Hz, 1H), 4.60 (dd, J = 5.2, 2.4 Hz,
1H), 4.55-4.49 (m, 1H), 4.19 (q, J = 9.6 Hz, 1H), 3.83 (s, 3H), 3.75 (s, 3H), 3.22-3.13 (m, 1H),
2.98-2.91 (m, 1H), 1.32 (s, 9H); 13C{1H} NMR (101 MHz, CDCl3) δ 159.7, 157.7, 153.4, 149.3,
144.2, 139.5, 129.0, 127.0, 123.7, 123.0, 121.2, 121.1, 120.1, 112.2, 112.1, 111.3, 111.0, 80.2,
57.3, 56.4, 56.3, 52.2, 43.1, 29.8, 28.6, 28.4; FT-IR (KBr) 3131, 1690, 1633, 1579, 1552, 1460,
1400, 1328, 1259, 1158 cm-1; HRMS (ESI-TOF) m/z: [M+H]+ Calcd for C29H31N4O4 499.2340;
Found 499.2356.
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6-(Phenylsulfonyl)-1-(pyrimidin-2-yl)-1,2,3,6,6a,12a-hexahydrobenzo[a]pyrrolo[2,3-
g]carb-azole 3q. Brown solid; yield 43% (51 mg); mp 196-197 °C; Rf = 0.25 (1:9 ethyl
acetate/hexane); 1H NMR (400 MHz, CDCl3) δ 8.21 (d, J = 4.8 Hz, 2H), 7.97 (d, J = 7.6 Hz,
1H), 7.65-7.59 (m, 3H), 7.42 (t, J = 7.6 Hz, 2H), 7.34 (d, J = 8.0 Hz, 1H), 7.29-7.27 (m, 1H),
7.13 (t, J = 7.2 Hz, 1H), 7.07 (d, J = 8.4 Hz, 1H), 6.84 (d, J = 6.4 Hz, 1H), 6.67 (t, J = 4.8 Hz,
1H), 6.09 (d, J = 9.6 Hz, 1H), 5.61 (d, J = 10.4 Hz, 1H), 5.07 (dd, J = 10.0, 5.6 Hz, 1H), 4.65-
4.60 (m, 1H), 4.06-3.98 (m, 1H), 3.67 (dd, J = 10.4, 6.0 Hz, 1H), 3.29-3.20 (m, 2H), 2.88-2.81
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(m, 1H); C{1H} NMR (151 MHz, CDCl3) δ 160.6, 157.7, 141.1, 139.9, 137.8, 132.6, 131.9,
131.8, 129.2, 128.7, 128.5, 128.1, 127.5, 127.2, 126.6, 126.5, 126.4, 123.3, 123.2, 116.1, 112.5,
63.5, 51.7, 42.0, 29.0; FT-IR (KBr) 3129, 1633, 1400, 1163, 1091 cm-1. HRMS (ESI-TOF)
m/z: [M+H]+ Calcd for C28H23N4O2S 479.1536; Found 479.1551.
1-(Pyrimidin-2-yl)-6-(m-tolylsulfonyl)-1,2,3,6,6a,12a-hexahydrobenzo[a]pyrrolo[2,3-g]-
carbazole 3r. Yellow solid; yield 51% (63 mg); mp 228-229 °C; Rf = 0.28 (1: 9 ethyl
acetate/hexane); 1H NMR (400 MHz, CDCl3) δ 8.21 (d, J = 4.8 Hz, 2H), 7.96 (d, J = 7.8 Hz,
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1H), 7.43 (t, J = 8.0 Hz, 1H), 7.40 (d, J = 11.6 Hz, 1H), 7.32 (dd, J = 8.0, 3.2 Hz, 2H), 7.28-
7.24 (m, 2H), 7.13 (t, J = 7.6 Hz, 1H), 7.08 (d, J = 7.6 Hz, 1H), 6.84 (d, J = 5.6 Hz, 1H), 6.68
(t, J = 4.8 Hz, 1H), 6.08 (d, J = 9.6 Hz, 1H), 5.57 (d, J = 10.4 Hz, 1H), 5.08 (dd, J = 10.0, 5.6
Hz, 1H), 4.67-4.61 (m, 1H), 4.07-3.99 (m, 1H), 3.66 (dd, J = 10.0, 5.6 Hz, 1H), 3.28-3.19 (m,
1H), 2.88-2.82 (m, 1H), 2.26 (s, 3H); 13C{1H} NMR (151 MHz, CDCl3) δ 160.7, 157.6, 141.4,
139.8, 139.3, 137.7, 133.4, 132.5, 132.1, 131.8, 129.0, 128.8, 128.5, 128.0, 128.0, 127.2, 126.5,
126.5, 124.7, 123.3, 116.1, 112.5, 63.5, 51.8, 42.1, 29.0, 21.5; FT-IR (KBr) 3129, 1631, 1400,
1159 cm-1; HRMS (ESI-TOF) m/z: [M+H]+ Calcd for C29H25N4O2S 493.1693; Found
493.1705.
