Synthesis of sterically congested polycyclic aromatic hydrocarbons: Rhodium(III)-catalyzed cascade oxidative annulation of aryl ketoximes with diphenylacetylene by sequential cleavage of multiple C-H bonds

Article abstract of DOI:10.1002/adsc.201400292

The rhodium(III)-catalyzed oxidative annulations of aryl ketoximes with diphenylacetylene by the cleavage of three C-H bonds, one C-O bond and the formation of four C-C bonds, one C-N bonds simultaneously have been developed. This protocol is scalable and

Full text of DOI:10.1002/adsc.201400292

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DOI: 10.1002/adsc.201400292
Synthesis of Sterically Congested Polycyclic Aromatic
Hydrocarbons: Rhodium(III)-Catalyzed Cascade Oxidative
G
Annulation of Aryl Ketoximes with Diphenylacetylene by
À
Sequential Cleavage of Multiple C H Bonds
Bin Liu,a Fang Hu,a and Bing-Feng Shia,b,*
a
Department of Chemistry, Zhejiang University, Hangzhou 310027, Peopleꢀs Republic of China
Fax : (+86)-571-8795-1895, phone: (+86)-571-8795-1352; e-mail: bfshi@zju.edu.cn
State Key Laboratory of Bioorganic & Natural Products Chemistry, Shanghai Institute of Organic Chemistry, Chinese
b
Academy of Sciences, Shanghai 200032, Peopleꢀs Republic of China
Received: March 24, 2014; Revised: April 22, 2014; Published online: July 17, 2014
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201400292.
Abstract: The rhodium
ACHTUNGTRNE(NUNG III)-catalyzed oxidative an- highly congested polycyclic aromatic/heteroaromatic
nulations of aryl ketoximes with diphenylacetylene hydrocarbons.
À
À
by the cleavage of three C H bonds, one C O bond
and the formation of four C C bonds, one C N
À
À
À
bonds simultaneously have been developed. This Keywords: alkynes; C H activation; oxidative annu-
protocol is scalable and compatible with various lation; polycyclic aromatic hydrocarbons (PAHs);
functional groups, providing an expeditious access to rhodium
Introduction
of reaction typically uses heteroatoms to direct cyclo-
metalation at the ortho C H bond, followed by oxida-
À
Polycyclic aromatic and heteroaromatic hydrocarbons tive annulation with alkynes (Figure 1). Miura,[5a] Fag-
are an important class of compounds because of their nou[5b] and several groups have achieved tremendous
wide applications in materials science, as nanotubes, successes for the synthesis of heterocycles via hetero-
light emitters, semiconductors, light-absorption dyes, cyclization with 1 equivalent of alkynes in the pres-
and in liquid crystals.[1] Numerous synthetic methodol- ence of [Cp*RhCl2]2/AgSbF6/Cu
ACTHNUGTRNE(UNG OAc)2 catalyst
ogies for the construction of these polycyclic aromatic system (Figure 1, a).[5] The construction of polycyclic
systems have been developed in the past decades,[2] aromatic hydrocarbons via oxidative annulations with
among which, transition metal-catalyzed cross-cou- 2 equivalents of alkynes has also been well investigat-
pling reactions of organometallic reagents with organ- ed (Figure 1, b).[6] In these reports, however, the oxi-
ic halides are popular methods for the formation of dative annulation reactions are mainly restricted to
functionalized polycyclic aromatic and heteroaromatic the coupling of various aromatic substrates with one
hydrocarbons.[3] However, these methods are typically or two equivalents alkynes via the cleavage of one or
[5,6]
À
limited by the availability of the starting materials two C H bonds.
Our continued interest in metal-
[9]
À
and multistep procedures. Moreover, the construction catalyzed C H activation and the reactions through
of more densely arylated arenes still poses a significant the cleavage of more than one C H bonds promoted
À
challenge, since the cross-coupling reactions are usu- us to explore the synthesis of highly congested isoqui-
[6d,e]
À
ally sensitive to steric hindrance.
nolines through C H activation.
Herein we de-
oximes undergo
À
Transition metal-catalyzed direct C H bond func- scribe a new process in which aryl ket
U
tionalization has unimpeachably emerged as a power- an efficient oxidative annulation with three equiva-
ful tool for the step- and atom-economical construc- lents of diphenylacetylene, by the cleavage of three
À
À
tion of complex organic molecules in modern organic C H bonds, one C O bond with formation of four
chemistry.[4] Recently, the Rh
annulations of various aromatic substrates with alk- protocol provides an expeditious access to the highly
ynes have been extensively investigated.[5–7] This kind
AHCTUNGERTG(NNUN III)-catalyzed oxidative C C bonds and one C N bond simultaneously. This
À
À
ACHTUNGTRENNUNG
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Synthesis of Sterically Congested Polycyclic Aromatic Hydrocarbons
Table 1. Optimization of reaction conditions.[a]
[a]
Reaction conditions: 1a (0.4 mmol), [Cp*RhCl2]2, 2a
(1.2 mmol), Cu(OAc)2 (0.8 mmol), NaOAc (0.2 mmol), in
AHCTUNGTRENNUNG
2 mL MeOH. Yields are given for isolated products after
chromatography.
