Rhodium-Catalyzed One-Pot Access to N-Polycyclic Aromatic Hydrocarbons from Aryl Ketones through Triple C-H Bond Activations

Article abstract of DOI:10.1021/acs.joc.0c02582

A Rh-catalyzed pot and step economic synthesis of aza-polycyclic aromatic hydrocarbons (N-PAHs) from readily available aryl ketones and alkynes has been disclosed. Additionally, a novel synthetic application of the well-known aminating reagent hydroxylamine-O-sulfonic acid (HOSA) has been explored as an in situ redox-neutral directing group for the formation of N-PAHs via isoquinoline. Multiple bond formation in a single operation through a cascade of triple C-H bond activations is the beauty of this protocol. The challenging annulations of two different alkynes in a regioselective fashion have been demonstrated effectively. Mechanistic studies reveal that 3,4-diphenyl-1-methylisoquinoline is an active intermediate for this one-pot transformation.

Full text of DOI:10.1021/acs.joc.0c02582

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Article
Rhodium-Catalyzed One-Pot Access to N‑Polycyclic Aromatic
Hydrocarbons from Aryl Ketones through Triple C−H Bond
Activations
Pragati Biswal, Shyam Kumar Banjare, Bedadyuti Vedvyas Pati, Smruti Ranjan Mohanty,
and Ponneri Chandrababu Ravikumar*
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ABSTRACT: A Rh-catalyzed pot and step economic synthesis of aza-polycyclic aromatic hydrocarbons (N-PAHs) from readily
available aryl ketones and alkynes has been disclosed. Additionally, a novel synthetic application of the well-known aminating reagent
hydroxylamine-O-sulfonic acid (HOSA) has been explored as an in situ redox-neutral directing group for the formation of N-PAHs
via isoquinoline. Multiple bond formation in a single operation through a cascade of triple C−H bond activations is the beauty of
this protocol. The challenging annulations of two different alkynes in a regioselective fashion have been demonstrated effectively.
Mechanistic studies reveal that 3,4-diphenyl-1-methylisoquinoline is an active intermediate for this one-pot transformation.
syntheses of N-PAHs. Consequently, developing a straightfor-
ward methodology for the construction of highly conjugated
PAHs is highly desirable.
INTRODUCTION
■
Over the past few decades, synthesis of polycyclic aromatic
hydrocarbons (PAHs) has gained significant attention among
synthetic and material chemists. These compounds have been
extensively employed in optoelectronics and advanced organic
materials, which can be attributed to their structural features.1 It
has been observed that incorporation of heteroatoms such as
boron (B), nitrogen (N), and sulfur (S) into the aromatic
frameworks of PAHs could modulate its electronic properties.2
Particularly, nitrogen-containing PAHs (N-PAHs) have a key
significance in organic electronics because of nitrogen’s
influence on electronic modulation and the role in stabilizing
the PAHs.3 Moreover, nitrogen-atom-containing π-extended
organic compounds are of prominent interest in organic light-
emitting diodes (OLEDs) and organic field-effect transistors
(OFETs).4 Because of the unique electronics of the nitrogen
atom, N-containing compounds are being used as model
synthetic equivalents for nitrogen-doped graphene in current
studies.4d,e Hence, the presence of heterocyclic rings in PAHs
has a dramatic impact on organic solar cells, sensors, field-effect
transistors, and the photophysical properties. Despite much
exploration and advancement in this field, the common issues
involved in this field are complicated and involves multistep
During the past few decades, transition metal-catalyzed
directed C−H bond functionalization has greatly improved
the arsenal of synthetic chemistry by creating an attractive
transformative platform for the construction of complex organic
scaffolds.5 Miura et al. have reported the Rh-catalyzed synthesis
of polyarylated naphthyl- and anthrylazoles en route to the
cleavage of multiple C−H bonds by taking N-phenylazoles and
diarylalkynes as reacting partners.6a Likewise, Jioa and co-
workers have disclosed the synthesis of polyarylated naph-
thylamides and isoquinolinone derivatives from benzamides and
alkynes.6b Very recently, Dong et al. have addressed the
synthesis of azahelicenes from N-phenyl-7-azaindole, which
has significant applications in photophysics.6c Moreover, the
Received: October 30, 2020
https://dx.doi.org/10.1021/acs.joc.0c02582
© XXXX American Chemical Society
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A

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Figure 1. Transition metal-catalyzed oxidative annulation reactions with alkyne.
Ackerman group has developed a rhoda-electrocatalyzed
synthesis of N-PAHs enabled by cascade of C−H activations.6d
In addition, the use of redox-neutral directing groups is of
current interest in the synthetic community. Such method-
ologies contribute greatly toward green synthesis, as it obviates
the use of extra metal oxidants.7
In transition metal-catalyzed C−H bond activation, various
types of redox-neutral directing groups have been well
documented for different transformations.8 In this context,
possibility of using acetophenone and alkyne for the synthesis of
polyarylated aromatic hydrocarbons in a one-pot strategy
through a cascade of triple C−H bond activations (Figure
1b). Salient features of this methodology includes (i) pot as well
as step economic synthesis, (ii) a novel application of obscure
redox-neutral directing group HOSA, (iii) cascade of triple C−
H bond functionalization, and (iv) four C−C and two C−N
bond formations in single reactor.
RESULTS AND DISCUSSION
isoquinoline synthesis has been depicted by taking different
■
preinstalled redox-neutral directing groups with Rh, Co, Ru, and
Ir (Figure 1a).9 Although there are several reports on the
synthesis of isoquinolines employing redox-neutral strategy with
preformed imines, the synthesis of N-PAHs is limited to only
one report (Figure 1a).10 Thus, development of a simpler
protocol to achieve complex value-added scaffolds is highly
desirable in synthetic organic chemistry.
In this context, a pot economy protocol is being considered as
an efficient approach in synthetic organic chemistry. One-pot
synthesis is a promising green approach to contemporary
synthesis because it minimizes the steps, pursues multiple new
bond formations in a single operation, addresses the waste of
chemicals, and more importantly minimizes wasteful efforts.11 In
our previous work, we documented the synthetic application of
the well-known aminating reagent hydroxylamine-O-sulfonic
acid (HOSA) as a new redox-neutral directing group for the one-
pot synthesis of isoquinolines from readily available aryl
ketones.8f In our continuous pursuit to expand our stockpile
of new synthetic applications of HOSA, we envisaged the
We commenced our investigation by taking acetophenone (1a),
diphenylacetylene (2a) as model substrate, and HOSA as N-
transfer reagent (Table 1). To our delight, a preliminary attempt
with 5 mol % of (1,2,3,4,5-pentamethylcyclopentadienyl
rhodium(III) chloride dimer {[Cp*RhCl2]2}, 50 mol % of
AgOAc as additive, and 2 equiv of Cu(OAc)2 as oxidant in 1 mL
of MeOH at 70 °C afforded 30% isolated yield of the desired
product 3aa along with 12% of 4aa (Table 1, entry 1). Addition
of 1 equiv of AgOAc lowered the overall yields. As addition of
extra additive gave lower yield of 3aa (entry 2), we presumed
that lowering the additive loading for the first annulation step
could improve the yields. To our delight, when the oxidant
Cu(OAc)2 was added after the complete conversion of
acetophenone (5 h) to isoquinoline (4aa), we obtained 21%
of 3aa along with improved yield of isoquinoline 4aa to 57%,
which is the active starting material for the second and third C−
H bond activations (Table 1, entry 3). Next, we moved to screen
the reaction at different temperatures (Table 1, entries 4−6).
From these screenings, 110 °C was found to be the optimal
B
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a b
,
Table 1. Optimization of Reaction Conditions
b
entry
catalyst
[Cp*Rh(Cl)2]2
additive
AgOAc
oxidant
temp and time
(3aa/4aa)
1
2
3
4
5
6
7
8
9
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2 (1)
Cu(OAc)2 (1.5)
Cu(OAc)2 (2.5)
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
−
70 °C, 12 h
70 °C, 12 h
70 °C, 12 h
100 °C, 12 h
110 °C, 12 h
120 °C, 12 h
110 °C, 12 h
110 °C, 12 h
110 °C, 12 h
110 °C, 18 h
110 °C, 18 h
110 °C, 18 h
110 °C, 18 h
110 °C, 18 h
110 °C, 18 h
110 °C, 18 h
110 °C, 18 h
110 °C, 18 h
110 °C, 18 h
30/12
25/14
21/57
27/22
61/11
34/18
23/60
46/37
55/trace
71/trace
21/nd
nd/50
nd/nd
11/67
nd/nd
nd/nd
nd/nd
trace/85
nd/nd
[Cp*Rh(Cl)2]2
[Cp*Rh(Cl)2]2
[Cp*Rh(Cl)2]2
[Cp*Rh(Cl)2]2
[Cp*Rh(Cl)2]2
[Cp*Rh(Cl)2]2
[Cp*Rh(Cl)2]2
[Cp*Rh(Cl)2]2
[Cp*Rh(Cl)2]2
[Cp*Rh(Cl)2]2
[Cp*Rh(Cl)2]2
[Cp*Rh(Cl)2]2
[Cp*Rh(CH3CN)3][SbF6]2
[Cp*Co(CO)I2
[RuCl2(p-cymene)]2
[Cp*Rh(Cl)2]2
[Cp*Rh(Cl)2]2
−
AgOAc (100 mol %)
AgOAc
AgOAc
AgOAc
AgOAc
AgOAc
AgOAc
AgOAc
AgOAc
AgOAc
AgOAc
AgOAc
−
c
c
c
c
c
c
c
cd
,
10
11
12
13
14
15
16
17
18
19
ce
,
c,f
cg
,
c
c
c
c
c
c
AgOAc
AgOAc
−
AgOAc
AgOAc
Cu(OAc)2
a
Reaction conditions: 1a (0.10 mmol), 2a (0.45 mmol), HOSA (0.11 mmol), catalyst (5 mol %), AgOAc (50 mol %), solvent (0.1 M), temp (°C),
b
c
12 h. NMR yields by using 1,3,5-trimethoxybenzene as internal standard. Reactions were heated at 70 °C for 5 h without Cu(OAc)2, and then
Cu(OAc)2 was added followed by stirring. Isolated yield. DCE as the solvent. CH3CN as the solvent. TFE as the solvent. nd = not detected.