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1-(Pyrimidin-2-yl)-6-((3-(trifluoromethyl)phenyl)sulfonyl)-1,2,3,6,6a,12a-hexahydro-
benzo-[a]pyrrolo[2,3-g]carbazole 3s. Colorless solid; yield 63% (86 mg); mp 220-221 °C; Rf
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= 0.26 (1:9 ethyl acetate/hexane); H NMR (400 MHz, CDCl3) ) δ 8.19 (d, J = 4.8 Hz, 2H),
7.93 (d, J = 8.0 Hz, 1H), 7.81 (t, J = 8.4 Hz, 3H), 7.55 (t, J = 8.0 Hz, 1H), 7.34 (d, J = 8.0 Hz,
1H), 7.30-7.28 (m, 1H), 7.15 (t, J = 7.6 Hz, 1H), 7.10 (d, J = 7.6 Hz, 1H), 6.85 (d, J = 7.2 Hz,
1H), 6.68 (t, J = 4.8 Hz, 1H), 6.09 (d, J = 10.4 Hz, 1H), 5.67 (d, J = 10.0 Hz, 1H), 5.07 (dd, J
= 10.0, 5.6 Hz, 1H), 4.66-4.60 (m, 1H), 4.07-4.00 (m, 1H), 3.70 (dd, J = 10.4, 6.0 Hz, 1H),
3.27-3.18 (m, 1H), 2.88-2.82 (m, 1H);13C{1H} NMR (151 MHz, CDCl3) δ 160.4, 157.6, 140.6,
140.0, 138.6, 133.2, 132.1 (q, JC-F = 33.2 Hz), 131.7, 131.4, 130.7, 129.8, 129.3 (q, JC-F = 3.4
Hz), 128.7, 128.5, 128.2, 127.1, 126.6, 125.94 (q, JC-F = 271.2 Hz), 125.90, 124.5 (q, JC-F = 3.7
Hz), 123.5, 123.0, 115.8, 112.6, 63.7, 51.8, 42.0, 28.9; 19F NMR (377 MHz, CDCl3) δ -62.87.
FT-IR (KBr) 3129, 1609, 1578, 1553, 1462, 1400, 1326, 1168, 1133, 1104 cm-1; HRMS (ESI-
TOF) m/z: [M+H]+ Calcd for C29H22F3N4O2S 547.1410; Found 547.1419.
6-((4-Chlorophenyl)sulfonyl)-1-(pyrimidin-2-yl)-1,2,3,6,6a,12a-hexahydrobenzo[a]-
pyrrolo-[2,3-g]carbazole 3t. Colorless solid; yield 69% (59 mg); mp 240-241 °C; Rf = 0.28
(1: 9 ethyl acetate/hexane); 1H NMR (400 MHz, CDCl3) δ 8.27 (d, J = 4.8 Hz, 2H), 7.92 (d, J
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= 7.6 Hz, 1H), 7.55 (d, J = 8.4 Hz, 2H), 7.41 (d, J = 8.4 Hz, 2H), 7.31 (d, J = 8.0 Hz, 1H), 7.29-
7.25 (m, 1H), 7.13 (t, J = 7.2 Hz, 1H), 7.07 (d, J = 7.6 Hz, 1H), 6.84 (d, J = 7.2 Hz, 1H), 6.72
(t, J = 4.8 Hz, 1H), 6.09 (d, J = 9.6 Hz, 1H), 5.57 (d, J = 10.0 Hz, 1H), 5.09 (dd, J = 10.0, 5.6
Hz, 1H), 4.67-4.61 (m, 1H), 4.04 (q, J = 9.6 Hz, 1H), 3.65 (dd, J = 10.4, 6.0 Hz, 1H), 3.29-3.20
(m, 1H), 2.88-2.82 (m, 1H); 13C{1H} NMR (101 MHz, CDCl3) δ 160.6, 157.8, 141.0, 140.0,
139.5, 136.1, 133.0, 131.8, 131.7, 129.5, 129.0, 128.7, 128.6, 128.2, 127.3, 126.7, 126.4, 123.5,
123.0, 116.3, 112.7, 63.6, 51.8, 42.1, 29.0; FT-IR (KBr) 3125, 1719, 1631, 1577, 1400, 1166,
1088 cm-1; HRMS (ESI-TOF) m/z: [M+H]+ Calcd for C28H22ClN4O2S 513.1147; Found
513.1161.