NaOAc was not added.
Under air.
[b]
[c]
groups were compatible with the optimized conditions
and reacted efficiently with diphenylacetylene to give
the corresponding highly congested annulation prod-
ucts (up to 96% yield). Aryl ketoxime 1c bearing an
ortho-methyl group gave a reduced yield (entry 2,
23%), likely due to the steric hindrance. When meta-
substituted aryl ketoximes were applied, good regio-
Figure 1. RhACHTUNGTRENNUNG(III)-catalyzed oxidative annulation with al-
kynes via C H activation.
À
À
selectivity favoring activation of the less hindered C
H bonds was achieved (entries 3, 5 and 9). The unpro-
congested
1-methyl-4-phenyl-3-(5,6,7,8-tetraphenyl- tected phenol group is also compatible with the pres-
naphthalen-1-yl)isoquinolines.
ent reaction protocol; affording 3h in 81% yield
(entry 7). Various ketoximes bearing other valuable
functional groups, such as acetylamino, chloro, fluoro
and trifluoromethyl, could react smoothly with alkyne
2a to afford the annulated products in good yields
Results and Discussion
We commenced our study by investigating the cou- (entries 7–12).
pling of 3,4-dihydronaphthalen-1(2H)-one O-methyl We were delighted to find that the RhACTHNUGTRNEUN(G III)-cata-
oxime 1a and 3 equivalents of diphenylacetylene 2a lyzed annulation reaction was also compatible with
with [Cp*RhCl2]2 (5.0 mol%) as catalyst in the pres- heteroaromatic ketoximes (Table 3). Heteroarenes,
ence of CuACHTUNGTRENNUNG(OAc)2 under N2 in MeOH at 1108C. The such as pyrrole, thiophene and indole, all reacted with
reaction proceeded smoothly to afford the product in alkyne 2a in good to excellent yields (entries 1–4).
70% yield (Table 1, entry 1). The yield was reduced When 3-substituted thiophene was applied, activation
when the reaction was carried out at 1008C or in the of the C-4 position was achieved regioselectively
absence of NaOAc (entries 2 and 3). We were delight- under standard reaction conditions (entry 3). More-
ed to find that the yield was improved to 83% when over, the congested polycyclic structure was con-
the reaction was run for only 2 h even with the re- firmed by an X-ray analysis of compound 3q
duced loading of catalyst (entry 6, 2.5 mol% (Table 3).[10] However, complicated mixtures were ob-
[Cp*RhCl2]2). The yield dropped dramatically when tained when other substituted diphenylacetylenes
the reaction was conducted under an air atmosphere were employed to this reaction protocol.
(entry 6).
To compare the activity difference of aryl ketox-
With the optimized conditions in hand, the sub- imes, we performed a set of intermolecular competi-
strate scope of this annulation process was explored tion experiments between ketoximes 1g and 1k with
extensively (Table 2). Substrates bearing both elec- alkyne 2a under the standard reaction conditions. The
tron-withdrawing groups and electron-donating result indicated that electron-rich ketoxime 1g was
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Table 2. Substrate scope of aryl ketoximes.[a]
[a]
Yields are given for isolated products after chromatography.
transformed preferentially (Scheme 1), hence render- tion was stopped after 10 min. A primary KIE value
À
ing an electrophilic C H bond activation.
(kH/kD =3) was obtained, indicating that the cleavage
À
To further evaluate the efficiency and practicality of the C H bond in the phenyl ring of ketoxime is
of this reaction, a 4-mmol scale reaction was conduct- most likely involved in the rate-determining step
ed using 1b as substrate and the reaction proceeded (Scheme 3).[11]
smoothly to furnish the product 3b in good yield
(Scheme 2, 76% yield, 1.95 g of 3b).
On the basis of these preliminary results and litera-
ture precedents,[5,6] a plausible mechanism for the
To gain further insight into the mechanism of this present catalytic process is proposed (Figure 2). The
cascade reaction, we carried out a deuterium competi- [Cp*RhCl2]2 presumably dissociates into the coordina-
tion experiment between substrate 1b and 1b-d5 tively unsaturated monomer, which can exchange
under the standard reaction conditions and the reac- with acetate ligand to form Cp*RhACHTNUTGRNEUNG(OAc)2. The first
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Table 3. Synthesis of sterically congested polycyclic heteroaromatic hydrocarbons.
