Sequential σ-Bond Insertion/Benzannulation Involving Arynes: Selective Synthesis of Polysubstituted Naphthalenes

Article abstract of DOI:10.1021/acs.joc.8b01207

An interesting σ-bond insertion/benzannulation reaction for the synthesis of polysubstituted naphthalene derivatives has been developed from readily accessible ketones, arynes, and alkynoates. This practical and transition-metal-free method provides a novel route to diverse naphthalenes through a substrate-controlled rearrangement reaction with the cleavage of C-C bonds.

Full text of DOI:10.1021/acs.joc.8b01207

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Article
Sequential #-Bond Insertion/Benzannulation Involving
Arynes: Selective Synthesis of Polysubstituted Naphthalenes
Wen-Ming Shu, Shan Liu, Jian-Xin He, Shuai Wang, and An-Xin Wu
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.8b01207 • Publication Date (Web): 07 Jun 2018
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Sequential σꢀBond Insertion/Benzannulation
Involving Arynes: Selective Synthesis of
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Polysubstituted Naphthalenes
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, ‡
WenꢀMing Shu,* *
, † Shan Liu,† JianꢀXin He,† Shuai Wang,† and AnꢀXin Wu
† College of Chemistry and Environmental Engineering, Yangtze University, Jingzhou 434023, P.
R. China
‡ Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, College of Chemistry,
Central China Normal University, Wuhan 430079, P. R. China
†
E-mail: shuwm@yangtzeu.edu.cn.
‡ E-mail: chwuax@mail.ccnu.edu.cn.
ABSTRACT
: An interesting σꢀbond insertion/benzannulation reaction for the
synthesis of polysubstituted naphthalene derivatives has been developed from readily
accessible ketones, arynes, and alkynoates. This practical and transitionꢀmetalꢀfree
method provides a novel route to diverse naphthalenes through a substrateꢀcontrolled
rearrangement reaction with the cleavage of CꢀC bonds.
INTRODUCTION
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Substituted naphthalenes are important motifs widely found in natural products,
pharmaceuticals, and biologically active molecules, such as parvinaphthol B,
justicidin B, and amonafide (Figure 1).1 In addition, they have numerous applications
in supramolecular chemistry and materials science.2
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Figure 1. Selected examples of activated naphthalenes.
Accordingly, much effort has been devoted to their regioselective synthesis over
recent years, and many useful synthetic methods to this field were accomplished.3
These strategies include Diels−Alder reactions,4 transitionꢀmetal or Lewis acid
catalyzed annulations,5 and rearrangements of strained rings.6 Despite some progress
in this area, these methods cannot directly synthesize α–CN substituted naphthalene
derivatives. As the cyano group is easily converted into various different functional
groups, it is of significant interest to develop efficient and direct methods for the
construction of naphthalene ring with a versatile cyano group at the α position.7
Arynes are indispensable reactive intermediates in organic synthesis and have
received considerable attention over recent years.8 Due to their high reactivity and
ease of preparation (only in the presence of fluoride),9 they have the potential to take
part in a large number of novel reactions to construct various organic compounds.10 In
particular, the annulation of benzynes has been shown to be one of the most powerful
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and reliable approaches for preparing naphthalene derivatives.11 For example, the
Diels–Alder reaction of arynes and conjugated dienes can directly and efficiently
afford a variety of promising natural products and useful naphthalene skeletons
(Scheme 1a).12 Huang and coworkers reported a novel multicomponent reaction of
arynes, αꢀketo sulfones, and Michaelꢀtype acceptors for the synthesis of
polysubstituted naphthols and naphthalenes (Scheme 1b).13 Recently, our group
developed a novel formal [2+2+2] cycloaddition reaction involving arynes for the
efficient and convenient synthesis of naphthalene derivatives from simple available
substances under mild conditions (Scheme 1c).14 With our continued interest in
arynes, we herein report a sequential σꢀbond insertion/annulation reaction for the
direct synthesis of α–CN naphthalenes. In addition, interesting naphthalene
derivatives with acyl group abscission were also obtained (Scheme 1d).
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Scheme 1. Methods for Accessing Polysubstituted Naphthalenes Involving
Arynes.
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RESULTS AND DISCUSSION
Initially, we tested the combination of benzoylacetonitrile (1a),
2ꢀ(trimethylsilyl)phenyl triflate (2a), methyl phenylpropargylate (3a) and CsF in
CH3CN as the model reaction, and the results are summarized in Table 1. To our
delight, desired product 4a was furnished with 43% yield in the absence of base (entry
1). Subsequently, the influence of base (such as K2CO3, Na2CO3, Cs2CO3, NaHCO3,
NaOH, KOH, K3PO4, and NaOEt) in the reaction was examined (entries 2–9).
Pleasingly, Cs2CO3 worked well in this transformation, affording the product in 74%
yield (entry 4). Then, different solvents were evaluated and CH3CN was found to be
the most efficient solvent for this reaction (entries 10–15). Following the above
investigation, the ratio of substrates was evaluated (entries 16–18), and a higher yield
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was observed with the ratio 1:1:1.2 (entry 16). Moreover, decreased yields were
observed at lower reaction temperatures (entries 19 and 20). Thus, the optimized
conditions were established as follows: benzoylacetonitrile 1a (0.1 mmol),
2ꢀ(trimethylsilyl)phenyl triflate 2a (0.1 mmol), and methyl phenylpropargylate 3a
(0.12 mmol) in the presence of CsF (3.0 equiv) and Cs2CO3 (3.0 equiv) in CH3CN at
80 °C for 15 h.
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Table 1. Optimization of the Reaction Conditionsa
ratio of
1a:2a:3a (%)
yieldb
entry solvent
base
temp (°C)
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
toluene
THF
ꢀ
1:1:1
1:1:1
1:1:1
1:1:1
1:1:1
1:1:1
1:1:1
1:1:1
1:1:1
1:1:1
1:1:1
1:1:1
1:1:1
1:1:1
1:1:1
1:1:1.2
1:1:1.5
2:1:1
1:1:1.2
1:1:1.2
43
70
39
74
0
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80
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70
K2CO3
Na2CO3
Cs2CO3
NaHCO3
NaOH
68
43
38
45
0
KOH
K3PO4
NaOEt
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
9
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19
20
32
0
DCE
EtOAc
EtOH
67
0
dioxane
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
0
79
76
64
43
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a Reaction conditions: CsF (3.0 equiv), base (3.0 equiv), and solvent (2 mL) for 15 h.
bIsolated yields.