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6-((4-Iodophenyl)sulfonyl)-1-(pyrimidin-2-yl)-1,2,3,6,6a,12a-hexahydrobenzo[a]pyrrolo-
[2,3-g]carbazole 3u. Colorless solid; yield 67% (101 mg); mp 246-247 °C; Rf = 0.29 (1: 9
ethyl acetate/hexane); 1H NMR (600 MHz, CDCl3) δ 8.30 (d, J = 4.8 Hz, 2H), 7.92 (d, J = 7.8
Hz, 1H), 7.78 (d, J = 8.4 Hz, 2H), 7.30 (t, J = 8.4 Hz, 3H), 7.27 (d, J = 8.4 Hz, 1H), 7.13 (t, J
= 7.2 Hz, 1H), 7.07 (d, J = 7.8 Hz, 1H), 6.84 (d, J = 7.2 Hz, 1H), 6.74 (t, J = 4.8 Hz, 1H), 6.09
(d, J = 10.2 Hz, 1H), 5.56 (d, J = 10.2 Hz, 1H), 5.09 (dd, J = 9.6, 5.4 Hz, 1H), 4.64 (t, J = 9.6
Hz, 1H), 4.04 (q, J = 10.2 Hz, 1H), 3.67 (dd, J = 10.2, 5.4 Hz, 1H), 3.28-3.22 (m, 1H), 2.85
(dd, J = 15.6, 9.0 Hz, 1H); 13C{1H} NMR (101 MHz, CDCl3) δ 160.6, 157.9, 140.9, 140.0,
138.4, 137.3, 132.9, 131.7, 131.6, 128.8, 128.6, 128.5, 128.1, 127.2, 126.6, 126.3, 123.4, 123.0,
116.1, 112.6, 100.3, 63.5, 51.7, 42.0, 28.9; FT-IR (KBr) 3129, 1573, 1546, 1400, 1163, 1087
cm-1; HRMS (ESI-TOF) m/z: [M+H]+ Calcd for C28H22IN4O2S 605.0503; Found 605.0513.
1-(Pyrimidin-2-yl)-6-tosyl-1,2,3,6,6a,12a-hexahydrobenzo[a]pyrrolo[2,3-g]carbazole 3v.
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Yellow solid; yield 54% (66 mg); mp 230-231 °C; Rf = 0.28 (1:9 ethyl acetate/hexane); H
NMR (600 MHz, CDCl3) δ 8.20 (d, J = 4.2 Hz, 2H), 7.96 (d, J = 7.8 Hz, 1H), 7.52 (d, J = 8.4
Hz, 2H), 7.32 (d, J = 9.6 Hz, 1H), 7.27 (d, J = 8.4 Hz, H), 7.22 (d, J = 8.0 Hz, 2H), 7.12 (t, J =
7.8 Hz, 1H), 7.06 (d, J = 7.8 Hz, 1H), 6.83 (d, J = 7.2 Hz, 1H), 6.68 (t, J = 4.8 Hz, 1H), 6.08
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(d, J = 10.2 Hz, 1H), 5.60 (d, J = 10.2 Hz, 1H), 5.08 (dd, J = 10.2, 6.0 Hz, 1H), 4.65-4.61 (m,
1H), 4.02 (q, J = 10.2 Hz, 1H), 3.74 (dd, J = 10.2, 6.0 Hz, 1H), 3.27-3.21 (m, 1H), 2.84 (dd, J
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= 15.0, 9.0 Hz, 1H), 2.42 (s, 3H); C{1H} NMR (151 MHz, CDCl3) δ 160.7, 157.6, 143.4,
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141.3, 139.8, 135.1, 132.5, 132.1, 131.8, 129.7, 128.8, 128.5, 128.0, 127.6, 127.2, 126.5, 126.4,
123.4, 123.3, 116.2, 112.4, 63.4, 51.7, 42.1, 28.9, 21.8; FT-IR (KBr) 3129, 1631, 1571, 1544,
1400, 1163, 1091 cm-1; HRMS (ESI-TOF) m/z: [M+H]+ Calcd for C29H25N4O2S 493.1693;
Found 493.1703.