À
step is likely to be a rate-determining ortho-C H cycle and the second-step annulation. The mechanism
bond activation of aryl ketoxime 1 with the assistance of the second-step annulation of functionalized 1-
of the oxime nitrogen to give arylrhodium intermedi- methyl-3,4-diphenylisoquinoline C with alkyne is con-
ate A. Alkyne may then coordinate with A, followed sistent with that reported by Li[6c] and Miura.[6a,d]
À
by regioselective insertion into the Rh C bond of A
to afford the seven-membered intermediate B. Finally,
À
À
subsequent C N bond formation and N O bond Conclusions
cleavage of intermediate B via a concerted redox pro-
cess in a redox neutral manner in the presence of In conclusion, we have demonstrated a rhodiumACHTUNGTRENNUNG(III)-
NaOAc affords the first-step product C and regener- catalyzed cascade oxidative annulation reaction of
ates the active Rh
AHCTUNGTRENNUNG
Scheme 1. Intermolecular competition experiments between ketoximes 1g and 1h.
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Scheme 2. Gram-scale synthesis of 3b.
using CuACHTUNGTRENNUNG(OAc)2 as an oxidant, generating highly con-
gested 1-methyl-4-phenyl-3-(5,6,7,8-tetraphenylnaph-
thalen-1-yl)isoquinolines in good yields. This reaction
protocol features a short reaction time, high compati-
bility with various functional groups and high yields.
Figure 2. Proposed mechanism.
Experimental Section
General Methods
3.0 equiv.), CuACHTNUTRGNE(NUG OAc)2 (0.8 mmol, 2.0 equiv.), NaOAc
Commercial grade solvents were dried by known proce-
dures. The other materials and solvents were purchased
from commercial suppliers and used without additional pu-
rification. Aryl ketoximes 1a–1p were prepared according to
the literature.[12] NMR spectra were recorded for 1H at
400 MHz, and 13C at 100 MHz using TMS as internal stan-
dard. Chemical shifts are given relative to CDCl3 (7.26 ppm
(0.2 mmol, 0.5 equiv.) and 2 mL MeOH in a 50-mL Schlenck
tube (purged with N2) was heated at 1108C for 2 h. Then
the reaction mixture was cooled to room temperature and
a saturated solution of Na2S (2 mL) was added and the
whole stirred for 5 min. The resulting mixture was extracted
with dichloromethane. The organic layer was dried over
Na2SO4, concentrated under reduced pressure and separated
on a silica gel column with petroleum ether/ethyl acetate as
the eluent to give the desired product 3.
3-Phenyl-2-(5,6,7,8-tetraphenylnaphthalen-1-yl)-8,9-dihy-
dro-7H-benzo[de]quinoline (3a): obtained as a yellow solid
according to the general procedure; yield: 224 mg (83%).
1H NMR (400 MHz, CDCl3): d=7.43–7.38 (m, 3H), 7.34–
7.31 (m, 1H), 7.27- 7.08 (m, 10H), 7.03–6.99 (m, 2H), 6.96
(m, J=7.2 Hz, 1 H), 6.87–6.81 (m, 1H), 6.78–6.66 (m, 9H),
6.56–6.50 (m, 3H), 6.16 (t, J=7.2 Hz, 1H), 3.13–2.98 (m,
4H), 2.15- 2.08 (m, 2H); 13C NMR (100 MHz, CDCl3): d=
157.5, 151.7, 141.0, 140.9, 140.8, 140.1, 140.0, 139.3, 138.3,
138.1, 137.7, 135.5, 133.4, 133.3, 132.1, 131.5, 131.3, 131.0,
130.5, 130.2, 129.3, 129.0, 127.6, 127.3, 127.1, 127.0, 126.4,
1
for H NMR, 77.16 ppm for 13C NMR). Data are presented
as follows: chemical shift, integration, multiplicity (br=
broad, s=singlet, d=doublet, t=triplet, q=quartet, m=
multiplet), coupling constants in Hertz (Hz). Mass spectros-
copy data of the products were collected on an HR-MS-
TOF instrument or a low-resolution MS instrument using EI
ionization.
General Procedure for the Annulation of Aryl
Ketoximes with Internal Alkynes
A mixture of aryl ketoxime 1 (0.4 mmol), [Cp*RhCl2]2
(0.01 mmol, 0.025 equiv.), diphenylacetylene 2a (1.2 mmol,
Scheme 3. Kinetic isotope effect.
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126.3, 125.9, 125.3, 125.2, 125.0, 124.7, 124.4, 124.1, 123.5,
123.2, 34.2, 30.8, 23.3; HR-MS (EI-TOF): m/z=675.2932,
calcd. for C52H37N (M+): 675.2926.