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With the optimized reaction conditions in hand, a wide variety of
αꢀcyanoacetophenones (1) were then explored, as shown in Scheme 2. The results
demonstrated that αꢀcyanoacetophenones bearing various electronꢀneutral (H),
electronꢀdonating (3–Me, 3–OMe), and halogen (4–F, 4–Cl, 3, 4–2Cl, 3–Br, and
4–Br) substituents attached to the benzene ring all reacted smoothly with 2a and 3a, to
afford various polysubstituted naphthalene derivatives in 56%–79% yields (4a–4h).
Furthermore, moderate to good yields were also obtained for heteroaromatic (2ꢀfuryl,
2ꢀthienyl and 3ꢀ(1ꢀmethylꢀ1Hꢀindol)ꢀyl) group substrates (67%–81%; 4i–4k). Much to
our satisfaction, even when the substrate contained a sterically hindered 1ꢀnaphthyl
group, the expected product (4l) was obtained in 65% yield. The structure of 4a was
identified by singleꢀcrystal Xꢀray diffraction (see Supporting Information (SI)).
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Scheme 2. Scope of αꢀCyano Ketonesa
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aReactions were carried out with 1 (0.5 mmol, 1.0 equiv), 2a (0.5 mmol, 1.0 equiv),
3a (0.6 mmol, 1.2 equiv), CsF (3.0 equiv) and Cs2CO3 (3.0 equiv) in the CH3CN
(5mL) at 80 °C for 15 h. Isolated yields are shown.
Encouraged by the above results, we then examined the scope of the
2ꢀ(trimethylsilyl)aryl triflates (2) (Scheme 3). Symmetrically substituted
2,3ꢀnaphthalyne and 4,5ꢀdimethoxybenzyne precursors were explored, and the
corresponding products were obtained in moderate to good yields (51%–82%; 5a–5h).
The generality of alkynoates (3) was investigated next, and ethyl phenylpropargylate
was also tolerated in the reaction, leading to the expected product 5i in 80% yield.
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Much to our satisfaction, dimethyl acetylenedicarboxylate also participated in the
annulation reaction, affording the naphthalene product 5j in 45% yield. The structure
of 5j was further confirmed by singleꢀcrystal Xꢀray (see SI). Moreover, methyl and
ethyl propiolate were also tolerated in this annulation to afford the corresponding
products 5k and 5l in 78% and 42% yields, respectively.
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Scheme 3. Scope of 2ꢀ(Trimethylsilyl)aryl Triflates, and Alkynoatesa
aIsolated yields.
Interestingly, when using 1,3ꢀdiketones (6) instead of αꢀcyanoacetophenones in the
reaction, an unexpected product was observed (Scheme 4). We afforded different
naphthalene derivatives, lacking the benzoyl group at the αꢀposition of the product.
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Subsequently, the scope of the 2ꢀ(trimethylsilyl)aryl triflates (2) and alkynoates (3)
were examined. To our delight, symmetrically substituted benzyne precursors were all
compatible in the current reaction system, giving the corresponding products in
56%–84% yields (7a–7d). 1,3ꢀBis(4ꢀmethoxyphenyl)propaneꢀ1,3ꢀdione (6b) was also
a viable substrate in this transformation, furnishing the desired products 7e–7h in
moderate to good yields (65%–79%). Moreover, nonsymmetrical arynes derived from
precursors were investigated in the annulation. When the 4ꢀmethylbenzyne precursor
involved in the reaction, we afforded a mixture of products 7j/7j′ in 59% yield. But
the sole product 7i gained in 48% yield by using 3ꢀmethoxybenzyne precursor as
substrate. Furthermore, the structure of 7f was determined by Xꢀray crystallographic
analysis (see SI).
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Scheme 4. Scope of dibenzoylmethanesa
CO2R2
O
O
R3
TMS
OTf
CsF, Cs2CO3
CH3CN, 80 °C
R1
R1
+
+
Ar
Ar
CO2R2
R3
Ar
6
2
3
7
Ph
CO2Me
MeO
MeO
Ph
Ph
CO2Me
Ph
CO2Me
CO2Et
7c, 84%
7d, 56%
7a, 81%
7b, 77%
Ph
CO2Me
MeO
MeO
Ph
CO2Me
Ph
CO2Et
Ph
CO2Me
OMe
OMe
OMe
OMe
7g, 78%
7h, 65%
7e, 79%
7f, 70%
Ph
CO2Me
Ph
CO2Me
Me
Ph
and
Me
CO2Me
OMe
7j
7j'
59% (7j / 7j' = 6/5)
7i, 48%
aIsolated yields.
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To provide some insights into the reaction mechanism, a series of control
experiments was carried out (Scheme 5). When the reaction of ketone 1a and
2ꢀ(trimethylsilyl)phenyl triflate 2a was carried out in the presence of CsF in CH3CN
at 80 °C for 2 h, product 815 was afforded in 85% yield (Scheme 5a). Similarly,
dibenzoylmethane 6a reacted with benzyne precursor 2a to give compound 916 at
room temperature (Scheme 5b). Much to our satisfaction, compounds 8 and 9 were
transformed into the desired products 4a and 7a in the presence of Cs2CO3 in
excellent yields (Scheme 5c and 5d). These results indicate that compounds 8 and 9
are the intermediates in the annulation reaction.
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Scheme 5. Control Experimentsa
CN
O
TMS
CsF
CN
(a)
Ph
+
O
CH3CN, 80 °C, 2 h
OTf
Ph
8, 85%
1a
2a
2a
3a
3a
Ph
O
O
O
TMS
OTf
CsF
(b)
+
Ph
Ph
O
CH3CN, rt, 2 h
Ph
6a
9, 74%
CN
CN
Ph
Cs2CO3
(c)
+
Ph
CO2Me
O
CH3CN, 80 °C, 15 h
CO2Me
Ph
Ph
8
4a, 82%
Ph
O
Ph
Cs2CO3
(d)
+
Ph
CO2Me
O
CH3CN, 80 °C, 15 h
CO2Me
Ph
Ph
7a, 80%
9
aIsolated products.