d
e
f
g
temperature (Table 1, entry 5). A few conditions were screened
to know the influence of oxidant equivalents (Table 1, entries 7−
9). It was observed that increasing or lowering the equivalents of
oxidant did not improve the yield of 3aa.
also worked smoothly with thiomethyl and trifluoromethyl
groups, delivering 57% yields of 3da and 3ea, respectively.
Delightfully, substrates with easily transformable halo groups, F,
Br, and I, also behaved smoothly under the reaction conditions,
giving moderate to good yields of 3fa, 3ga, 3ha, and 3ja. This
protocol was found compatible with a free hydroxy substituent,
affording 78% of 3la. To make more conjugated molecules, we
examined this protocol with 4-phenylacetophenone and 1-
acetylnaphthalene, which delivered their respective products
3ma and 3na in good yields.
Acetophenone having a dioxolane ring reacted in a completely
regioselective fashion, yielding 3oa in 31% yield. It is noteworthy
that heteroaromatic aryl ketones such as furan, thiophene, and
indole delivered their respective products 3pa, 3qa, and 3ra in
moderate to very good yields. It is worth mentioning that the
unsymmetrical ketones 1i, 1j, 1l, and 1o underwent annulation
in a regioselective manner, delivering their respective products
3ia, 3ja, 3la, and 3oa. Pleasingly, when 1-tetralone was subjected
to the standard reaction condition, 55% of the corresponding N-
PAH (3sa) was isolated. A variety of carbonyl compounds
obtained by the replacement of the methyl group of
acetophenone (1t, 1u, 1v, 1w, and 1x) were also investigated
for the formation of N-PAHs under the standard reaction
conditions. Of these carbonyl compounds, propiophenone (1u)
was only successful in providing the desired N-PAHs (3ua). To
extend the generality of this protocol, various disubstituted
alkynes were investigated. Diaryl alkynes such as 4,4′-
dichlorodiphenylacetylene (2b) afforded the corresponding
annulated product 3cb in moderate yield. In contrast, the
alkynes having electron-donating groups such as Me and OMe
are very less reactive and produced 3ac and 3ad, respectively, in
A better yield of 3aa was observed on increasing the reaction
time to 18 h with almost total consumption of the starting
material (entry 10). The reaction failed to produce better results
when we attempted to replace MeOH by DCE, CH3CN, and
TFE (Table 1, entries 11−13). The replacement of catalytic
system [Cp*RhCl2]2 and AgOAc with cationic rhodium catalyst
[Cp*Rh(CH3CN)3][SbF6]2 had a deleterious impact on the
reaction, resulting in only 11% of 3aa (Table 1, entry 14).
Similarly, attempts to replace the catalyst [Cp*RhCl2]2 by
[Cp*Co(CO)I2] and [RuCl2(p-cymene)]2 resulted in complete
loss of reactivity (Table 1, entries 15 and 16). Next, to check the
influence of [Cp*RhCl2]2, AgOAc and Cu(OAc)2 on the
reaction, three control experiments were carried out (Table 1,
entries 17−19). The reaction did not furnish isoquinoline 4aa in
the absence of silver additive (Table 1, entry 17). This indicates
that AgOAc is playing a major role to make the active catalyst
Cp*Rh(OAc)2. Moreover, the presence of Cu(OAc)2 is also
essential as oxidant to regenerate the catalyst (Table 1, entry
18). Similarly, we did not observe the formation of 3aa in the
absence of [Cp*RhCl2]2 (Table 1, entry 19).
With the acquired optimized reaction conditions, we started
examining various substituted acetophenones. We were pleased
to see that this protocol is quite general with many structurally
and electronically diverse compounds. Acetophenone bearing
electron-donating groups such as p-Me, p-OMe, m-Me, and o-
OMe afforded good to excellent yields of the respective
annulated product (Scheme 1, 3ba, 3ca, 3ia, 3ka). The protocol
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a b
,
Scheme 1. Evaluation of Aryl Ketones for One-Pot Synthesis of N-Polycyclic Aromatic Hydrocarbons
a
Reaction conditions: 1a (0.10 mmol), 2a (0.45 mmol), HOSA (0.11 mmol), [Cp*RhCl2]2 (5 mol %), AgOAc (50 mol %), MeOH (0.1 M), 70−
b
c
110 °C, 12−18 h. Isolated yields. Isolated yield of 1 mmol scale reaction.
trace amounts. Taking advantage of the sequential addition of
different alkynes, we hypothesized to construct unsymmetrical
annulated products by using two different types of alkynes (alk-1
and alk-2). Gratifyingly, when 1a was reacted with 2b and 2a, it
delivered 50% of 3ae. In a similar vein, we were able to construct
3af and 3cf in 53% and 43% yields, respectively. Unfortunately,
D
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terminal alkynes failed to produce 3ag and 3ah under the
standard reaction conditions. Further, to show the synthetic
utility of this protocol, a 1 mmol scale reaction was performed,
which gave 65% of 3aa (Scheme 1).
Scheme 3. Proposed Catalytic Cycle
To gain mechanistic insight, we have performed few control
experiments. When 1-methyl-3,4-diphenylisoquinoline (4aa)
was subjected to the standard reaction conditions, it afforded
92% of 3aa (Scheme 2a). This indicates that formation of 3aa is
Scheme 2. Mechanistic and Kinetic Experiments
known amination reagent HOSA has been used here as N-
transfer reagent, thus exploring the synthetic applications of this
aminating reagent. Control experiments and mechanistic studies
clarify the role of each reagent and details of the mechanism.
This methodology tolerates a wide range of functional groups
including a free hydroxy (OH) group, showing the importance
of this protocol. Moreover, the easily synthesizable, highly
arylated N-PAH products could be applicable in optoelec-
tronics. We expect that this synthetic protocol could gain the
attention of synthetic and material chemists significantly.
EXPERIMENTAL SECTION
■
General Information.8f Acetophenone derivatives were bought
from Sigma-Aldrich, Alfa-Aesar, Avra, TCI, and Spectrochem and used
without any further purification. For column chromatography, silica gel
(230−400 mesh) from Acme Co. was used. A gradient elution using
distilled hexane and ethyl acetate was performed, based on Merck
aluminum TLC sheets. All isolated compounds were characterized by
1H NMR and 13C NMR spectroscopy (Bruker-400 MHz) and HRMS.
going through intermediate 4aa. To understand the catalytic
activity, a few kinetic experiments were conducted (Scheme 2b−
d). No H/D scrambling could be confirmed at the ortho-
position of acetophenone 1a when the standard reaction was
carried out with CD3OD in the absence or presence of a
coupling partner (Scheme 2b,c). Moreover, a kinetic isotope
effect (KIE) for the intermolecular kinetic experiment was found
to be 5.6 (Scheme 2d). All these experiments indicate that the
Rh-catalyzed C−H activation step might be involved in the rate-
limiting step.12
A plausible mechanism has been proposed for the formation
of 3aa based on the performed mechanistic experiments and
previous literature reports (Scheme 3).8f,10 At first, active
rhodium catalyst A is generated from [Cp*RhCl2]2 and AgOAc,
which then undergoes cyclometalation irreversibly with in situ-
generated arylmethyl imine 1, giving cyclometalated species B.
The coordination and insertion of alkyne into the C−Rh bond of
B gave C, followed by cyclization in a redox-neutral manner to
give the annulated product D. The catalyst activates the second
C−H bond directed by the coordinating N atom from
isoquinoline. Subsequent insertion of 2 equiv of alkyne led to
intermediates F and G. Intermediate G undergoes reductive
elimination, affording 3aa and Cp*Rh(I) catalyst, which is again
reoxidized by Cu(II) salt, to participate in the next catalytic
cycle.