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6-((4-Methoxyphenyl)sulfonyl)-1-(pyrimidin-2-yl)-1,2,3,6,6a,12a-hexahydrobenzo[a]
pyrrolo[2,3-g]carbazole 3w. Colorless solid; yield 58% (74 mg); mp 233-234 °C; Rf = 0.26
(1:9 ethyl acetate/hexane); 1H NMR (600 MHz, CDCl3) δ 8.22 (d, J = 4.8 Hz, 2H), 7.95 (d, J
= 7.8 Hz, 1H), 7.55 (d, J = 9.0 Hz, 2H), 7.31 (d, J = 8.4 Hz, 1H), 7.27 (d, J = 5.4 Hz, 1H), 7.12
(t, J = 7.8 Hz, 1H), 7.06 (d, J = 7.8 Hz, 1H), 6.89 (d, J = 8.4 Hz, 2H), 6.83 (d, J = 7.2 Hz, 1H),
6.69 (t, J = 4.8 Hz, 1H), 6.08 (d, J = 10.2 Hz, 1H), 5.56 (d, J = 10.2 Hz, 1H), 5.09 (dd, J = 9.6,
5.4 Hz, 1H), 4.65-4.61 (m, 1H), 4.02 (q, J = 10.8 Hz, 1H), 3.82 (s, 3H), 3.68 (dd, J = 10.2, 6.0
Hz, 1H), 3.27-3.21 (m, 1H), 2.84 (dd, J = 15.6, 8.4 Hz, 1H); 13C{1H} NMR (151 MHz, CDCl3)
δ 163.2, 160.6, 157.7, 141.4, 139.8, 132.5, 132.1, 131.7, 129.5, 129.3, 128.7, 128.5, 128.0,
127.1, 126.6, 126.5, 123.2, 123.2, 116.4, 114.4, 112.5, 63.3, 55.7, 51.7, 42.0, 29.0; FT-IR (KBr)
3130, 1632, 1595, 1400, 1260, 1155, 1091, 1021 cm-1; HRMS (ESI-TOF) m/z: [M+H]+ Calcd
for C29H25N4O3S 509.1642; Found 509.1648.
6-((4-Nitrophenyl)sulfonyl)-1-(pyrimidin-2-yl)-1,2,3,6,6a,12a-hexahydrobenzo[a]-
pyrrolo-[2,3-g]carbazole 3x. Yellow solid; yield 70% (91 mg); mp 237-238 °C; Rf = 0.24 (1:9
ethyl acetate/hexane); 1H NMR (400 MHz, CDCl3) δ 8.25-8.23 (m, 2H), 8.15 (d, J = 4.8 Hz,
2H), 7.91 (d, J = 8.0 Hz, 1H), 7.81-7.79 (m, 2H), 7.33 (d, J = 7.6 Hz, 1H), 7.30-7.26 (m, 1H),
7.15 (t, J = 7.2 Hz, 1H), 7.10 (d, J = 7.6 Hz, 1H), 6.85 (d, J = 7.6 Hz, 1H), 6.68 (t, J = 4.8 Hz,
1H), 6.10 (d, J = 10.0 Hz, 1H), 5.65 (d, J = 10.0 Hz, 1H), 5.06 (dd, J = 10.0, 5.6 Hz, 1H), 4.67-
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4.61 (m, 1H), 4.04 (q, J = 11.2 Hz, 1H), 3.70 (dd, J = 10.0, 5.6 Hz, 1H), 3.30-3.21 (m, 1H),
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2.90-2.83 (m, 1H); C{1H} NMR (101 MHz, CDCl3) δ 160.5, 157.6, 150.4, 143.4, 140.4,
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140.1, 131.7, 131.2, 128.7, 128.62, 128.61, 128.4, 127.3, 126.7, 125.8, 124.2, 123.6, 122.7,
115.8, 112.8, 63.8, 51.8, 42.0, 28.9; FT-IR (KBr) 3129, 1632, 1573, 1528, 1400, 1167, 1087
cm-1; HRMS (ESI-TOF) m/z: [M+H]+ Calcd for C28H22N5O4S 524.1387; Found 524.1391.