1-Methyl-4-phenyl-3-(5,6,7,8-tetraphenylnaphthalen-1-yl)-
ACHTUNGTRENNUNGisoquinoline (3b): obtained as a white solid according to the
(s, 3H), 2.35 (s, 3H); 13C NMR (100 MHz, CDCl3): d=
155.8, 151.8, 140.9, 140.8, 140.0, 139.3, 138.3, 138.1, 137.8,
137.6, 135.4, 133.4, 133.3, 132.2, 131.5, 131.4, 131.2, 131.0,
130.4, 130.3, 128.9, 128.2, 127.8, 127.3, 127.1, 127.0, 126.6,
126.5, 126.4, 126.2, 125.9, 125.4, 125.2, 125.0, 124.8, 124.7,
124.4, 124.2, 22.2, 22.1; HR-MS (EI-TOF): m/z=663.2934,
calcd. for C51H37N (M+): 663.2926.
general procedure; yield: 190 mg (73%). 1H NMR
(400 MHz, CDCl3): d=7.85–7.82 (m, 1H), 7.39–7.29 (m,
6H), 7.28–7.19 (m, 5H), 7.17–7.11 (m, 4H), 7.03 (d, J=
7.6 Hz, 1H), 6.98 (d, J=7.6 Hz, 1H), 6.89–6.83 (m, 2H),
6.80–6.65 (m, 9H), 6.55–6.54 (m, 2H), 6.46 (t, J=7.4 Hz,
1H), 6.13 (t, J=7.4 Hz, 1H), 2.74 (s, 3H); 13C NMR
(100 MHz, CDCl3): d=156.2, 151.1, 140.9, 140.8, 140.2,
139.1, 138.2, 137.8, 137.5, 135.2, 133.5, 133.4, 132.1, 131.6,
131.4, 131.3, 131.2, 131.0, 130.5, 130.3, 129.4, 129.2, 127.6,
127.4, 127.2, 127.1, 126.6, 126.5, 126.4, 126.3, 126.1, 125.9,
125.8, 125.3, 125.2, 125.1, 125.0, 124.7, 124.5, 22.3; HR-MS
(EI-TOF): m/z=649.2770, calcd. for C50H35N (M+):
649.2770.
7-Methoxy-1-methyl-4-phenyl-3-(5,6,7,8-tetraphenylnaph-
thalen-1-yl)isoquinoline (3f): obtained as a white solid ac-
cording to the general procedure; yield: 190 mg (70%).
1H NMR (400 MHz, CDCl3): d=7.88 (s, 1H), 7.45–7.35 (m,
5H), 7.29–7.21 (m, 4H), 7.19–7.13 (m, 4H), 7.03 (d, J=
7.2 Hz, 1H), 6.98 (d, J=7.6 Hz, 1H), 6.92–6.83 (m, 2H),
6.80–6.70 (m, 8H), 6.66 (d, J=6.8 Hz, 1H), 6.57–6.50 (m,
3H), 6.19 (t, J=7.4 Hz, 1H), 2.71 (s, 3H); 13C NMR
(100 MHz, CDCl3): d=156.6, 155.5, 152.9, 141.4, 141.0,
140.8, 140.2, 139.8, 139.2, 138.2, 138.0, 137.9, 133.4, 133.0,
132.5, 131.4, 131.3, 130.9, 130.4, 129.9, 129.2, 127.7, 127.6,
127.3, 126.5, 126.4, 126.2, 125.8, 125.5, 125.4, 125.2, 125.0,
124.8, 124.6, 124.3, 117.8, 109.8, 55.6, 22.9; HR-MS (EI-
TOF): m/z=679.2870, calcd. for C51H37NO (M+): 679.2875.
6-Methoxy-1-methyl-4-phenyl-3-(5,6,7,8-tetraphenylnaph-
thalen-1-yl)isoquinoline (3g): obtained as a white solid ac-
cording to the general procedure; yield: 260 mg (96%).
1H NMR (400 MHz, CDCl3): d=7.82 (d, J=9.2 Hz, 1H),
7.42–7.38 (m, 3H), 7.24–7.19 (m, 3H), 7.18–7.11 (m, 4H),
7.09–7.06 (m, 1H), 7.04–6.99 (m, 3H), 6.91 (t, J=7.4 Hz,
1H), 6.87–6.82 (m, 1H), 6.80–6.78 (m,3H), 6.75–6.67 (m,
7H), 6.57–6.50 (m, 3H), 6,19 (t, J=7.2 Hz, 1H), 3.68 (s,
3H), 2.69 (s, 3H); 13C NMR (100 MHz, CDCl3): d=160.1,
155.5, 152.4, 140.9, 140.8, 140.2, 140.1, 140.0, 139.3, 138.3,
138.1, 137.8, 137.7, 137.2, 133.5, 133.4, 133.3, 132.1, 131.5,
131.2, 131.0, 130.4, 130.1, 128.7, 127.6, 127.5, 127.4, 127.2,
127.1, 127.0, 126.6, 126.5, 126.4, 126.3, 125.8, 125.3, 125.2,
125.0, 124.7, 124.4, 121.5, 118.7, 55.2, 22.2; HR-MS (EI-
TOF): m/z=679.2883, calcd. for C51H37NO (M+): 679.2875.