1
Copies of the H NMR, 13C NMR, and 19F NMR can be found in
Supporting Information. Nuclear magnetic resonance spectra were
recorded on a Bruker 400 MHz instrument. HRMS signal analysis was
performed using micro a TOF Q-II mass spectrometer. X-ray analysis
was conducted using a Rigaku Smartlab X-ray diffractometer in our
institute. All 1H NMR experiments were reported in parts per million
(ppm) and were measured relative to the signals for residual chloroform
(7.26 ppm) in the deuterated solvent. All 13C NMR spectra were
reported in ppm relative to CDCl3 (77.36 ppm). Chemical shift
multiplicities are represented as follows: s = singlet, d = doublet, t =
triplet, q = quartet, m = multiplet, dd = doublet of doublet, dt = doublet
of triplet, td = tripet of doublet. The starting materials 2b,13 2c,13 2d,13
acetophenone-d5,14 and 4aa8f were prepared by following the reported
procedure.
General Procedure for Rhodium-Catalyzed Annulation
Reaction (A). To an oven-dried 25 mL Schlenk tube, charged with a
magnetic stirring bar, were added dry MeOH (0.1 M, 1 mL), aryl
ketone (0.1 mmol, 1 equiv), and HOSA (0.11 mmol, 1.1 equiv)
sequentially under nitrogen atmosphere. To this solution were added
alkyne (0.45 mmol, 4.5 equiv), [Cp*RhCl2]2(0.005 mmol, 0.05 equiv),
and AgOAc (0.05 mmol, 0.5 equiv). Then the reaction mixture was
stirred (500 rpm) at 70 °C in a preheated aluminum block for 5−7 h.
The reaction was monitored by TLC. After complete conversion of aryl
ketone to corresponding isoquinoline, the reaction mixture was allowed
to attain ambient temperature. To the above reaction mixture was
added Cu(OAc)2 (0.2 mmol, 2 equiv) under nitrogen atmosphere and
CONCLUSION
■
In summary, highly arylated N-PAHs have been synthesized in a
one-pot strategy from readily available aryl ketones and alkynes
through a cascade of three C−H bond activations. The well-
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again heated at 110 °C in a preheated aluminum block for 12−20 h. The
reaction was monitored by TLC. After complete conversion, the
reaction mixture was transferred in to a 50 mL round-bottom flask. The
reaction vial was washed two to three times with ethyl acetate (10−15
mL). The solvent was removed under reduced pressure to obtain a
crude mixture which was extracted with ethyl acetate (3 × 10 mL) and
saturated sodium bicarbonate (10 mL). The organic layer was dried
over anhydrous Na2SO4 and then purified through column
chromatography by using 230−400 mesh silica, giving 46 mg (71%)
of 3aa.
General Procedure for Rhodium-Catalyzed Annulation
Reaction (B). To an oven-dried 25 mL Schlenk tube, charged with a
magnetic stirring bar, were added dry MeOH (0.1 M, 1 mL), aryl
ketone (0.11 mmol, 1.1 equiv), and HOSA (0.12 mmol, 1.2 equiv)
sequentially under nitrogen atmosphere. To this solution were added
alkyne-1 (0.1 mmol, 1 equiv), [Cp*RhCl2]2(0.005 mmol, 0.05 equiv),
and AgOAc (0.05 mmol, 0.5 equiv). Then the reaction mixture was
stirred (500 rpm) at 70 °C in a preheated aluminum block for 5−7 h.
The reaction was monitored by TLC. After complete conversion of aryl
ketone to the corresponding isoquinoline, the reaction mixture was
allowed to attain ambient temperature. To the above reaction mixture
was added alkyne-2 (0.35 mmol, 3.5 equiv) and Cu(OAc)2 (0.2 mmol,
2 equiv) under nitrogen atmosphere and again heated at 110 °C in a
preheated aluminum block for 12−20 h. The reaction was monitored
by TLC. After complete conversion, the reaction mixture was
transferred in to a 50 mL round-bottom flask. The reaction vial was
washed two to three times with ethyl acetate (10−15 mL). The solvent
was removed under reduced pressure to obtain a crude mixture which
was extracted with ethyl acetate (3 × 10 mL) and saturated sodium
bicarbonate (10 mL). The organic layer was dried over anhydrous
Na2SO4 and then purified by column chromatography using 230−400
mesh silica, giving the corresponding N-PAHs.
General Procedure for a 1 mmol Scale Reaction To
Synthesize 3aa. To an oven-dried 25 mL Schlenk tube, charged
with a magnetic stirring bar, were added dry MeOH (0.1 M, 10 mL),
aryl ketone (1 mmol, 1 equiv), and hydroxylamine-O-sulfonic acid (1.1
mmol, 1.1 equiv) sequentially under nitrogen atmosphere. To this
solution were added alkyne (4.5 mmol, 4.5 equiv), [Cp*RhCl2]2 (0.05
mmol, 0.05 equiv), and AgOAc (0.5 mmol, 0.5 equiv). Then the
reaction mixture was stirred (500 rpm) at 70 °C in a preheated
aluminum block for 5 h. The reaction was monitored by TLC. After
complete conversion of aryl ketone to the corresponding isoquinoline,
the reaction mixture was allowed to attain ambient temperature. To the
above reaction mixture was added Cu(OAc)2 (2 mmol, 2 equiv) under
nitrogen atmosphere and again heated at 110 °C in a preheated
aluminum block for 18 h. The reaction was monitored by TLC. After
complete conversion, the reaction mixture was transferred to a 50 mL
round-bottom flask. The reaction vial was washed two to three times
with ethyl acetate (20−30 mL). The solvent was removed under
reduced pressure to afford a crude mixture which was extracted with
ethyl acetate (3 × 10 mL) and saturated sodium bicarbonate (10 mL).
The organic layer was dried over anhydrous Na2SO4 and then purified
by column chromatography using 230−400 mesh silica, giving 422 mg
(65%) of 3aa.
1-Methyl-4-phenyl-3-(5,6,7,8-tetraphenylnaphthalen-1-yl)-
isoquinoline (3aa).10 Prepared according to general procedure A. The
crude reaction mixture was purified by column chromatography, giving
a pale brown solid (45 mg) in 71% yield; mp 143−145 °C; Rf = 0.2
(10% EtOAc/hexane); 1H NMR (CDCl3, 400 MHz): δ 7.92−7.90 (m,
1H), 7.45−7.38 (m, 6H), 7.26−7.20 (m, 4H), 7.17−7.11 (m, 4H), 7.02
(t, J = 8.0 Hz, 2H), 6.91−6.88 (m, 1H), 6.85−6.82 (m, 1H), 6.79−6.66
(m, 9H), 6.54 (d, J = 4.0 Hz, 2H), 6.47 (t, J = 8.0 Hz, 1H), 6.12 (t, J =
8.0 Hz, 1H), 2.76 (s, 3H); 13C{1H} NMR (CDCl3, 100 MHz): δ 156.3,
141.1, 141.0, 140.9, 140.3 (2C), 138.5, 138.4, 137.9, 135.4, 133.6,
133.5, 132.2, 131.7, 131.6 (2C), 131.5, 131.4 (2C), 131.3, 131.2, 130.6,
130.4, 127.7, 127.6, 127.5, 127.4, 126.7 (2C), 126.6, 126.4, 126.3,
126.1, 126.0, 125.9, 125.5, 125.4, 125.3, 125.2, 124.8, 124.6, 22.3; IR
(KBr, cm−1): 3056, 2870, 1602, 1441; HRMS (ESI) m/z: [M + H]+
calcd for C50H36N 650.2842; found 650.2878.
1,6-Dimethyl-4-phenyl-3-(5,6,7,8-tetraphenylnaphthalen-1-yl)-
isoquinoline (3ba).10 Prepared according to general procedure A. The
crude reaction mixture was purified by column chromatography, giving
a brown solid (40 mg) in 60% yield; mp 173−175 °C; Rf = 0.3 (10%
EtOAc/hexane); 1H NMR (CDCl3, 400 MHz): δ 7.80 (d, J = 8.0 Hz,
1H), 7.41−7.38 (m, 3H), 7.27 (d, J = 8.0 Hz, 2H), 7.23−7.19 (m, 4H),
7.16−7.10 (m, 4H), 7.02 (t, J = 8.0 Hz, 2H), 6.92 (t, J = 8.0 Hz, 1H),
6.85−6.83 (m, 1H), 6.79−6.77 (m, 3H), 6.74−6.67 (m, 6H), 6.53−
6.48 (m, 3H), 6.13 (t, J = 8.0 Hz, 1H), 2.72 (s, 3H), 2.36 (s, 3H);
13C{1H} NMR (CDCl3, 100 MHz): δ 156.0, 141.1 (2C), 141.0, 140.3,
140.2, 138.5, 138.3, 137.9, 135.6, 133.6, 133.4, 132.3, 131.7, 131.6
(2C), 131.5, 131.4, 131.3, 131.2, 130.6, 130.4, 128.5, 127.8, 127.5,
127.3, 127.2, 126.7 (2C), 126.6, 126.5, 126.4, 126.1, 125.5, 125.4, 125.2
(2C), 124.9, 124.8, 124.6, 124.3, 22.3, 22.1; IR (KBr, cm−1): 3054,
2868, 1600, 1440.