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6-((4-(tert-Butyl)phenyl)sulfonyl)-1-(pyrimidin-2-yl)-1,2,3,6,6a,12a-hexahydrobenzo[a]-
pyrrolo[2,3-g]carbazole 3y. Colorless solid; yield 55% (73 mg); mp 251-252 °C; Rf = 0.27
(1:9 ethyl acetate/hexane); 1H NMR (600 MHz, CDCl3) δ 8.21 (d, J = 4.2 Hz, 2H), 7.99 (d, J
= 7.2 Hz, 1H), 7.59 (d, J = 9.0 Hz, 2H), 7.44 (d, J = 8.4 Hz, 2H), 7.35 (d, J = 7.8 Hz, 1H), 7.28-
7.25 (m, 1H), 7.13 (t, J = 7.8 Hz, 1H), 7.06 (d, J = 7.8 Hz, 1H), 6.84 (d, J = 7.8 Hz, 1H), 6.64
(t, J = 4.8 Hz, 1H), 6.09 (d, J = 10.2 Hz, 1H), 5.63 (d, J = 10.2 Hz, 1H), 5.10 (dd, J = 10.0, 5.4
Hz, 1H), 4.65-4.62 (m, 1H), 4.03 (q, J = 10.8 Hz, 1H), 3.92 (dd, J = 10.2, 5.4 Hz, 1H), 3.28-
3.22 (m, 1H), 2.85 (dd, J = 15.6, 9.0 Hz, 1H), 1.32 (s, 9H); 13C{1H} NMR (151 MHz, CDCl3)
δ 160.5, 157.6, 156.6, 141.3, 139.8, 135.4, 132.4, 132.1, 131.8, 128.8, 128.5, 128.0, 127.4,
127.2, 126.4, 126.1, 126.0, 123.4, 123.3, 115.9, 112.3, 63.2, 51.6, 42.2, 35.3, 31.4, 28.9; FT-
IR (KBr) 3129, 1577, 1551, 1400, 1166, 1113, 1084 cm-1; HRMS (ESI-TOF) m/z: [M+H]+
Calcd for C32H31N4O2S 535.2162; Found 535.2177.
6-(Naphthalen-2-ylsulfonyl)-1-(pyrimidin-2-yl)-1,2,3,6,6a,12a-hexahydrobenzo[a]-
pyrrolo-[2,3-g]carbazole 3z. Brown solid; yield 52% (69 mg); mp 174-175 °C; Rf = 0.27 (1:9
ethyl acetate/hexane); 1H NMR (600 MHz, CDCl3) δ 8.26 (d, J = 4.8 Hz, 2H), 8.0 (d, J = 7.8
Hz, 1H), 7.89 (d, J = 7.8 Hz, 1H), 7.86 (d, J = 8.4 Hz, 1H), 7.81 (d, J = 8.4 Hz, 1H), 7.64 (t, J
= 7.2 Hz, 2H), 7.55 (t, J = 7.2 Hz, 1H), 7.51 (dd, J = 8.4, 1.2 Hz, 1H), 7.39 (d, J = 7.8 Hz, 1H),
7.28 (t, J = 7.2 Hz, 1H), 7.13 (t, J = 7.2 Hz, 1H), 7.10 (d, J = 7.8 Hz, 1H), 6.82 (d, J = 7.2 Hz,
1H), 6.44 (t, J = 4.8 Hz, 1H), 6.04 (d, J = 10.2 Hz, 1H), 5.68 (d, J = 9.6 Hz, 1H), 4.96 (dd, J =
10.2, 6.0 Hz, 1H), 4.60-4.56 (m, 1H), 3.99 (q, J = 10.8 Hz, 1H), 3.52 (dd, J = 9.6, 5.4 Hz, 1H),
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3.27-3.21 (m, 1H), 2.84 (dd, J = 15.6, 9.0 Hz, 1H); 13C{1H} NMR (151 MHz, CDCl3) δ 160.4,
157.4, 141.2, 139.9, 135.0, 134.9, 132.6, 132.4, 131.9, 131.7, 129.7, 129.1, 128.9, 128.71,
128.67, 128.5, 128.0, 127.8, 127.4, 127.0, 126.5, 126.4, 123.3, 123.1, 122.9, 116.2, 112.2, 63.5,
51.6, 41.9, 28.9; FT-IR (KBr) 3129, 1624, 1576, 1552, 1400, 1161, 1134, 1073 cm-1; HRMS
(ESI-TOF) m/z: [M+H]+ Calcd for C32H25N4O2S 529.1693; Found 529.1705.