1-Methyl-4-phenyl-3-(5,6,7,8-tetraphenylnaphthalen-1-yl)-
d4-1-Methyl-4-phenyl-3-(5,6,7,8-tetraphenylnaphthalen-1-
yl)isoquinoline (3b-d4): obtained as a white solid according
to the general procedure; yield: 10 mg (15%). 1H NMR
(400 MHz, CDCl3): d=7.43–7.37 (m, 3H), 7.28–7.20 (m,
4H), 7.18–7.11 (m, 4H), 7.03 (d, J=7.2 Hz, 1H), 6.98 (d, J=
7.6 Hz, 1H), 6.89–6.82 (m, 2H), 6.79–6.65 (m, 9 H), 6.5–6.53
(m, 2H), 6.46 (t, J=7.4 Hz, 1H), 6.12 (t, J=7.4 Hz, 1H),
2,74 (s, 3H).
1,8-Dimethyl-4-phenyl-3-(5,6,7,8-tetraphenylnaphthalen-1-
yl)isoquinoline (3c): obtained as a white solid according to
the general procedure; yield: 60 mg (23%). 1H NMR
(400 MHz, CDCl3): d=7.41–7.39 (m, 2H), 7.35–7.32 (m,
1H), 7.27–7.18 (m, 7H), 7.17–7.10 (m, 4H), 7.02–6.92 (m,
2H), 6.91 (t, J=7.4 Hz, 1H), 6.85–6.83 (m, 1H), 6.77–6.65
(m, 9H), 6.54–6.49 (m, 3H), 6.13 (t, J=7.4H, 1H), 2.89 (s,
3H), 2. 83 (s, 3H); 13C NMR (100 MHz, CDCl3): d=155.9,
151.0, 141.0, 140.9, 140.8, 140.2, 140.1, 138.9, 138.3, 138.2,
138.1, 137.7, 137.2, 135.4, 133.4, 133.3, 132.0, 131.4, 131.3,
131.2, 131.0, 129.5, 129.4, 128.5, 127.6, 127.4, 127.1, 126.8,
126.6, 126.4, 126.3, 125.8, 125.2, 125.0, 124.6, 124.5, 29.3,
25.9; HR-MS (EI-TOF): m/z=663.2930, calcd. for C51H37N
(M+): 663.2926.
1,7-Dimethyl-4-phenyl-3-(5,6,7,8-tetraphenylnaphthalen-1-
yl)isoquinoline (3d): obtained as a white solid according to
the general procedure; yield: 184 mg (69%). 1H NMR
(400 MHz, CDCl3): d=7.66 (s, 1H), 7.42–7.32 (m, 4H),
7.28–7.17 (m, 5H), 7.15–7.10 (m, 4H), 7.03 (d, J=7.6 Hz,
1H), 6.98 (d, J=7.6 Hz, 1H), 6.89–6.82 (m, 2H), 6.79–6.69
(m, 8H), 6.66 (d, J=7.6 Hz, 1H), 6.54 (d, J=6.4 Hz, 1 H),
6.48 (d, J=7.4 Hz, 1H), 6.15 (t, J=7.6 Hz, 1H), 2.71 (s,
3H), 2,50 (s, 3H); 13C NMR (100 MHz, CDCl3): d=155.4,
150.9, 140.9, 140.2, 140.1, 139.2, 139.3, 138.3, 138.2, 137.8,
137.7, 135.8, 133.4, 132.1, 131.4, 131.3, 131.2, 131.1, 130.4,
130.3, 129.1, 127.6, 127.4, 127.0, 126.6, 126.4, 126.2, 125.8,
125.3, 125.2, 125.0, 124.7, 124.5, 124.1, 22.3, 22.0; HR-MS
(EI-TOF): m/z=663.2933, calcd. for C51H37N (M+):
663.2926.
1,6-Dimethyl-4-phenyl-3-(5,6,7,8-tetraphenylnaphthalen-1-
yl)isoquinoline (3e): obtained as a white solid according to
the general procedure; yield: 211 mg (79%). 1H NMR
(400 MHz, CDCl3): d=7.79 (d, J=8.4 Hz, 1H), 7.41–7.37
(m, 3H), 7.28–7.19 (m, 6H), 7.16–7.10 (m, 4H), 7.04–6.98,
(m, 2H), 6.91 (t, J=7.4 Hz, 1H), 6.87–6.82 (m, 1H), 6.79–
6.62 (m, 9H), 6.54–6.48 (m, 3H), 6.13 (t, J=7.4H, 1H), 2.70
AHCTUNGTREGiNNUN soquinolin-6-ol (3h): obtained as a white solid according to
the general procedure; yield: 216 mg (81%). 1H NMR
(400 MHz, CDCl3): d=7.72–7.69 (m, 1H), 7.35–7.31 (m,
2H), 7.22–7.18 (m, 1H), 7.14–7.11 (m, 3H), 7.06–6.91 (m,
8H), 6.85–6.81 (m, 1H), 6.78–6.74 (m, 2H), 6.73–6.64 (m,
6H), 6.59 (s, 1H), 6.53–6.47 (m, 3H), 6.13 (t, J=7.4 Hz,
1H), 2,58 (s, 3H); 13C NMR (100 MHz, CDCl3): d=155.3,
140.8, 140.7, 140.1, 138.4, 138.1, 137.6, 133.4, 133.2, 132.2,
131.4, 131.3, 131.2, 131.1, 131.0, 130.9, 130.5, 129.9, 127.6,
127.5, 127.3, 127.0, 126.6, 126.5, 126.4, 126.3, 126.0, 125.4,
125.3, 125.1, 124.8, 124.3, 107.9, 21.2; HR-MS (EI-TOF):
m/z=665.2720, calcd. for C50H35NO (M+): 665.2719.