6-Methoxy-1-methyl-4-phenyl-3-(5,6,7,8-tetraphenylnaphtha-
len-1-yl)isoquinoline (3ca).10 Prepared according to general proce-
dure A. The crude reaction mixture was purified by column
chromatography, giving a pale yellow solid (65 mg) in 95% yield; mp
144−146 °C; Rf = 0.2 (20% EtOAc/hexane); 1H NMR (CDCl3, 400
MHz): δ 7.77 (d, J = 8.0 Hz, 1H), 7.39−7.34 (m, 3H), 7.21−7.16 (m,
4H), 7.10 (q, J = 8.0 Hz, 4H), 7.03−6.99 (m, 3H), 6.91−6.87 (m, 1H),
6.83−6.79 (m, 1H), 6.75−6.73 (m, 3H), 6.70−6.62 (m, 7H), 6.53−
6.48 (m, 3H), 6.16 (t, J = 8.0 Hz, 1H), 3.64 (s, 3H), 2.67 (s, 3H);
13C{1H} NMR (CDCl3, 100 MHz): δ 160.4, 155.6, 141.0 (2C), 140.9,
140.3, 140.2, 138.5, 138.2, 137.9, 137.8, 137.3, 133.6, 133.4, 132.2,
131.6, 131.4 (2C), 131.3 (2C), 131.1, 130.6, 130.2, 127.7, 127.6, 127.5,
127.4, 127.2, 126.7, 126.6 (2C), 126.4, 126.0, 125.4 (2C), 125.1, 124.9,
124.6, 121.6, 118.3, 104.4, 55.4, 22.2; IR (KBr, cm−1): 3055, 2868,
1618, 1441, 1028.
1-Methyl-6-(methylthio)-4-phenyl-3-(5,6,7,8-tetraphenylnaph-
thalen-1-yl)isoquinoline (3da). Prepared according to general
procedure A. The crude reaction mixture was purified by column
giving a pale yellow solid (40 mg) in 57% yield; mp 145−147 °C; Rf =
0.2 (10% EtOAc/hexane); 1H NMR (CDCl3, 400 MHz): δ 7.78 (d, J =
8.0 Hz, 1H), 7.43−7.38 (m, 3H), 7.29 (dd, J = 8.0 Hz, 4 Hz, 1H), 7.25−
7.21 (m, 4H), 7.17−7.10 (m, 5H), 7.03−6.98 (m, 2H), 6.91 (t, J = 8.0
Hz, 1H), 6.87−6.83 (m, 1H), 6.79−6.67 (m, 9H), 6.56−6.50 (m, 3H),
6.18 (t, J = 8.0 Hz, 1H), 2,69 (s, 3H), 2.32 (s, 3H). 13C{1H} NMR
(CDCl3, 100 MHz): δ 156.0, 152.7, 141.1, 141.0, 140.9, 140.2 (2C),
139.2, 138.5, 138.3, 137.8, 137.4, 135.7, 133.6, 133.4, 132.2, 131.6,
131.5, 131.4 (2C), 131.3 (2C), 131.1, 130.6, 130.3, 128.4, 127.7, 127.6,
127.5, 127.3, 127.2, 126.7 (2C), 126.5, 126.4, 126.0, 125.6, 125.5,
125.4, 125.2, 125.0, 124.9, 124.6, 123.5, 120.3, 22.2, 15.1; IR (KBr,
cm−1): 3055, 2837, 1601, 1440; HRMS (ESI) m/z: [M + H]+ calcd for
C51H38NS 696.2719; found 696.2690.
1-Methyl-4-phenyl-3-(5,6,7,8-tetraphenylnaphthalen-1-yl)-6-
(trifluoromethyl)isoquinoline (3ea).10 Prepared according to general
procedure A. The crude reaction mixture was purified by column
chromatography, giving a pale yellow solid (25 mg) in 57% yield; mp
119−121 °C; Rf = 0.3 (10% EtOAc/hexane); 1H NMR (CDCl3, 400
MHz): δ 8.02 (d, J = 8.8 Hz, 1H), 7.76 (s, 1H), 7.62 (dd, J = 8.4 Hz, 1.2
Hz, 1H), 7.45 (dd, J = 8.4 Hz, 1.2 Hz, 1H),7.40−7.36 (m, 2H), 7.30−
7.11 (m, 9H), 7.04 (d, J = 7.2 Hz, 1H), 6.99 (d, J = 7.6 Hz, 1H), 6.89 (t,
J = 7.6 Hz, 1H), 6.85−6.82 (m, 1H), 6.78−6.76 (m, 2H), 6.74−6.66
(m, 6H), 6.56−6.52 (m, 2H), 6.47 (t, J = 7.6 Hz, 1H), 6.13 (t, J = 7.6
Hz, 1H), 2.78 (s, 3H); 13C{1H} NMR (CDCl3, 100 MHz): δ 156.5,
153.6, 141.1, 141.0, 140.8, 140.6, 140.2, 138.8, 138.7, 138.6, 137.7,
136.5, 134.7, 133.8, 133.6, 132.1, 131.6 (2C), 131.5, 131.4, 131.3,
131.1, 131.0, 130.7, 130.3, 130.0, 127.9, 127.8, 127.7, 127.6 (2C),
127.2, 126.9 (q, JC−F = 270.8 Hz), 126.8, 126.6 (2C), 126.5, 126.1,
125.6, 125.5, 125.3, 125.0, 124.6, 123.8 (q, JC−F = 4.0 Hz), 121.9 (q,
J
C−F = 2.9 Hz), 22.5; 19F NMR (CDCl3, 376 MHz): δ −62.7; IR (KBr,
cm−1): 3057, 2852, 1601, 1441, 1311.
6-Fluoro-1-methyl-4-phenyl-3-(5,6,7,8-tetraphenylnaphthalen-
1-yl)isoquinoline (3fa).10 Prepared according to general procedure A.
The crude reaction mixture was purified by column chromatography,
giving a brown solid (30 mg) in 45% yield; mp 135−137 °C; Rf = 0.3
(10% EtOAc/hexane); 1H NMR (CDCl3, 400 MHz): δ 7.94−7.90 (m,
1H), 7.44−7.36 (m, 3H), 7.28 (d, J = 8.0 Hz, 1H), 7.23−7.19 (m, 3H),
F
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7.17−7.12 (m, 5H), 7.06−6.97 (m, 3H), 6.89−6.82 (m, 2H), 6.79−
6.70 (m, 8H), 6.66 (d, J = 8.0 Hz, 1H), 6.59−6.54 (m, 2H), 6.48 (t, J =
8.0 Hz, 1H), 6.19−6.16 (m, 1H), 2.73 (s, 3H); 13C{1H} NMR (CDCl3,
100 MHz): δ 163.1 (d, JC−F = 248.0 Hz), 156.2, 153.0, 141.1, 141.0,
140.9, 140.4, 140.2, 139.9, 138.6, 138.4, 137.8, 137.3 (d, JC−F = 10.0
Hz), 137.2, 133.7, 133.5, 132.0, 131.6 (2C), 131.5, 131.4 (d, JC−F = 3
Hz), 131.3, 131.2, 130.7, 130.2, 128.3 (2C), 127.8, 127.6 (d, JC−F = 3.0
Hz), 127.5, 126.9, 126.7 (d, JC−F = 3.0 Hz), 126.6 (2C), 126.5, 126.0,
125.5, 125.4, 125.2, 124.9, 124.6, 123.2, 116.3 (d, JC−F = 25 Hz), 109.7
(d, JC−F = 22 Hz), 22.5; 19F NMR (CDCl3, 376 MHz): δ −108.6; IR
(KBr, cm−1): 3055, 2852, 1601, 1400, 1188.
6-Bromo-1-methyl-4-phenyl-3-(5,6,7,8-tetraphenylnaphthalen-
1-yl)isoquinoline (3ga). Prepared according to general procedure A.
The crude reaction mixture was purified by column chromatography,
giving a pale yellow solid (49 mg) in 67% yield; mp 113−115 °C; Rf =
0.3 (10% EtOAc/hexane); 1H NMR (CDCl3, 400 MHz): δ 7.74 (d, J =
8.0 Hz, 1H), 7.55 (d, J = 4.0 Hz, 1H), 7.49 (dd, J = 8.8 Hz, 0.8 Hz, 1H),
7.41−7.36 (m, 2H), 7.35 (dd, J = 6.8 Hz, 0.8 Hz, 1H), 7.28 (d, J = 8 Hz,
1H), 7.20 (dt, J = 7.2 Hz, 2.4 Hz, 3H), 7.13−7.12 (m, 3H), 7.09−7.07
(m, 1H), 7.01−6.96 (m, 2H), 6.89 (t, J = 8.0 Hz, 1H), 6.84−6.80 (m,
1H), 6.76−6.71 (m, 3H), 6.69−6.65 (m, 5H), 6.61 (d, J = 4.0 Hz, 1H),
6.54−6.47 (m, 3H), 6.16 (t, J = 8.0 Hz, 1H), 2.70 (s, 3H); 13C{1H}
NMR (CDCl3, 100 MHz): δ 156.4, 153.2, 141.1, 141.0, 140.8, 140.4,
140.2, 138.8, 138.6, 138.4, 137.7, 136.8, 136.7, 133.7, 133.5, 132.1,
131.6, 131.5, 131.4 (2C), 131.3 (2C), 131.1, 130.6, 130.3, 129.7, 128.2,
127.8, 127.6 (2C), 127.5, 127.1, 127.0, 126.7 (2C), 126.6 (2C), 126.5,
126.1, 125.7, 125.5, 125.2, 125.0, 124.6, 124.3, 22.4; IR (KBr, cm−1):
3056, 2852, 1599, 1441, 652; HRMS (ESI) m/z: [M + H]+ calcd for
C50H35BrN 728.1947; found 728.1949.