On the basis of the abovementioned experimental results, a possible mechanism for
this reaction is shown in Scheme 6 (using 4a and 7a as examples). Initially, ketone 1
transformed into anion 1′ in the presence of CsF, which subsequently reacted with
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benzyne 2a′ (generated in situ generated from 2ꢀ(trimethylsilyl)phenyl triflate 2a) to
afford cyclobutane intermediate A.10b, 17 Subsequent cleavage of the benzylic CꢀC
bond then afforded compounds 8 and 9 via intermediate A.18 Intermediates 8 and 9
then underwent a coupling annulation with methyl 3ꢀphenylpropiolate 3a giving
intermediates B and C, respectively. Finally, intermediate B was transformed to the
desired product 4a via an aromatization reaction with elimination of H2O.
Intermediate C was transformed into intermediate D, which was subsequently
converted to product 7a by the rearrangementꢀaromatization process, with loss of
cesium benzoate.19
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Scheme 6. A Possible Mechanism
CONCLUSION
In summary, we have developed a novel sequential σꢀbond insertion/benzannulation
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reaction of ketones, arynes, and alkynoates to synthesize two classes of naphthalene
derivatives under mild conditions. A detailed study of the mechanism demonstrated
that the ketone substituent plays a key role in the reactivity of the subsequent
annulation process to give different naphthalene products. Further studies on these
practical methods for the construction of natural products and functional organic
molecules are in progress in our laboratory.
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EXPERIMENTAL SECTION
General Information. All substrates and reagents were commercial and used without
further purification. TLC analysis was performed using preꢀcoated glass plates.
Column chromatography was performed using silica gel (200ꢀ300 mesh). IR spectra
were recorded on a PerkinꢀElmer PEꢀ983 infrared spectrometer as KBr pellets with
1
absorption in cmꢀ1. H NMR spectra were determined at 25 °C on a Varian Mercury
400 or 600 MHz spectrometer. Chemical shifts are given in ppm relative to the
13
internal standard of tetramethylsilane (TMS). C spectra were recorded in CDCl3 or
DMSOꢀd6 on 100/150 MHz NMR spectrometers and resonances (δ) in ppm. HRMS
were obtained on an ApexꢀUltra MS equipped with an atmosphericꢀpressure chemical
ionization source or electrospray ionization (ESI) source. The melting points were
determined using XTꢀ4 apparatus and recorded without correction. The Xꢀray
crystalꢀstructures were obtained on a Bruker APEX DUO CCD system.
General Procedure for the Synthesis of 4aꢀ4l, 5aꢀ5l 7aꢀ7i, and 7j/7j′ (4a as
example). The mixture of benzoyl acetonitrile 1a (72.6 mg, 0.5 mmol),
2ꢀtrimethylsilylphenyl triflate 2a (149.2 mg, 0.5 mmol), methyl 3ꢀphenylpropiolate 3a
(96.1 mg, 0.6 mmol) was added in CH3CN (5 mL). Then, added CsF (227.9 mg, 3.0
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mmol) and Cs2CO3 (488.7 mg, 3.0 mmol) in the solvent and the resulting mixture was
stirred at reflux for 15 h. After the reaction completed, and then added 100 mL water
to the mixture, extracted with EtOAc three times (3 × 100 mL). Dried over anhydrous
Na2SO4 and concentrated under reduced pressure. The residue was purified by column
chromatography on silica gel (petroleum ether/EtOAc = 5/1) to afford the desired
product 4a.
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methyl 4ꢀcyanoꢀ1,3ꢀdiphenylꢀ2ꢀnaphthoate (4a): Yield 79% (143.5 mg); white solid;
m.p. 171–172 °C; 1H NMR (600 MHz, CDCl3): δ (ppm) 8.39 (d, J = 8.4 Hz, 1H), 7.76
(t, J = 7.8 Hz, 1H), 7.69 (d, J = 8.4 Hz, 1H), 7.57 (t, J = 7.8 Hz, 1H), 7.54–7.44 (m,
13
8H), 7.39 (d, J = 6.0 Hz, 2H), 3.23 (s, 3H); C NMR (150 MHz, CDCl3): δ (ppm)
167.8, 143.0, 142.6, 136.7, 136.3, 132.7, 131.0, 129.6, 129.1, 129.0, 128.5, 128.4,
128.2, 128.0, 127.8, 125.7, 116.7, 110.1, 51.9; IR (KBr, cmꢀ1): 2357, 2221,1734, 1638,
1566, 1488, 1441, 1384, 1305, 1230, 1185, 1152, 1117, 1045, 1016, 984, 845, 818,
765, 700, 605, 569, 486; HRMS (ESI): m/z [M+H]+ calcd for C25H18NO2: 364.1332;
found: 364.1327.
methyl 4ꢀcyanoꢀ3ꢀphenylꢀ1ꢀ(pꢀtolyl)ꢀ2ꢀnaphthoate (4b): Yield 71% (134.0 mg);
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white solid; m.p. 145–146 °C; H NMR (600 MHz, CDCl3): δ (ppm) 8.38 (d, J = 8.4
Hz, 1H), 7.76 (t, J = 7.8 Hz, 1H), 7.73 (d, J = 8.6 Hz, 1H), 7.56 (t, J = 7.2 Hz, 1H),
7.52–7.46 (m, 5H), 7.28 (q, J = 7.2 Hz, 4H), 3.25 (s, 3H), 2.45 (s, 3H); 13C NMR (100
MHz, CDCl3): δ (ppm) 167.6, 142.8, 142.5, 138.1, 136.6, 133.0, 132.5, 132.5, 130.9,
129.4, 129.3, 128.9, 128.8, 128.8, 128.2, 127.7, 127.6, 125.4, 116.5, 109.7, 51.9, 21.5;
IR (KBr, cmꢀ1): 1734, 1638, 1493, 1429, 1384, 1304, 1226, 1185, 1151, 1117, 1044,
1016, 816, 767, 690, 621, 570; HRMS (ESI): m/z [M+Na]+ calcd for C26H19NNaO2:
400.1308; found: 400.1307.
methyl 4ꢀcyanoꢀ1ꢀ(4ꢀmethoxyphenyl)ꢀ3ꢀphenylꢀ2ꢀnaphthoate (4c): Yield 77%
(151.5 mg); yllow solid; m.p. 179–180 °C; 1H NMR (600 MHz, CDCl3): δ (ppm) 8.38
(d, J = 8.4 Hz, 1H), 7.78–7.70 (m, 2H), 7.61–7.53 (m, 1H), 7.53–7.43 (m, 5H), 7.31
13
(d, J = 9.0 Hz, 2H), 7.02 (d, J = 8.4 Hz, 2H), 3.88 (s, 3H), 3.27 (s, 3H); C NMR
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(150 MHz, CDCl3): δ (ppm) 167.9, 159.6, 143.0, 142.4, 136.8, 132.9, 132.7, 131.3,
130.9, 129.6, 129.1, 129.0, 128.4, 128.3, 127.9, 127.8, 125.7, 116.7, 113.7, 109.8,
55.3, 52.0; IR (KBr, cmꢀ1): 2219, 1726, 1639, 1609, 1514, 1493, 1431, 1383, 1294,
1245, 1181, 1155, 1119, 1022, 992, 843, 818, 765, 694, 622, 575, 529, 482; HRMS
(ESI): m/z [M+Na]+ calcd for C26H19NNaO3: 416.1257; found: 416.1252.