N-(1-Methyl-4-phenyl-3-(5,6,7,8-tetraphenylnaphthalen-1-
yl)isoquinolin-6-yl)acetamide (3i): obtained as a yellow solid
according to the general procedure; yield: 200 mg (71%).
1H NMR (400 MHz, CDCl3): d=7.87 (s, 2H), 7.42–7.36 (m,
4H), 7,29 (s, 1H), 7.24–7.20 (m, 4H), 7.16–7.13 (m, 4H),
7.02 (d, J=7.2 Hz, 1H), 6.98 (d, J=Hz, 1H), 6.90–6.82 (m,
2H), 6.79–6.76 (m, 2H), 6.75–6.65 (m, 7H), 6.57–6.37 (m,
4H), 6.16 (t, J=7.4 Hz, 1H), 2.70 (s, 3H), 2.10 (s, 3H);
13C NMR (100 MHz, CDCl3): d=168.5, 155.8, 140.9, 140.8,
140.1, 139.0, 138.2, 137.7, 137.4, 136.0, 133.5, 133.2, 132.0,
131.5, 131.4, 131.3, 131.1, 131.0, 130.5, 130.1, 128.7, 127.6,
127.5, 127.4, 127.3, 127.1, 126.6, 126.5, 126.4, 126.3, 125.8,
125.4, 125.3, 125.0, 124.8, 124.4, 123.0, 119.7, 113.5, 24.8,
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22.1; HR-MS (EI-TOF): m/z=706.2976, calcd. for
C52H38N2O (M+): 706.2984.
solid according to the general procedure; yield: 227 mg
(87%). 1H NMR (400 MHz, CDCl3): d=7.48 (dd, J1 =
1.2 Hz, J2 =4.4 Hz, 1H), 7.37 (dd, J1 =1.2 Hz, J2 =6.8 Hz,
7-Chloro-1-methyl-4-phenyl-3-(5,6,7,8-tetraphenylnaph-
thalen-1-yl)isoquinoline (3j): obtained as a yellow solid ac-
cording to the general procedure; yield: 193 mg (71%).
1H NMR (400 MHz, CDCl3): d=7.88 (s, 1H), 7.45–7.35 (m,
5H), 7.29–7.21 (m, 4H), 7.19–7.13 (m, 4H), 7.03 (d, J=
7.2 Hz, 1H), 6.98 (d, J=7.6 Hz, 1H), 6.92–6.83 (m, 2H),
6.80–6.70 (m, 8H), 6.66 (d, J=6.8 Hz, 1H), 6.57–6.50 (m,
3H), 6.19 (t, J=7.4 Hz, 1H), 2.71 (s, 3H); 13C NMR
(100 MHz, CDCl3): d=155.3, 152.2, 140.9, 140.8, 140.7,
140.3, 140.1, 138.7, 138.5, 138.3, 137.6, 136.9, 133.6, 133.5,
133.4, 131.9, 131.8, 131.4, 131.3, 131.1, 131.0, 126.3, 125.9,
125.4, 125.3, 125.1, 124.9, 124.4, 124.1, 22.2; HR-MS (EI-
TOF): m/z=683.2385, calcd. for C50H34ClN (M+): 683.2380.
6-Chloro-1-methyl-4-phenyl-3-(5,6,7,8-tetraphenylnaph-
thalen-1-yl)isoquinoline (3k): obtained as a yellow solid ac-
cording to the general procedure; yield: 220 mg (80%).
1H NMR (400 MHz, CDCl3): d=7.85 (d, J=8.8 Hz, 1H),
7.44–7.36 (m, 5H), 7.28–7.21 (m, 4H), 7.18–7.12 (m, 4H),
7.03 (d, J=7.6 Hz, 1H), 6.98 ( d, J=8.0 Hz, 1H), 6.92–6.82
(m, 2H), 6.80–6.75 (m, 3H), 6.73–6.66 (m, 6H), 6.57–6.49
(m, 3H), 6.18 (t, J=7.2 Hz, 1H), 2.73 (s, 3H); 13C NMR
(100 MHz, CDCl3): d=156.2, 153.1, 140.9, 140.8, 140.7,
140.3, 140.0, 138.7, 138.5, 138.3, 137.6, 136.7, 136.3, 135.8,
133.5, 133.3, 131.9, 131.4, 131.3, 131.2, 131.1, 131.0, 130.5,
130.1, 128.5, 127.6, 127.4, 127.3, 127.0, 126.9, 126.8, 126.4,
126.3, 125.9, 125.5, 125.3, 125.1, 124.8, 124.4, 124.0, 22.3;
HR-MS (EI-TOF): m/z=683.2379, calcd. for C50H34ClN
(M+): 683.2380.