6-Iodo-1-methyl-4-phenyl-3-(5,6,7,8-tetraphenylnaphthalen-1-
yl)isoquinoline (3ha). Prepared according to general procedure A. The
crude reaction mixture was purified by column chromatography, giving
a pale yellow solid (48 mg) in 62% yield; mp 117−119 °C; Rf = 0.3
(10% EtOAc/hexane); 1H NMR (CDCl3, 400 MHz): δ 7.82 (d, J = 1.6
Hz, 1H), 7.72 (dd, J = 8.8 Hz, 1.6 Hz, 1H), 7.61 (d, J = 8.8 Hz, 1H), 7.42
(dd, J = 8.4 Hz, 1.2 Hz, 1H), 7.36 (dd, J = 6.8 Hz, 1.6 Hz, 1H), 7.30−
7.28 (m, 1H), 7.23−7.22 (m, 1H), 7.21−7.20 (m, 1H), 7.17−7.14 (m,
2H), 7.13−7.10 (m, 2H), 7.02 (d, J = 7.6 Hz, 1H), 6.98 (td, J = 7.6 Hz,
1.2 Hz, 1H), 6.92−6.88 (m, 1H), 6.86−6.83 (m, 1H), 6.79−6.75 (m,
4H), 6.73−6.66 (m, 7H), 6.54−6.49 (m, 3H), 6.18−6.14 (m, 1H), 2.70
(s, 3H). 13C{1H} NMR (CDCl3, 100 MHz): δ 156.5, 141.1, 141.0,
140.8, 140.4, 140.2, 138.6, 138.4, 137.7, 136.8 (2C), 135.1, 134.8,
133.6, 133.4, 132.1, 131.6 (2C), 131.5 (2C), 131.4, 131.3 (2C), 131.1,
130.6, 130.3, 127.8, 127.7, 127.6, 127.4, 126.9, 126.8, 126.7(2C), 126.6,
126.5, 126.1, 125.7, 125.4, 125.2, 125.0, 124.6, 97.2, 22.2; IR (KBr,
cm−1): 3056, 2856, 1592, 1440, 583; HRMS (ESI) m/z: [M + H]+
calcd for C50H35IN 776.1809; found 776.1793.
1,7-Dimethyl-4-phenyl-3-(5,6,7,8-tetraphenylnaphthalen-1-yl)-
isoquinoline (3ia).10 Prepared according to general procedure A. The
crude reaction mixture was purified by column chromatography, giving
a pale brown solid (53 mg) in 80% yield; mp 152−154 °C; Rf = 0.2
(10% EtOAc/hexane); 1H NMR (CDCl3, 400 MHz): δ 7.66 (s, 1H),
7.42−7.32 (m, 4H), 7.28−7.25 (m, 2H), 7.22−7.18 (m, 3H), 7.15−
7.10 (m, 4H), 7.01 (dd, J = 16.0 Hz, 8.0 Hz, 2H), 6.88 (t, J = 8.0 Hz,
1H), 6.84−6.82 (m, 1H), 6.79−6.70 (m, 8H), 6.66 (d, J = 4.0 Hz, 1H),
6.55 (d, J = 8.0 Hz, 2H), 6.48 (t, J = 8.0 Hz, 1H), 6.16−6.13 (m, 1H),
2.71 (s, 3H), 2.49 (s, 3H); 13C{1H} NMR (CDCl3, 100 MHz): δ 155.6,
151.1, 141.1, 141.0, 140.3, 140.2, 139.4, 138.5, 138.3, 137.9, 137.8,
135.9, 133.6, 133.5, 132.3, 131.7 (2C), 131.6 (2C), 131.5 (2C), 131.4,
131.3, 131.2, 130.6, 130.4, 129.2, 127.7, 127.5, 127.3, 127.2, 126.7
(2C), 126.5, 126.4, 126.1, 125.9, 125.5, 125.4, 125.1, 124.8, 124.6,
124.2, 22.4, 22.1; IR (KBr, cm−1): 3055, 2917, 1601, 1410.
6.79 (m, 2H), 6.74−6.69 (m, 5H), 6.65 (d, J = 7.2 Hz, 1H), 6.56−6.50
(m, 3H), 6.20−6.18 (m, 1H), 2.70 (s, 1H); 13C{1H} NMR (CDCl3,
100 MHz) δ 155.4, 152.5, 141.1, 141.0, 140.9, 140.4, 140.2, 138.8,
138.7, 138.4, 137.0, 134.0, 133.7, 133.5, 132.9, 132.0, 131.6 (2C),
131.4, 131.3, 131.2, 130.6, 130.3, 128.1, 127.8, 127.7, 127.6, 127.5
(2C), 127.0, 126.9, 126.8, 126.7, 126.6, 126.5, 126.1, 125.6, 125.5,
125.2, 125.1, 124.6, 120.2, 22.4; IR (KBr, cm−1): 3055, 2852, 1601,
1408, 651; HRMS (ESI) m/z: [M + H]+ calcd for C50H35BrN
728.1947; found 728.1987.
8-Methoxy-1-methyl-4-phenyl-3-(5,6,7,8-tetraphenylnaphtha-
len-1-yl)isoquinoline (3ka). Prepared according to general procedure
A. The crude reaction mixture was purified by column chromatography,
giving a pale yellow solid (45 mg) in 66% yield; mp 273−275 °C; Rf =
0.2 (10% EtOAc/hexane); 1H NMR (CDCl3, 400 MHz): δ 7.41−7.34
(m, 3H), 7.28 (t, J = 8.0 Hz, 1H), 7.22−7.09 (m, 8H), 7.01 (dd, J = 16.0
Hz, 8.0 Hz, 2H), 6.91 (dd, J = 16.0 Hz, 8.0 Hz, 2H), 6.85−6.81 (m,
1H), 6.78−6.66 (m, 10H), 6.58−6.55 (m, 2H), 6.51 (t, J = 8.0 Hz, 1H),
6.22−6.19 (m, 1H), 3.92 (s, 3H), 2.89 (s, 3H); 13C{1H} NMR (CDCl3,
100 MHz): δ 158.1, 156.1, 152.0, 141.1, 141.0, 140.9, 140.3, 140.2,
139.3, 138.5, 138.3, 138.2, 138.0, 133.6, 133.4, 132.1, 131.7, 131.6
(2C), 131.5, 131.4 (2C), 131.3, 131.2, 130.6, 130.3, 129.5, 128.5, 127.7,
127.5, 127.3, 127.2, 126.7, 126.6, 126.5 (2C), 126.4, 126.0, 125.4 (2C),
125.1, 124.9, 124.6, 118.9, 118.3, 105.8, 55.8, 28.9; IR (KBr, cm−1):
3055, 2877, 2837, 1611, 1440, 1027; HRMS (ESI) m/z: [M + H]+ calcd
for C51H38NO 680.2948; found 680.2932.
1,7-Dimethyl-4-phenyl-3-(5,6,7,8-tetraphenylnaphthalen-1-yl)-
isoquinolin-6-ol (3la). Prepared according to general procedure A. The
crude reaction mixture was purified by column chromatography, giving
a pale brown solid (53 mg) in 78% yield; mp 242−244 °C; Rf = 0.2
(30% EtOAc/hexane); 1H NMR (CDCl3, 400 MHz): δ 7.55 (s, 1H),
7.27 (d, J = 8.4 Hz, 1H), 7.17−7.09 (m, 4H), 7.05 (d, J = 6.8 Hz, 1H),
7.02−7.00 (m, 1H), 6.98−6.91 (m, 3H), 6.89−6.85 (m, 1H), 6.81−
6.75 (m, 6H), 6.71−6.65 (m, 5H), 6.63−6.60 (m, 1H), 6.59 (s, 1H),
6.54−6.49 (m, 3H), 6.45 (d, J = 7.6 Hz, 1H), 6.16−6.13 (m, 1H), 2.50
(s, 3H), 2.31 (s, 3H); 13C{1H} NMR (CDCl3, 100 MHz): δ 154.4,
141.0 (2C), 140.9, 140.2, 140.1, 138.3, 138.1, 137.9, 137.8, 136.4,
133.6, 133.2, 132.5, 131.6, 131.4 (2C), 131.3, 131.2, 130.5, 129.8,
128.5, 127.7, 127.5 (2C), 127.2, 127.0, 126.9, 126.7 (2C), 126.6, 126.5,
126.4, 126.1 (2C), 125.5, 125.4, 125.2, 124.9, 124.2, 121.3, 107.3, 21.0,
17.2; IR (KBr, cm−1): 3443, 3056, 2868, 1440; HRMS (ESI) m/z: [M +
H]+ calcd for C51H38NO 680.2948; found 680.2906.