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methyl 4ꢀcyanoꢀ1ꢀ(4ꢀfluorophenyl)ꢀ3ꢀphenylꢀ2ꢀnaphthoate (4d): Yield 69% (131.6
mg); white solid; m.p. 156–158 °C; 1H NMR (600 MHz, CDCl3): δ (ppm) 8.40 (d, J =
8.4 Hz, 1H), 7.78 (t, J = 7.8 Hz, 1H), 7.66 (d, J = 8.4 Hz, 1H), 7.59 (t, J = 7.8 Hz, 1H),
7.51–7.47 (m, 5H), 7.38–7.36 (m, 2H), 7.20 (t, J = 8.6 Hz, 2H), 3.26 (s, 3H); 13C
NMR (100 MHz, CDCl3): δ (ppm) 167.3, 162.5 (d, JCꢀF = 230 Hz), 142.7, 141.2,
136.4, 132.7 (d, JCꢀF = 27.8 Hz), 131.9 (d, JCꢀF =3.5 Hz), 131.4, 131.3, 130.8, 129.6,
129.5, 128.9, 128.9, 128.3, 127.9, 127.3, 125.6, 116.3, 115.3 (d, JCꢀF =21.5 Hz), 110.2,
52.0; IR (KBr, cmꢀ1):2222, 1733, 1638, 1605, 1512, 1494, 1433, 1383, 1304, 1228,
1186, 1154, 1116, 1044, 1016, 989, 903, 847, 819, 798, 767, 692, 622, 573, 537;
HRMS (ESI): m/z [M+H]+ calcd for C25H17FNO2: 382.1238; found: 382.1234.
methyl 1ꢀ(4ꢀchlorophenyl)ꢀ4ꢀcyanoꢀ3ꢀphenylꢀ2ꢀnaphthoate (4e): Yield 70% (139.3
mg); white solid; m.p. 193–194 °C; 1H NMR (600 MHz, CDCl3): δ (ppm) 8.40 (d, J =
8.4 Hz, 1H), 7.78 (t, J = 7.6 Hz, 1H), 7.65 (d, J = 8.4 Hz, 1H), 7.59 (t, J = 7.8 Hz, 1H),
7.53–7.43 (m, 7H), 7.34 (d, J = 8.4 Hz, 2H), 3.27 (s, 3H); 13C NMR (100 MHz,
CDCl3): δ (ppm) 167.2, 142.7, 140.9, 136.3, 134.5, 134.5, 132.6, 132.5, 130.9, 130.6,
129.6, 128.9, 128.9, 128.4, 128.2, 128.0, 127.2, 125.6, 116.3, 110.3, 52.1; IR (KBr,
cmꢀ1): 2225, 1734, 1634, 1487, 1434, 1306, 1233, 1185, 1153, 1118, 1044, 1015, 989,
903, 843, 817, 769, 730, 699, 622, 571, 517; HRMS (ESI): m/z [M+Na]+ calcd for
C25H16ClNNaO2: 420.0762; found: 420.0755.
methyl 4ꢀcyanoꢀ1ꢀ(3,4ꢀdichlorophenyl)ꢀ3ꢀphenylꢀ2ꢀnaphthoate (4f): Yield 63%
(136.2 mg); white solid; m.p. 140–141 °C; 1H NMR (600 MHz, CDCl3): δ (ppm) 8.41
(d, J = 8.4 Hz, 1H), 7.82–7.79 (m, 1H), 7.65–7.61 (m, 2H), 7.59 (d, J = 8.4 Hz, 1H),
7.53–7.51 (m, 1H), 7.51–7.46 (m, 5H), 7.25–7.24 (m, 1H), 3.30 (s, 3H); 13C NMR
(100 MHz, CDCl3): δ (ppm) 167.0, 142.7, 139.4, 136.2, 135.9, 132.9, 132.6, 132.5,
132.4, 131.4, 130.3, 130.2, 129.7, 129.0, 128.8, 128.3, 128.3, 126.9, 125.7, 116.1,
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110.7, 52.2; IR (KBr, cmꢀ1): 2221, 1731, 1638, 1496, 1408, 1384, 1307, 1222, 1186,
1153, 1122, 1044, 1016, 958, 902, 818, 766, 690, 623, 569; HRMS (ESI): m/z
[M+Na]+ calcd for C25H15Cl2NNaO2: 454.0372; found: 454.0366.
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methyl 1ꢀ(3ꢀbromophenyl)ꢀ4ꢀcyanoꢀ3ꢀphenylꢀ2ꢀnaphthoate (4g): Yield 75% (165.9
mg); white solid; m.p. 153–155 °C; 1H NMR (600 MHz, CDCl3): δ (ppm) 8.40 (d, J =
8.4 Hz, 1H), 7.79–7.77 (m, 1H), 7.66 (d, J = 8.4 Hz, 1H), 7.63–7.59 (m, 2H),
7.58–7.56 (m, 1H), 7.52–7.47 (m, 5H), 7.38 (t, J = 7.8 Hz, 1H), 7.35–7.33 (m, 1H),
3.28 (s, 3H); 13C NMR (150 MHz, CDCl3): δ (ppm) 167.5, 143.0, 140.7, 138.3, 136.5,
132.7, 132.7, 132.5, 131.7, 130.6, 129.8, 129.1, 129.0, 128.5, 128.4, 128.3, 127.4,
125.8, 122.3, 116.4, 110.6, 52.1; IR (KBr, cmꢀ1): 2221, 1725, 1638, 1556, 1496, 1437,
1412, 1307, 1232, 1187, 1154, 1120, 1075, 1044, 1016, 993, 955, 917, 849, 802, 764,
722, 699, 636, 576; HRMS (ESI): m/z [M+Na]+ calcd for C25H16BrNNaO2: 464.0257;
found: 464.0251.