1H), 6.94–6.93 (m, 2H), 6.85–6.75
7H), 6.59–6.53 (m, 2H), 6.49–6.44AHCUTNGTRENNUNG
ACHTUNGTRENNUNG
8.0 Hz, 1H), 3,96 (s, 3H), 2.74 (s, 3H); 13C NMR (100 MHz,
CDCl3): d=147.0, 141.1, 140.4, 140.2, 139.6, 138.3, 137.7,
134.2, 133.7, 133.3, 133.0, 132.0, 131.7, 131.4, 131.2, 130.8,
130.3, 129.9, 129.4, 127.7, 127.5, 127.4, 127.3, 127.0, 126.5,
126.4, 126.3, 126.2, 126.1, 125.8, 125.2, 125.1, 124.8, 124.7,
124.6, 124.1, 36.9, 22.6; HR-MS (EI-TOF): m/z=652.2877,
calcd. for C49H36N2 (M+): 652.2878.
7-Methyl-4-phenyl-5-(5,6,7,8-tetraphenylnaphthalen-1-
yl)thienoACTHNUTRGENUG[N 2,3-c]pyridine (3o): obtained as a yellow solid ac-
cording to the general procedure; yield: 218 mg (83%).
1H NMR (400 MHz, CDCl3): d=7.49 (d, J=8.4 Hz, 1H),
7.45 (d, J=5.2 Hz, 1H), 7.28–7.24 (m, 2H), 7.22–7.13 (m,
7H), 7.08–7.04 (m, 3H), 6.93 (d, J=7.6 Hz, 1H), 6.86–6.80
(m 2H), 6.78–6.76 (m, 2H), 6.75–6.62 (m, 5H), 6.63–6.60
(m, 2H), 6.55–6.49 (m, 2H), 6.25 (t, J=7.4 Hz, 1H), 2.59 (s,
3H); 13C NMR (100 MHz, CDCl3): d=157.8, 150.0, 144.5,
140.9, 140.8, 140.4, 140.2, 138.6, 138.5, 138.3, 138.0, 137.6,
133.8, 133.6, 131.9, 131.5, 131.3, 131.2, 131.1,130.3, 130.1,
128.2, 127.6, 127.5, 127.4, 126.6, 126.5, 126.4, 126.2, 125.5,
125.1, 125.0, 124.5, 124.1, 23.3; HR-MS (EI-TOF): m/z=
655.2331, calcd. for C48H33NS (M+): 655.2334.
4-Methyl-7-phenyl-6-(5,6,7,8-tetraphenylnaphthalen-1-
yl)thienoACTHNUTRGNEUNG
[3,4-c]pyridine(3p): 1H NMR (400 MHz, CDCl3):
d=7.50 (m,1H), 7.42 (m, 1H), 7.33–7.28 (m, 2H), 7.26–7.24
(m, 2H), 7.23–7.19 (m, 6H), 7.17–7.13 (m, 3H), 7.08 (d, J=
7.2 Hz, 1H), 6.96 (d, J=7.6 Hz, 1H), 6.85–6.81 (m, 2H),
6.80–6.66 (m,8H), 6.60 (d, J=6.8 Hz, 1H), 6.54–6.48 (m,
2H), 6.32 (t, J=7.6 Hz, 1H), 2.64 (s, 3H); 13C NMR
(100 MHz, CDCl3): d=151.7, 151.3, 148.3, 140.9, 140.8,
140.4, 140.1, 138.6, 138.3, 138.2, 137.5, 133.6, 133.4, 131.8,
131.6, 131.4, 131.2, 131.0, 130.3, 129.4, 127.8, 127.6, 127.4,
127.2, 126.7, 126.5, 126.4, 126.3, 125.7, 125.3, 125.1, 125.0,
124.6, 124.5, 122.3, 22.4; HR-MS (ESI): m/z=655.2336,
calcd, for C48H33NS (M+): 655.2334.