1-Methyl-4,6-diphenyl-3-(5,6,7,8-tetraphenylnaphthalen-1-yl)-
isoquinoline (3ma). Prepared according to general procedure A. The
crude reaction mixture was purified by column chromatography, giving
a pale yellow solid (45 mg) in 63% yield; mp 155−157 °C; Rf = 0.2
(10% EtOAc/hexane); 1H NMR (CDCl3, 400 MHz): δ 8.03 (d, J = 8.0
Hz, 1H), 7.76 (s, 1H), 7.62 (dd, J = 12.0 Hz, 4.0 Hz, 1H), 7.45 (dd, J =
12.0 Hz, 4.0 Hz, 1H),7.40−7.36 (m, 2H), 7.29−7.13 (m, 11H), 7.04 (d,
J = 8.0 Hz, 1H), 6.99 (d, J = 8.0 Hz, 1H), 6.90 (t, J = 8.0 Hz, 1H), 6.86−
6.83 (m, 1H), 6.80−6.66 (m, 11H), 6.55−6.52 (m, 2H), 6.48 (t, J = 8.0
Hz, 1H), 6.13 (t, J = 8.0 Hz, 1H), 2.78 (s, 3H);13C{1H} NMR (CDCl3,
100 MHz): δ 156.2, 153.2, 140.8, 140.6, 140.5, 140.2, 139.8, 138.4,
138.3, 138.2, 137.3, 136.1, 134.3, 133.4, 133.2, 131.7, 131.3, 131.2,
131.1 (2C), 131.0, 130.8, 130.3, 130.0, 129.6, 127.5 (2C), 127.4, 127.3
(2C), 126.9, 126.4 (2C), 126.3 (2C), 126.2, 125.8, 125.3, 125.2, 125.0,
124.7, 124.3, 123.4 (2C), 121.6 (2C), 22.2; IR (KBr, cm−1): 3056,
2857, 1600, 1441; HRMS (ESI) m/z: [M + H]+ calcd for C56H40N
726.3155; found 726.3129.
1-Methyl-4-phenyl-3-(5,6,7,8-tetraphenylnaphthalen-1-yl)-
benzo[h]isoquinoline (3na). Prepared according to general procedure
A. The crude reaction mixture was purified by column chromatography,
giving a brown solid (45 mg) in 64% yield; mp 258−259 °C; Rf = 0.2
1
(10% EtOAc/hexane); H NMR (CDCl3, 400 MHz): δ 8.62 (d, J =
7-Bromo-1-methyl-4-phenyl-3-(5,6,7,8-tetraphenylnaphthalen-
1-yl)isoquinoline (3ja). Prepared according to general procedure A.
The crude reaction mixture was purified by column chromatography,
giving a brown solid (10 mg) in 14% yield; mp 140−142 °C; Rf = 0.2
(10% EtOAc/hexane); 1H NMR (CDCl3, 400 MHz): δ 8.05 (s, 1H),
7.50 (d, J = 8.8 Hz, 1H), 7.43 (d, J = 8.4 Hz, 1H), 7.39−7.31 (m, 4H),
7.23−7.21 (m, 3H), 7.18−7.12 (m, 5H), 7.03 (d, J = 7.6 Hz, 1H), 6.98
(d, J = 7.6 Hz, 1H), 6.90 (t, J = 7.6 Hz, 1H), 6.84−6.82 (m, 1H), 6.80−
12.0 Hz, 1H), 7.84 (d, J = 8.0 Hz, 1H), 7.69 (t, J = 8.0 Hz, 1H), 7.65−
7.58 (m, 2H), 7.53 (d, J = 8.0 Hz, 1H), 7.42 (d, J = 8.0 Hz, 1H), 7.35 (d,
J = 8.0 Hz, 1H), 7.33−7.25 (m, 3H), 7.24−7.20 (m, 2H), 7.16−7.09
(m, 4H), 7.03 (d, J = 8.0 Hz, 1H), 7.00−6.95 (m, 2H), 6.87−6.83 (m,
1H), 6.78−6.65 (m, 9H), 6.56−6.44 (m, 2H), 6.39 (d, J = 8.0 Hz, 1H),
5.95 (t, J = 8.0 Hz, 1H), 3.08 (s, 3H); 13C{1H} NMR (CDCl3, 100
MHz): δ 154.1, 153.5, 141.0 (2C), 140.8, 140.2, 138.5, 138.3, 137.8
G
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(2C), 136.1, 133.4 (2C), 133.0, 132.3, 131.6 (2C), 131.5 (2C), 131.4,
131.3 (2C), 131.0, 130.9, 130.7, 130.5, 130.4, 129.9, 128.8, 127.8,
127.6, 127.5, 127.4, 127.3, 126.7 (3C), 126.6 (3C), 126.5, 126.4, 126.2,
125.8, 125.4, 125.2, 124.6 (2C), 124.3, 123.8, 29.9; IR (KBr, cm−1):
3054, 2856, 1601, 1440; HRMS (ESI) m/z: [M + H]+ calcd for
C54H38N 700.2999; found 700.2983.
125.2, 124.7, 124.5, 122.4, 122.1, 120.6, 117.7, 116.8, 109.1, 32.4, 23.5;
IR (KBr, cm−1): 3055, 2852, 1601, 1441.
3-Phenyl-2-(5,6,7,8-tetraphenylnaphthalen-1-yl)-8,9-dihydro-
7H-benzo[de]quinoline (3sa).10 Prepared according to general
procedure A. The crude reaction mixture was purified by column
chromatography, giving a pale brown solid (37 mg) in 55% yield; mp
125−127 °C; Rf = 0.3 (20% EtOAc/hexane); 1H NMR (CDCl3, 400
MHz): δ 7.43−7.39 (m, 3H), 7.36−7.32 (m, 1H), 7.28−7.24 (m, 4H),
7.22−7.19 (m, 2H), 7.17−7.14 (m, 2H), 7.12−7.09 (m, 2H), 7.04−
6.99 (m, 2H), 6.92 (t, J = 7.6 Hz, 1H), 6.88−6.83 (m, 1H), 6.79−6.75
(m, 3H), 6.71−6.67 (m, 6H), 6.57−6.51 (m, 3H), 6.17 (t, J = 7.6 Hz,
1H), 3.09−3.00 (m, 4H), 2.14−2.10 (m, 2H); 13C{1H} NMR (CDCl3,
100 MHz): δ 157.6, 141.2, 141.0, 140.9, 140.3, 140.2, 138.5, 138.3,
138.2, 137.8, 135.6, 133.5, 133.4, 132.3, 131.6, 131.5(2C), 131.4(2C),
131.3, 131.1, 130.7, 130.4, 127.7, 127.5, 127.3, 127.2, 126.7(2C),
126.5(2C), 126.4, 126.1, 125.5, 125.4, 125.2, 124.8, 124.6, 124.3, 123.6,
123.3, 34.3, 30.9, 23.5; IR (KBr, cm−1): 3056, 2867, 1601, 1441.
1-Ethyl-4-phenyl-3-(5,6,7,8-tetraphenylnaphthalen-1-yl)-
isoquinoline (3ua). Prepared according to general procedure A. The
crude reaction mixture was purified by column chromatography, giving
a pale yellow solid (35 mg) in 53% yield; mp 106−108 °C; Rf = 0.2 (5%
EtOAc/hexane); 1H NMR (CDCl3, 400 MHz): δ 7.98−7.95 (m, 1H),
7.48−7.40 (m, 6H), 7.28−7.25 (m, 2H), 7.23−7.20 (m, 2H), 7.16−
7.14 (m, 2H), 7.12−7.09 (m, 2H), 7.05 (t, J = 7.6 Hz, 1H), 6.98 (d, J =
7.6 Hz, 1H), 6.90−7.83 (m, 2H), 6.78−6.75 (m, 3H), 6.72−6.64 (m,
6H), 6.50−6.45 (m, 3H), 6.11 (t, J = 7.6 Hz, 1H), 3.29−3.20 (m, 1H),
3.03−2.94 (m, 1H), 1.38 (t, J = 7.6 Hz, 3H); 13C{1H} NMR (CDCl3,
100 MHz): δ 161.0, 152.1, 141.1(2C), 141.0, 140.3, 140.1, 139.6, 138.4,
138.2, 137.8, 137.6, 135.6, 133.4, 132.3, 131.6, 131.5(2C), 131.4(2C),
131.3, 131.1, 130.6, 130.5, 129.3, 127.8, 127.5(2C), 127.2, 127.1,
126.7(2C), 126.6, 126.5(2C), 126.4(2C), 126.2, 126.1, 125.5, 125.4,
125.2, 125.1, 125.0, 124.6, 29.2, 14.3; IR (KBr, cm−1): 3055, 2930,
1601, 1441; HRMS (ESI) m/z: [M + H]+ calcd for C51H38N 664.2999;
found 664.3055.