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methyl 1ꢀ(4ꢀbromophenyl)ꢀ4ꢀcyanoꢀ3ꢀphenylꢀ2ꢀnaphthoate (4h): Yield 56% (123.8
mg); white solid; m.p. 207–207 °C; 1H NMR (600 MHz, CDCl3): δ (ppm) 8.40 (d, J =
8.4 Hz, 1H), 7.78 (t, J = 7.2 Hz, 1H), 7.65–7.63 (m, 3H), 7.59 (t, J = 7.8 Hz, 1H),
7.49–7.47 (m, 5H), 7.27 (d, J = 7.8 Hz, 2H), 3.27 (s, 3H); 13C NMR (100 MHz,
CDCl3): δ (ppm) 167.3, 142.8, 141.0, 136.4, 135.0, 132.6, 131.4, 131.2, 130.6, 129.6,
129.0, 128.9, 128.3, 128.1, 127.3, 125.7, 122.9, 116.4, 110.4, 52.2; IR (KBr, cmꢀ1):
1733, 1638, 1619, 1431, 1385, 1305, 1185, 1151, 1118, 1044, 1013, 816, 768, 726,
689, 618; HRMS (ESI): m/z [M+Na]+ calcd for C25H16BrNNaO2: 464.0257; found:
464.0251.
methyl 4ꢀcyanoꢀ1ꢀ(furanꢀ2ꢀyl)ꢀ3ꢀphenylꢀ2ꢀnaphthoate (4i): Yield 81% (143.1 mg);
yellow solid; m.p. 119–120 °C; 1H NMR (600 MHz, CDCl3): δ (ppm) 8.38 (d, J = 8.4
Hz, 1H), 8.15 (d, J = 8.4 Hz, 1H), 7.80 (t, J = 7.8 Hz, 1H), 7.69 (d, J = 7.2 Hz, 1H),
7.67 (s, 1H), 7.51–7.45 (m, 5H), 6.74 (d, J = 3.6 Hz, 1H), 6.64–6.61 (m, 1H), 3.45 (s,
3H); 13C NMR (100 MHz, CDCl3): δ (ppm) 167.5, 148.1, 143.8, 142.9, 136.2, 132.7,
132.6, 130.9, 130.1, 129.6, 128.9, 128.8, 128.3, 128.2, 127.0, 125.6, 116.2, 113.0,
111.5, 111.0, 52.3; IR (KBr, cmꢀ1): 1738, 1638, 1410, 1385, 1305, 1185, 1151, 1119,
1044, 1016, 957, 816, 762, 690, 620, 568; HRMS (ESI): m/z [M+Na]+ calcd for
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C23H15NNaO3: 376.0944; found: 376.0940.
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methyl 4ꢀcyanoꢀ3ꢀphenylꢀ1ꢀ(thiophenꢀ2ꢀyl)ꢀ2ꢀnaphthoate (4j): Yield 74% (136.7
mg); white solid; m.p. 165–166 °C; 1H NMR (600 MHz, CDCl3): δ (ppm) 8.38 (d, J =
8.4 Hz, 1H), 7.96 (d, J = 8.4 Hz, 1H), 7.78 (t, J = 8.4 Hz, 1H), 7.63 (t, J = 7.8 Hz, 1H),
7.55 (t, J = 3.6 Hz, 1H), 7.51–7.47 (m, 5H), 7.18 (d, J = 3.0 Hz, 2H), 3.34 (s, 3H); 13C
NMR (100 MHz, CDCl3): δ (ppm) 167.2, 142.6, 136.3, 135.6, 135.0, 134.1, 132.4,
131.7, 129.6, 129.6, 128.9, 128.9, 128.3, 128.1, 127.6, 127.3, 126.9, 125.5, 116.3,
110.9, 52.1; IR (KBr, cmꢀ1): 2224, 1735, 1638, 1493, 1434, 1385, 1304, 1223, 1185,
1152, 1126, 1044, 1016, 982, 846, 816, 762, 694, 618, 568; HRMS (ESI): m/z
[M+H]+ calcd for C23H16NO2S: 370.0896; found: 370.0891.
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methyl 4ꢀcyanoꢀ1ꢀ(1ꢀmethylꢀ3a,7aꢀdihydroꢀ1Hꢀindolꢀ3ꢀyl)ꢀ3ꢀphenylꢀ2ꢀnaphthoate
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(4k): Yield 67% (139.5 mg); yellow solid; m.p. 237–239 °C; H NMR (600 MHz,
CDCl3): δ (ppm) 8.00 (d, J = 8.4 Hz, 1H), 7.96 (d, J = 8.4 Hz, 1H), 7.69 (t, J = 7.8 Hz,
1H), 7.52–7.44 (m, 8H), 7.32 (t, J = 7.8 Hz, 1H), 7.24 (d, J = 7.8 Hz, 1H), 7.14 (t, J =
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7.2 Hz, 1H), 3.95 (s, 3H), 3.66 (s, 3H); C NMR (100 MHz, CDCl3): δ (ppm) 168.3,
142.2, 138.3, 137.1, 136.7, 131.3, 131.3, 130.8, 129.9, 129.9, 129.1, 128.6, 128.5,
128.2, 127.8, 127.2, 125.2, 122.2, 120.2, 120.0, 117.8, 111.6, 110.1, 109.7, 52.5, 33.4.;
IR (KBr, cmꢀ1): 1729, 1638, 1407, 1385, 1299, 1222, 1185, 1151, 1125, 1044, 1015,
816, 757, 690, 620, 569; HRMS (ESI): m/z [M+H]+ calcd for C28H21N2O2: 417.1598;
found: 417.1599.