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6-(Methylsulfonyl)-1-(pyrimidin-2-yl)-1,2,3,6,6a,12a-hexahydrobenzo[a]pyrrolo[2,3-g]-
carbazole 3ab. Colorless solid; yield 71% (74 mg); mp 249-250 °C; Rf = 0.26 (1:9 ethyl
acetate/hexane); 1H NMR (400 MHz, CDCl3) δ 8.54 (d, J = 4.8 Hz, 2H), 7.86 (d, J = 8.0 Hz,
1H), 7.28-7.25 (m, 1H), 7.21-7.15 (m, 2H), 7.07 (d, J = 8.0 Hz, 1H), 6.91 (d, J = 7.6 Hz, 1H),
6.81 (t, J = 4.4 Hz, 1H), 6.23 (d, J = 10.0 Hz, 1H), 5.84 (d, J = 10.4 Hz, 1H), 5.36 (dd, J = 10.0,
5.6 Hz, 1H), 4.92 (dd, J = 10.4, 5.6 Hz, 1H), 4.75-4.70 (m, 1H), 4.17-4.10 (m, 1H), 3.30-3.21
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(m, 1H), 2.95 (s, 3H), 2.93-2.87 (m, 1H); C{1H} NMR (101 MHz, CDCl3) δ 160.6, 158.0,
140.8, 140.1, 132.6, 132.0, 131.7, 129.0, 128.5, 128.2, 127.4, 126.5, 124.5, 123.7, 123.1, 114.6,
112.8, 63.7, 52.1, 42.7, 36.3, 28.9; FT-IR (KBr) 3126, 2927, 2855, 1637, 1577, 1553, 1400,
1263, 1156 cm-1; HRMS (ESI-TOF) m/z: [M+H]+ Calcd for C23H21N4O2S 417.1380; Found
417.1382.
Benzyl-1-(pyrimidin-2-yl)-2,3,6a,12a-tetrahydrobenzo[a]pyrrolo[2,3-g]carbazol-6(1H)-
yl)-sulfonyl)methanoate 3ac. Yellow solid; yield 66% (78 mg); mp 196-197 °C; Rf = 0.26
(1:9 ethyl acetate/hexane); 1H NMR (600 MHz, CDCl3) δ 8.50 (d, J = 4.8 Hz, 2H), 7.47 (d, J
= 7.2 Hz, 2H), 7.43 (d, J = 1.8 Hz, 1H), 7.35 (t, J = 7.2 Hz, 2H), 7.35 (d, J = 14.6 Hz, 1H), 7.30
(d, J = 4.2 Hz, 1H), 7.12 (t, J = 6.0 Hz, 2H), 6.99 (d, J = 8.4 Hz, 1H), 6.88 (t, J = 4.8 Hz, 1H),
6.76 (t, J = 4.8 Hz, 1H), 6.19 (d, J = 10.2 Hz, 1H), 6.05 (d, J = 10.8 Hz, 1H), 5.41-5.33 (m,
3H), 4.74 (dd, J = 10.2, 5.4 Hz, 1H), 4.67 (t, J = 9.6 Hz, 1H), 4.07 (q, J = 10.8 Hz, 1H), 3.23-
3.17 (m, 1H), 2.82 (dd, J = 15.6, 9.0 Hz, 1H); 13C{1H} NMR (151 MHz, CDCl3) δ 160.9, 158.0,
139.6, 136.3, 133.1, 132.2, 130.3, 128.7, 128.5, 128.4, 128.2, 127.9, 127.5, 127.5, 126.6, 124.0,
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