6-Methyl-9-phenyl-8-(5,6,7,8-tetraphenylnaphthalen-1-yl)-[1,3]-
dioxolo[4,5-f ]isoquinoline (3oa). Prepared according to general
procedure A. The crude reaction mixture was purified by column
chromatography, giving a gray solid (21 mg) in 31% yield; mp 155−137
1
°C; Rf = 0.5 (30% EtOAc/hexane); H NMR (CDCl3, 400 MHz): δ
7.54 (d, J = 8.0 Hz, 1H), 7.39 (dd, J = 8.0 Hz, 4.0 Hz, 1H), 7.36−7.33
(m, 1H), 7.31 (dd, J = 7.2 Hz, 1.2 Hz, 1H), 7.23−7.19 (m, 2H), 7.17−
7.10 (m, 6H), 7.05−7.00 (m, 2H), 6.98 (d, J = 8.0 Hz, 1H), 6.91 (t, J =
8.0 Hz, 1H), 6.87−6.83 (m, 1H), 6.79−6.68 (m, 9H), 6.64 (d, J = 8.0
Hz, 1H), 6.55−6.51 (m, 2H), 6.22 (t, J = 8.0 Hz, 1H), 5.83 (d, J = 1.2
Hz, 1H), 5.73 (d, J = 1.2 Hz, 1H), 2.67 (s, 3H); 13C{1H} NMR (CDCl3,
100 MHz): δ 156.4, 152.6, 147.4, 141.1, 141.0 (2C), 140.3, 140.2,
138.5, 138.4, 138.3, 137.9, 133.7, 133.4, 132.3, 131.6 (2C), 131.5,
131.4, 131.3 (2C), 131.1 (2C), 130.7, 130.3, 127.7, 127.5, 127.2, 126.7
(2C), 126.6, 126.5, 126.4, 126.3, 126.2, 126.0, 125.6, 125.4, 125.2,
124.9, 124.5, 123.2, 121.9, 120.7, 110.5, 101.5, 23.1; IR (KBr, cm−1):
3054, 2873, 1600, 1441, 1278; HRMS (ESI) m/z: [M + H]+ calcd for
C51H36NO2 694.2741; found 694.2727.
7-Methyl-4-phenyl-5-(5,6,7,8-tetraphenylnaphthalen-1-yl)furo-
[2,3-c]pyridine (3pa). Prepared according to general procedure A. The
crude reaction mixture was purified by column chromatography, giving
a pale yellow solid (32 mg) in 50% yield; mp 239−241 °C; Rf = 0.3
(10% EtOAc/hexane); 1H NMR (CDCl3, 400 MHz): δ 7.58 (d, J = 2.0
Hz, 1H), 7.54 (d, J = 8.0 Hz, 1H), 7.38 (d, J = 8.0 Hz, 1H), 7.29 (t, J =
8.0 Hz, 1H), 7.23−7.11 (m, 8H), 7.07−7.04 (m, 2H), 6.92 (d, J = 4.0
Hz, 1H), 6.83 (d, J = 8.0 Hz, 2H), 6.78−6.63 (m, 8H), 6.57−6.50 (m,
4H), 6.34 (t, J = 8.0 Hz, 1H), 2.56 (s, 3H); 13C{1H} NMR (CDCl3, 100
MHz): δ 151.4, 149.4, 147.2, 141.0 (2C), 140.9, 140.6, 140.3, 140.1,
139.0, 138.7, 138.5, 137.6, 137.5, 133.8, 133.5, 133.0, 131.9, 131.7,
131.6 (2C), 131.5, 131.4, 131.2 (2C), 130.4, 130.1, 127.8 (2C), 127.6
(2C), 126.9, 126.8, 126.7, 126.6 (2C), 126.5, 126.3, 125.7, 125.4, 125.2,
125.1, 124.8 (2C), 106.6, 18.5; IR (KBr, cm−1): 3056, 2853, 1601,
1441; HRMS (ESI) m/z: [M + H]+ calcd for C48H34NO 640.2635;
found 640.2646.
7-Methyl-4-phenyl-5-(5,6,7,8-tetraphenylnaphthalen-1-yl)-
thieno[2,3-c]pyridine (3qa).10 Prepared according to general
procedure A. The crude reaction mixture was purified by column
chromatography, giving a brown solid (43 mg) in 61% yield; mp 110−
112 °C; Rf = 0.3 (10% EtOAc/hexane); 1H NMR (CDCl3, 400 MHz):
δ 7.49 (d, J = 8.0 Hz, 1H), 7.45 (d, J = 5.2 Hz, 1H), 7.37 (d, J = 6.0 Hz,
1H), 7.28−7.13 (m, 10H), 7.09−7.04 (m, 2H), 6.93 (d, J = 4.0 Hz,
1H), 6.86−6.80 (m, 2H), 6.78−6.67 (m, 7H), 6.62−6.61 (m, 2H),
6.55−6.50 (m, 2H), 6.25 (t, J = 8.0 Hz, 1H), 2.59 (s, 3H); 13C{1H}
NMR (CDCl3, 100 MHz): δ 152.9, 150.1, 144.6, 141.0 (3C), 140.5,
140.3, 138.8, 138.7, 138.5, 138.1, 137.7, 133.9, 133.7, 133.5, 132.1,
131.6 (2C), 131.5, 131.4, 131.3, 131.2, 130.5, 130.2, 128.3, 127.8,
127.7, 127.6, 126.8, 126.7, 126.6 (2C), 126.5, 126.4, 125.7, 125.4, 125.2
(2C), 124.7, 124.6, 124.3, 23.4; IR (KBr, cm−1): 3054, 2855, 1600,
1440.
1,5-Dimethyl-4-phenyl-3-(5,6,7,8-tetraphenylnaphthalen-1-yl)-
5H-pyrido[4,3-b]indole (3ra).10 Prepared according to general
procedure A. The crude reaction mixture was purified by column
chromatography, giving a brown solid (53 mg) in 75% yield; mp 124−
126 °C; Rf = 0.5 (50% EtOAc/hexane); 1H NMR (CDCl3, 400 MHz):
δ 8.08 (d, J = 8.0 Hz, 1H), 7.47 (t, J = 8.0 Hz, 1H), 7.43−7.40 (m, 2H),
7.34−7.28 (m, 3H), 7.23−7.20 (m, 4H), 7.17−7.12 (m, 4H), 7.06 (d, J
= 8.0 Hz, 1H), 7.01 (d, J = 8.0 Hz, 1H), 6.85−6.77 (m, 5H), 6.74−6.68
(m, 5H), 6.63 (d, J = 8.0 Hz, 1H), 6.59−6.57 (m, 1H), 6.44 (t, J = 8.0
Hz, 1H), 6.22 (t, J = 8.0 Hz, 1H), 3.12 (s, 3H), 2.86 (s, 3H); 13C{1H}
NMR (CDCl3, 100 MHz): δ 154.9, 150.6, 143.3, 142.3, 141.1, 141.0,
140.9, 140.4, 140.3, 138.5, 138.4, 138.1, 133.8, 133.4, 132.4, 132.0,
131.6 (2C), 131.5, 131.4, 131.3, 131.2, 131.1, 130.6, 130.5, 127.8, 127.5
(2C), 127.2, 126.9, 126.8, 126.6 (2C), 126.5, 126.4, 126.0, 125.9, 125.4,
3-(4-Chloro-5,6,7,8-tetrakis(4-chlorophenyl)naphthalen-1-yl)-4-
(4-chlorophenyl)-6-methoxy-1-methylisoquinoline (3cb). Prepared
according to general procedure A. The crude reaction mixture was
purified by column chromatography, giving a pale yellow solid (26 mg)
1
in 30% yield; mp 128−130 °C; Rf = 0.3 (20% EtOAc/hexane); H
NMR (CDCl3, 400 MHz): δ 7.94 (d, J = 9.2 Hz, 1H), 7.51−7.47 (m,
2H), 7.24 (d, J = 2.4 Hz, 1H), 7.19 (s, 2H), 7.15 (dd, J = 8.8 Hz, 2.4 Hz,
2H), 7.08 (d, J = 8.4 Hz, 1H), 6.99−6.94 (m, 2H), 6.86−6.79 (m, 4H),
6.77−6.73 (m, 2H), 6.67 (d, J = 2.4 Hz, 1H), 6.51−6.45 (m, 3H), 6.39
(d, J = 8.4 Hz, 1H), 6.25 (dd, J = 8.0 Hz, 2 Hz, 1H), 6.04−5.98 (m, 2H),
3.70 (s, 3H), 2.75 (s, 3H); 13C{1H} NMR (CDCl3, 100 MHz): δ 161.0,
157.3, 139.2, 138.6, 138.2, 138.1, 137.7, 137.3, 136.4, 136.0, 135.6
(2C), 134.6, 132.9 (2C), 132.7, 132.5, 132.4, 132.3, 132.2, 132.1, 132.0,
131.9, 131.6, 131.4, 130.9, 130.4, 130.1, 129.1, 128.3, 128.1, 127.8
(2C), 127.7 (3C), 127.5 (2C), 127.2, 126.8, 121.5, 119.1, 103.6, 55.5,
22.1; IR (KBr, cm−1): 2855, 1412, 1027, 771; HRMS (ESI) m/z: [M +
H]+ calcd for C51H32Cl6NO 884.0610; found 884.0593.