6-Fluoro-1-methyl-4-phenyl-3-(5,6,7,8-tetraphenylnaphtha-
len-1-yl)isoquinoline (3l): obtained as a white solid accord-
1
ing to the general procedure; yield: 203 mg (76%). H NMR
(400 MHz, CDCl3): d=7.91 (dd, J1 =4.2 Hz, J2 =8.8 Hz,
1H), 7.44–7.36 (m, 3H), 7.29–7.22ACTHNUTRGNEUNG(m, 5H), 7.18–7.11 (m,
4H), 7.06–6.92 (m, 3H), 6.89–6.82 (m, 2H), 6.79–6.65 (m,
9H), 6.59–6.54 (m, 2H), 6.48 (t, J=7.4 Hz, 1H), 6.18 (t, J=
7.4 Hz, 1H), 2,73 (s, 3H); 13C NMR (100 MHz, CDCl3): d=
162.0 (d JC,F =233.8 Hz), 156.0, 152.8, 140.9, 140.8, 140.7,
140.3, 140.1, 138.8, 138.5, 138.3, 137.6, 137.0, 131.9, 131.4,
131.3, 131.1, 131.0, 130.6, 130.0, 128.1 (d, JC,F =9.5 Hz),
127.6, 127.4, 127.3, 126.8, 126.6 (d, JC,F =3.4 Hz), 126.4,
126.3, 125.8, 125.4, 125.3, 125.1, 124.8, 124.4, 123.0, 116.0(d,
1,5-Dimethyl-4-phenyl-3-(5,6,7,8-tetraphenylnaphthalen-1-
yl)-5H-pyridoACTHUNTGRNEUNG[4,3-b]indole (3q): obtained as a yellow solid
according to the general procedure; yield: 270 mg (96%).
1H NMR (400 MHz, CDCl3): d=8.07 (d, J=8.0 Hz, 1H),
7.49–7.39 (m, 3H), 7.33–7.28 (m, 3H), 7.24–7.11 (m, 9H),
7.06 (d, J=7.6 Hz, 1H), 7.01 (d, J=7.6 Hz, 1H), 6.87–6.77
(m, 6H), 6.74–6.61 (m, 5H), 6,63–6,57 (m, 2H), 6.44 (t, J=
7.6 Hz, 1H), 6.21 (t, J=7.2 Hz, 1H), 3,12 (s, 1H), 2. 85 ( s,
3H); 13C NMR (100 MHz, CDCl3): d=154.8, 150.5, 143.1,
142.2, 140.9, 140.8, 140.7, 140.2, 140.1, 138.6, 138.4, 138.2,
138.0, 136.7, 133.7, 133.2, 132.3, 131.9, 131.4, 131.2, 131.1,
130.9, 130.4, 127.6, 127.3, 127.0, 126.6, 126.4, 126.2, 125.9,
125.7, 125.2, 125.0, 124.5, 124.3, 122.3, 122.0, 120.5, 117.5,
116.7, 32.3, 23.3; HR-MS (EI-TOF): m/z=702.3028, calcd.
for C53H38N2 (M+): 702.3035.
J
C,F=25.3 Hz), 109.5 (d, JC,F =21.9 Hz), 22.4; HR-MS (EI-
TOF): m/z=667.2668, calcd. for C50H34FN (M+): 667.2675.
1-Methyl-4-phenyl-3-(5,6,7,8-tetraphenylnaphthalen-1-yl)-
6-(trifluoromethyl)isoquinoline (3m): obtained as a white
solid according to the general procedure; yield: 219 mg
1
(76%). H NMR (400 MHz, CDCl3): d=8.03 (d, J=8.4 Hz,
1H), 7.76 (s,1H), 7.62 (dd, J1 =1.2 Hz, J2 =8.0 Hz, 1H). 7.45
(d, J=8.4 Hz, 1H), 7.31–7.23 (m, 4H), 7.17–7.11 (m, 4H),
7.03 (d, J=7.2 Hz, 1H), 6.98 (d, J=7.6 Hz, 1H), 6.92–6.83
(m, 2H), 6.79–6.70 (m, 9H), 6.54–6.46 (m, 3H), 6.12 (t, J=
7.6 Hz, 1H), 2,78 (s, 3H); 13C NMR (100 MHz, CDCl3): d=
156.3, 153.4, 140.9, 140.8, 140.6, 140.3, 140.0, 138.6, 138.5,
138.3, 137.5, 136.3, 134.5, 133.5, 133.4, 131.9, 131.4, 131.3,
130.9, 130.5, 130.2, 129.8, 127.7, 127.6, 127.5, 127.4, 126.6,
126.5 (d, JC,F =3.8 Hz), 126.4, 126.0, 125.3, 125.1, 124.8,
124.5, 123.6 (d, JC,F =3.6 Hz), 122.7, 121.8, 22.4; HR-MS (EI-
TOF): m/z=717.2638, calcd. for C51H34F3N (M+): 717.2643.
1,7-Dimethyl-4-phenyl-5-(5,6,7,8-tetraphenylnaphthalen-1-
Acknowledgements
Financial support from the National Natural Science Founda-
tion of China (21002087, 21142002, 21272206), the Funda-
mental Research Funds for the Central Universities
yl)-1H-pyrroloACHTUNGTRENNUNG[2,3-c]pyridine (3n): obtained as a yellow
2694
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FULL PAPERS
Synthesis of Sterically Congested Polycyclic Aromatic Hydrocarbons
(2014QNA3008), Zhejiang Provincial NSFC (Z12B02000),
Qianjiang Project (2013R10033) and Specialized Research
Fund for the Doctoral Program of Higher Education
(20110101110005) is gratefully acknowledged.
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ꢁ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2014, 356, 2688 – 2696