methyl 4ꢀcyanoꢀ3ꢀphenylꢀ[1,1'ꢀbinaphthalene]ꢀ2ꢀcarboxylate (4l): Yield 65%
(134.4 mg); white solid; m.p. 167–168 °C; 1H NMR (600 MHz, CDCl3): δ (ppm) 8.44
(d, J = 8.4 Hz, 1H), 7.97 (d, J = 8.4 Hz, 1H), 7.93 (d, J = 8.4 Hz, 1H), 7.74 (t, J = 7.8
Hz, 1H), 7.57 (t, J = 7.8 Hz, 3H), 7.50–7.41 (m, 6H), 7.36–7.34 (m, 2H), 7.28 (d, J =
8.4 Hz, 1H), 3.00 (s, 3H); 13C NMR (100 MHz, CDCl3): δ (ppm) 167.2, 143.0, 141.2,
136.6, 133.7, 133.4, 133.0, 132.4, 132.1, 131.4, 129.6, 129.0, 128.9, 128.9, 128.3,
128.0, 127.9, 127.9, 127.7, 126.4, 126.0, 126.0, 125.6, 124.9, 116.6, 110.4, 51.8; IR
(KBr, cmꢀ1): 1729, 1637, 1408, 1385, 1303, 1185, 1151, 1125, 1044, 1015, 957, 816,
762, 688, 621, 567; HRMS (ESI): m/z [M+H]+ calcd for C29H20NO2: 414.1489; found:
414.1483.
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methyl 4ꢀcyanoꢀ6,7ꢀdimethoxyꢀ1,3ꢀdiphenylꢀ2ꢀnaphthoate (5a): Yield 79% (167.3
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mg); white solid; m.p. 220–221 °C; H NMR (600 MHz, CDCl3): δ (ppm) 7.60 (s,
1H), 7.52 – 7.43 (m, 7H), 7.41 – 7.36 (m, 2H), 6.91 (s, 1H), 4.10 (s, 3H), 3.76 (s, 3H),
3.21 (s, 3H); 13C NMR (100 MHz, CDCl3): δ (ppm) 167.8, 152.3, 150.5, 140.8, 140.6,
136.9, 136.7, 130.9, 129.6, 129.3, 129.0, 128.6, 128.3, 128.2, 126.6, 117.1, 108.0,
105.9, 104.0, 56.4, 55.8, 51.9; IR (KBr, cmꢀ1): 2221, 1726, 1620, 1570, 1508, 1469,
1430, 1385, 1342, 1265, 1242, 1213, 1186, 1127, 1033, 1011, 979, 880, 841, 765, 728,
703; HRMS (ESI): m/z [M+H]+ calcd for C27H22NO4: 424.1543; found: 424.1543.
methyl 4ꢀcyanoꢀ6,7ꢀdimethoxyꢀ3ꢀphenylꢀ1ꢀ(pꢀtolyl)ꢀ2ꢀnaphthoate (5b): Yield 81%
(177.2 mg); white solid; m.p. 235–236 °C; 1H NMR (600 MHz, CDCl3): δ (ppm) 7.59
(s, 1H), 7.51–7.42 (m, 5H), 7.30–7.26 (m, 4H), 6.96 (s, 1H), 4.10 (s, 3H), 3.78 (s, 3H),
3.23 (s, 3H), 2.44 (s, 3H); 13C NMR (100 MHz, CDCl3): δ (ppm) 168.0, 152.2, 150.4,
140.8, 138.0, 137.0, 133.6, 131.0, 129.6, 129.2, 129.0, 128.9, 128.6, 128.2, 126.8,
117.2, 107.8, 106.0, 104.0, 56.4, 55.9, 51.9, 21.6; IR (KBr, cmꢀ1): 2215, 1732, 1620,
1572, 1510, 1470, 1432, 1385, 1340, 1264, 1240, 1214, 1183, 1152, 1127, 1042, 1018,
983, 882, 838, 816, 759, 732, 703, 568, 527; HRMS (ESI): m/z [M+Na]+ calcd for
C28H23NNaO4: 460.1519; found: 460.1516.
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methyl 4ꢀcyanoꢀ1ꢀ(4ꢀfluorophenyl)ꢀ6,7ꢀdimethoxyꢀ3ꢀphenylꢀ2ꢀnaphthoate (5c):
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Yield 82% (181.0 mg); white solid; m.p. 239–240 °C; H NMR (600 MHz, CDCl3): δ
(ppm) 7.60 (s, 1H), 7.51–7.43 (m, 4H), 7.41–7.33 (m, 2H), 7.20 (t, J = 8.4 Hz, 2H),
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6.85 (s, 1H), 4.11 (s, 3H), 3.78 (s, 3H), 3.24 (s, 3H); C NMR (100 MHz, CDCl3): δ
(ppm) 167.8, 162.4 (d, JC,F = 246 Hz), 152.4, 150.7, 140.8, 139.4, 136.8, 132.6 (d, JC,F
= 3.5 Hz), 131.2 (d, JC,F = 8.1 Hz), 129.6, 129.0, 128.7, 128.2, 126.7, 117.0, 115.4 (d,
JC,F = 21.4 Hz), 108.2, 105.5, 104.1, 56.4, 55.9, 52.0; IR (KBr, cmꢀ1): 2217, 1735,
1622, 1508, 1469, 1432, 1385, 1343, 1265, 1243, 1216, 1186, 1128, 1046, 1015, 983,
880, 845, 817, 796, 757, 730, 698, 568, 527; HRMS (ESI): m/z [M+Na]+ calcd for
C27H20FNNaO4: 464.1269; found: 464.1269.
methyl 1ꢀ(4ꢀchlorophenyl)ꢀ4ꢀcyanoꢀ6,7ꢀdimethoxyꢀ3ꢀphenylꢀ2ꢀnaphthoate (5d):
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Yield 75% (171.7 mg); white solid; m.p. 242–243 °C; H NMR (600 MHz, CDCl3): δ
(ppm) 7.60 (s, 1H), 7.52–7.43 (m, 7H), 7.34 (d, J = 8.4 Hz, 2H), 6.84 (s, 1H), 4.10 (s,
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3H), 3.79 (s, 3H), 3.24 (s, 3H); C NMR (100 MHz, CDCl3): δ (ppm) 167.7, 152.4,
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150.7, 140.8, 139.2, 136.8, 135.1, 134.4, 130.9, 130.7, 129.6, 129.0, 128.7, 128.5,
128.2, 126.5, 116.9, 108.4, 105.4, 104.1, 56.4, 56.0, 52.0; IR (KBr, cmꢀ1): 2359, 2217,
1738, 1619, 1572, 1503, 1469, 1431, 1384, 1343, 1243, 1242, 1213, 1186, 1128, 1046,
1016, 880, 845, 815, 756, 727, 699, 574; HRMS (ESI): m/z [M+H]+ calcd for
C27H21ClNO4: 458.1154; found: 458.1151.