3-(4-Chloro-5,6,7,8-tetraphenylnaphthalen-1-yl)-4-(4-chloro-
phenyl)-1-methylisoquinoline (3ae). Prepared according to general
procedure B. The crude reaction mixture was purified by column
chromatography, giving a pale yellow solid (36 mg) in 50% yield; mp
274−276 °C; Rf = 0.3 (20% EtOAc/hexane); 1H NMR (CDCl3, 400
MHz): δ 7.96−7.92 (m, 1H), 7.49−7.42 (m, 5H), 7.32−7.23 (m, 3H),
7.16−7.07 (m, 3H), 6.96−6.91 (m, 3H), 6.89−6.83 (m, 2H), 6.78−
6.73 (m, 4H), 6.72−6.66 (m, 2H), 6.63−6.56 (m, 3H), 6.42 (dd, J = 8.0
Hz, 4 Hz, 1H), 6.33 (d, J = 8.0 Hz, 1H), 6.07 (d, J = 8.0 Hz, 1H), 5.94 (t,
J = 8.0 Hz, 1H), 2.69 (s, 3H); 13C{1H} NMR (CDCl3, 100 MHz): δ
157.2, 151.3, 141.3, 140.8, 140.6, 140.3, 140.0, 139.8, 138.9, 138.0,
136.3, 135.8, 135.7, 134.6, 133.4, 133.0, 132.2, 132.0, 131.8, 131.6
(2C), 131.4, 131.0, 130.5, 130.2, 130.0 (2C), 129.8, 128.9, 128.5, 128.1,
127.3, 127.2, 127.0, 126.9, 126.8, 126.7, 126.6, 126.3, 126.0, 125.8,
125.6, 125.5, 125.4, 125.2, 22.2; IR (KBr, cm−1): 3066, 2852, 1441,
696; HRMS (ESI) m/z: [M + H]+ calcd for C50H34Cl2N 718.2063;
found 718.2028.
4-Ethyl-1-methyl-3-(5,6,7,8-tetraphenylnaphthalen-1-yl)-
isoquinoline (3af). Prepared according to general procedure B. The
H
https://dx.doi.org/10.1021/acs.joc.0c02582
J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
pubs.acs.org/joc
Article
crude reaction mixture was purified by column chromatography, giving
a pale yellow solid (32 mg) in 53% yield; mp 240−242 °C; Rf = 0.2
(10% EtOAc/hexane); 1H NMR (CDCl3, 400 MHz): δ 7.91 (d, J = 8.0
Hz, 1H), 7.74 (d, J = 8.0 Hz, 1H), 7.68 (d, J = 8.0 Hz, 1H), 7.55−7.52
(m, 1H), 7.46−7.39 (m, 3H), 7.28−7.24 (m, 4H), 7.20−7.16 (m, 1H),
6.81−6.74 (m, 6H), 6.68−6.57 (m, 6H), 6.35−6.32 (m, 1H), 6.20 (t, J
= 8.0 Hz, 1H), 5.95 (t, J = 8.0 Hz, 1H), 2.79 (s, 3H), 2.72 (q, J = 8.0 Hz,
1H), 2.62 (q, J = 8.0 Hz, 1H), 1.17 (t, J = 8.0 Hz, 3H); 13C{1H} NMR
(CDCl3, 100 MHz): δ 154.9, 152.4, 141.3, 141.0 (2C), 140.6, 140.5,
140.1, 139.1, 138.6, 134.8, 133.9, 131.9, 131.8, 131.5 (2C), 131.4, 131.3
(2C), 130.5, 130.2 (2C), 129.4, 128.9, 128.2, 127.8, 127.7, 126.7, 126.6,
126.3, 126.2, 125.9, 125.8, 125.4, 125.1 (2C), 125.0, 124.6, 124.5,
123.8, 23.8, 22.4, 15.2; IR (KBr, cm−1): 3056, 2873, 1601, 1441; HRMS
(ESI) m/z: [M + H]+ calcd for C46H36N 602.2842; found 602.2804.
4-Ethyl-6-methoxy-1-methyl-3-(5,6,7,8-tetraphenylnaphthalen-
1-yl)isoquinoline (3cf). Prepared according to general procedure B.
The crude reaction mixture was purified by column chromatography,
giving a brown solid (27 mg) in 43% yield; mp 147−149 °C; Rf = 0.3
(20% EtOAc/hexane); 1H NMR (CDCl3, 400 MHz): δ 7.82 (d, J = 8.0
Hz, 1H), 7.43 (dd, J = 8.4 Hz, 1.2 Hz, 1H), 7.45−7.41 (m, 1H), 7.38
(dd, J = 6.8 Hz, 1.2 Hz, 1H), 7.29−7.22 (m, 4H), 7.20−7.16 (m, 1H),
7.09 (dd, J = 9.2 Hz, 2.4 Hz, 1H), 6.92 (d, J = 2.4 Hz, 1H), 6.83−6.74
(m, 6H), 6.70−6.63 (m, 5H), 6.60−6.58 (m, 1H), 6.39−6.36 (m, 1H),
6.23 (t, J = 8.0 Hz, 1H), 6.01 (t, J = 7.6 Hz, 1H), 3.91 (s, 3H), 2.74 (s,
3H), 2.61 (q, J = 8.0 Hz, 2H), 1.17 (t, J = 8.0 Hz, 3H); 13C{1H} NMR
(CDCl3, 100 MHz): δ 160.3, 154.2, 141.3, 141.1, 141.0, 140.5, 139.1
(2C), 138.6, 136.7, 133.9, 131.9, 131.8, 131.6, 131.5, 131.4, 131.3,
131.2, 130.5, 130.2, 130.1, 128.2, 128.1, 127.9, 127.8, 127.7, 126.7,
126.6, 126.3, 126.2, 125.4, 125.1, 125.0, 124.8, 124.6 (2C), 122.4,
117.7, 102.4, 55.6, 23.9, 22.2, 14.6; IR (KBr, cm−1): 3055, 2871, 1440,
1027; HRMS (ESI) m/z: [M + H]+ calcd for C47H38NO 632.2948;
found 632.2921.
Bedadyuti Vedvyas Pati − School of Chemical Sciences,
National Institute of Science Education and Research
(NISER) Bhubaneswar, HBNI, Khurda 752050, Odisha,
India
Smruti Ranjan Mohanty − School of Chemical Sciences,
National Institute of Science Education and Research
(NISER) Bhubaneswar, HBNI, Khurda 752050, Odisha,
India
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.joc.0c02582
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We are thankful to NISER, Department of Atomic Energy
(DAE), Council for Scientific and Industrial Research (CSIR),
New Delhi (grant 02(0256)/16/EMR II), and Science and
Engineering Research Board (SERB), New Delhi (grant
EMRII/2017/001475) for the financial support. Pragati Biswal
and Shyam K. Banjare thank DAE for a research fellowship.
B.V.P. and S.R.M. thank DST-INSPIRE program for financial
support. We thank Dr. Arindam Ghosh and Mr. Shreenibas Sa,
NISER Bhubaneswar, for solving the single-crystal X-ray data.
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Mechanistic studies and control experiments, NMR
spectra (1H, 13C, and 19F) of 3aa−3ua, 3cb, 3cf, 3ae,
and 3af, and X-ray crystallography data (PDF)
FAIR data, including the primary NMR FID files, for
compounds 3aa−3ua, 3cb, 3cf, 3ae, and 3af (ZIP)
Accession Codes
CCDC 2036544, 2036625, and 2038561 contain the supple-
mentary crystallographic data for this paper. These data can be
obtained free of charge via www.ccdc.cam.ac.uk/data_request/
cif, or by emailing data_request@ccdc.cam.ac.uk, or by
contacting The Cambridge Crystallographic Data Centre, 12
Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
AUTHOR INFORMATION
Corresponding Author
Ponneri Chandrababu Ravikumar − School of Chemical
Sciences, National Institute of Science Education and Research
(NISER) Bhubaneswar, HBNI, Khurda 752050, Odisha,
India; orcid.org/0000-0002-5264-820X; Email: pcr@
niser.ac.in
■
Authors
Pragati Biswal − School of Chemical Sciences, National Institute
of Science Education and Research (NISER) Bhubaneswar,
HBNI, Khurda 752050, Odisha, India
Shyam Kumar Banjare − School of Chemical Sciences, National
Institute of Science Education and Research (NISER)
Bhubaneswar, HBNI, Khurda 752050, Odisha, India
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