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methyl 4ꢀcyanoꢀ1,3ꢀdiphenylanthraceneꢀ2ꢀcarboxylate (5e): Yield 66% (136.5 mg);
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yellow solid; m.p. 318–319 °C; H NMR (600 MHz, CDCl3): δ (ppm) 8.97 (s, 1H),
8.26 (s, 1H), 8.13 (d, J = 8.4 Hz, 1H), 7.90 (d, J = 8.4 Hz, 1H), 7.62 (t, J = 7.2 Hz,
1H), 7.59–7.54 (m, 5H), 7.54–7.49 (m, 4H), 7.49–7.45 (m, 2H), 3.26 (s, 3H); 13C
NMR (100 MHz, CDCl3): δ (ppm) 167.6, 143.4, 142.8, 136.8, 136.4, 133.1, 132.3,
131.6, 129.6, 129.1, 128.9, 128.9, 128.6, 128.5, 128.4, 128.3, 128.2, 128.0, 127.7,
127.5, 126.7, 124.6, 116.9, 109.9, 52.0; IR (KBr, cmꢀ1): 2361, 2225, 1738, 1638, 1428,
1385, 1288, 1186, 1126, 1043, 1014, 815, 757, 702, 618, 568, 546; HRMS (ESI): m/z
[M+Na]+ calcd for C29H19NNaO2: 436.1308; found: 436.1308.
methyl 4ꢀcyanoꢀ3ꢀphenylꢀ1ꢀ(pꢀtolyl)anthraceneꢀ2ꢀcarboxylate (5f): Yield 51%
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(109.0 mg); yellow solid; m.p. 298–301 °C; H NMR (600 MHz, CDCl3): δ (ppm)
8.95 (s, 1H), 8.29 (s, 1H), 8.12 (d, J = 8.4 Hz, 1H), 7.90 (d, J = 8.4 Hz, 1H), 7.61 (t, J
= 7.2 Hz, 1H), 7.57–7.55 (m, 2H), 7.54–7.48 (m, 4H), 7.35 (s, 4H), 3.27 (s, 3H), 2.50
(s, 3H); 13C NMR (100 MHz, CDCl3): δ (ppm) 167.7, 143.4, 143.0, 138.3, 136.8,
133.3, 133.1, 132.2, 131.6, 129.5, 129.3, 129.1, 128.9, 128.9, 128.8, 128.4, 128.3,
128.0, 127.8, 127.5, 126.6, 124.6, 117.0, 109.7, 52.0, 21.6; IR (KBr, cmꢀ1): 1738,
1638, 1427, 1385, 1290, 1218, 1185, 1152, 1118, 1043, 1015, 815, 755, 690, 621, 567;
HRMS (ESI): m/z [M+Na]+ calcd for C30H21NNaO2: 450.1465; found: 450.1459.
methyl 4ꢀcyanoꢀ1ꢀ(4ꢀfluorophenyl)ꢀ3ꢀphenylanthraceneꢀ2ꢀcarboxylate (5g): Yield
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53% (114.3 mg); yellow solid; m.p. 298–299 °C; H NMR (600 MHz, CDCl3): δ
(ppm) 8.96 (s, 1H), 8.20 (s, 1H), 8.12 (d, J = 8.4 Hz, 1H), 7.90 (d, J = 8.4 Hz, 1H),
7.62 (t, J = 7.2 Hz, 1H), 7.58–7.54 (m, 3H), 7.53–7.49 (m, 3H), 7.46–7.44 (m, 2H),
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7.27–7.24 (m, 2H), 3.28 (s, 3H); C NMR (100 MHz, CDCl3): δ (ppm) 167.5, 162.6
(d, JC,F = 246.3 Hz), 143.2, 141.6, 136.6, 133.1, 132.3, 132.1 (d, JC,F = 3.5 Hz), 131.8,
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131.4 (d, JC,F = 8.2 Hz), 129.0, 128.9, 128.7, 128.6, 128.3, 128.3, 128.1, 128.0, 127.6,
127.4, 126.8, 124.7, 116.8, 115.4 (d, JC,F = 21.4 Hz), 110.1, 52.1; IR (KBr, cmꢀ1):
2222, 1737, 1640, 1604, 1508, 1431, 1383, 1287, 1231, 1186, 1155, 1116, 1043, 1014,
985, 885, 850, 815, 755, 704, 600, 554; HRMS (ESI): m/z [M+Na]+ calcd for
C29H18FNNaO2: 454.1214; found: 454.1200.
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methyl 1ꢀ(4ꢀchlorophenyl)ꢀ4ꢀcyanoꢀ3ꢀphenylanthraceneꢀ2ꢀcarboxylate (5h): Yield
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58% (129.9 mg); yellow solid; m.p. 310–311 °C; H NMR (600 MHz, CDCl3): δ
(ppm) 8.96 (s, 1H), 8.19 (s, 1H), 8.13 (d, J = 8.4 Hz, 1H), 7.91 (d, J = 8.4 Hz, 1H),
7.63 (t, J = 8.4 Hz, 1H), 7.57–7.49 (m, 8H), 7.42 (d, J = 7.8 Hz, 2H), 3.28 (s, 3H); 13C
NMR (100 MHz, CDCl3): δ (ppm) 167.4, 143.2, 141.3, 136.6, 134.7, 134.7, 133.1,
132.3, 131.7, 131.0, 129.0, 129.0, 128.9, 128.5, 128.4, 128.3, 128.0, 127.7, 127.3,
126.9, 124.8, 116.7, 110.2, 52.1; IR (KBr, cmꢀ1): 2362, 2227, 1736, 1639, 1488, 1430,
1289, 1195, 1167, 1105, 1041, 1015, 987, 858, 816, 753, 701, 549; HRMS (ESI): m/z
[M+H]+ calcd for C29H18ClNNaO2: 470.0918; found: 470.0914.
ethyl 4ꢀcyanoꢀ1,3ꢀdiphenylꢀ2ꢀnaphthoate (5i): Yield 80% (151.0 mg); white solid;
m.p. 94–95 °C; 1H NMR (600 MHz, CDCl3): δ (ppm) 8.39 (d, J = 8.4 Hz, 1H), 7.76 (t,
J = 7.2 Hz, 1H), 7.69 (d, J = 8.4 Hz, 1H), 7.57 (t, J = 7.8 Hz, 1H), 7.54 –7.52 (m, 2H),
7.51–7.47 (m, 6H), 7.1–7.39 (m, 2H), 3.72 (q, J = 7.2 Hz, 2H), 0.72 (t, J = 7.2 Hz,
3H); 13C NMR (100 MHz, CDCl3): δ (ppm) 166.9, 142.8, 142.2, 136.6, 136.1, 132.7,
132.5, 130.8, 129.6, 129.4, 129.0, 128.8, 128.3, 128.2, 128.0, 127.7, 127.5, 125.5,
116.5, 110.0, 61.2, 13.5; IR (KBr, cmꢀ1): 1729, 1637, 1409, 1384, 1305, 1226, 1182,
1151, 1117, 1044, 1013, 817, 763, 690, 622, 569; HRMS (ESI): m/z [M+Na]+ calcd
for C26H19NNaO2: 400.1308; found: 400.1305.
dimethyl 1ꢀcyanoꢀ4ꢀphenylnaphthaleneꢀ2,3ꢀdicarboxylate (5j): Yield 51% (88.0
mg); white solid; m.p. 162–164 °C; 1H NMR (600 MHz, CDCl3): δ (ppm) 8.48 (d, J =
8.4 Hz, 1H), 7.86–7.78 (m, 1H), 7.69 (d, J = 8.4 Hz, 1H), 7.65–7.63 (m, 1H),
7.52–7.49 (m, 3H), 7.33–7.31 (m, 2H), 4.06 (s, 3H), 3.55 (s, 3H); 13C NMR (150
MHz, CDCl3): δ (ppm) 167.4, 165.3, 144.0, 135.7, 132.9, 132.4, 130.4, 130.2, 129.7,
129.5, 128.7, 128.3, 128.0, 126.5, 115.4, 110.6, 53.5, 52.5; IR (KBr, cmꢀ1): 2362,
1728, 1638, 1432, 1384, 1306, 1260, 1220, 1185, 1128, 1044, 1015, 972, 815, 762,
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691, 610, 570; HRMS (ESI): m/z [M+Na]+ calcd for C21H15NNaO4: 368.0893; found:
368.0897.
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methyl 4ꢀcyanoꢀ1ꢀphenylꢀ2ꢀnaphthoate (5k): Yield 78% (112.0 mg); white solid;
m.p. 154–156 °C; 1H NMR (600 MHz, CDCl3): δ (ppm) 8.41 (s, 1H), 8.32 (d, J = 7.8
Hz, 1H), 7.78–7.76 (m, 1H), 7.67 (d, J = 8.6 Hz, 1H), 7.57–7.55 (m, 1H), 7.53–7.50
(m, 3H), 7.28–7.24 (m, 2H), 3.66 (s, 3H); 13C NMR (150 MHz, CDCl3): δ (ppm)
166.6, 146.8, 137.3, 133.2, 132.6, 132.4, 130.0, 129.0, 128.7, 128.1, 128.1, 127.4,
125.2, 117.1, 110.1, 52.4; IR (KBr, cmꢀ1): 1638, 1411, 1385, 1302, 1220, 1185, 1151,
1125, 1044, 1015, 816, 765, 689, 621, 569; HRMS (ESI): m/z [M+Na]+ calcd for
C19H13NNaO2: 310.0839; found: 310.0838.
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ethyl 4ꢀcyanoꢀ1ꢀphenylꢀ2ꢀnaphthoate (5l): Yield 42% (65.2 mg); white solid; m.p.
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118–119 °C; H NMR (600 MHz, CDCl3): δ (ppm) 8.40 (s, 1H), 8.32 (d, J = 8.4 Hz,
1H), 7.77 (t, J = 7.8 Hz, 1H), 7.68 (d, J = 8.4 Hz, 1H), 7.56 (t, J = 7.8 Hz, 1H),
7.52–7.46 (m, 3H), 7.29–7.26 (m, 2H), 4.09 (q, J = 7.2 Hz, 2H), 1.00 (t, J = 7.2 Hz,
3H); 13C NMR (150 MHz, CDCl3): δ (ppm) 166.5, 146.4, 137.6, 133.2, 132.6, 132.5,
129.9, 129.1, 128.7, 128.1, 128.1, 128.0, 125.2, 117.2, 110.1, 61.5, 13.6; IR (KBr,
cmꢀ1):1708, 1638, 1414, 1379, 1338, 1256, 1220, 1184, 1151, 1117, 1044, 1018, 901,
864, 816, 763, 691, 622, 571, 529; HRMS (ESI): m/z [M+Na]+ calcd for
C20H15NNaO2: 324.0995; found: 324.0990.
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methyl 1,3ꢀdiphenylꢀ2ꢀnaphthoate (7a): Yield 81% (137.1 mg); oil; H NMR (600
MHz, CDCl3): δ (ppm) 7.90 (d, J = 8.4 Hz, 1H), 7.87 (s, 1H), 7.60 (d, J = 8.4 Hz, 1H),
7.53 (d, J = 7.2 Hz, 1H), 7.51 (d, J = 7.2 Hz, 2H), 7.46 (d, J = 7.2 Hz, 2H), 7.39–7.44
(m, 6H), 7.36 (t, J = 7.8 Hz, 1H), 3.30 (s, 3H); 13C NMR (150 MHz, CDCl3): δ (ppm)
169.6, 140.6, 138.3, 137.7, 136.6, 133.4, 131.8, 131.1, 130.1, 128.5, 128.4, 128.3,
128.05, 128.0, 127.7, 127.5, 127.1, 126.8, 126.6, 51.7; IR (KBr, cmꢀ1):1732, 1640,
1492, 1433, 1384, 1303, 1267, 1226, 1184, 1151, 1129, 1110, 1043, 1016, 959, 894,
817, 795, 757, 700, 604, 575; HRMS (ESI): m/z [M+Na]+ calcd for C24H18NaO2:
361.1199; found: 361.1199.
ethyl 1,3ꢀdiphenylꢀ2ꢀnaphthoate (7b): Yield 77% (135.7 mg); yellow solid; m.p.
68–69 °C; 1H NMR (600 MHz, CDCl3): δ (ppm) 7.90 (d, J = 8.4 Hz, 1H), 7.87 (s, 1H),
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5H), 7.37 (t, J = 7.2 Hz, 1H), 3.79 (q, J = 7.2 Hz, 2H), 0.76 (t, J = 7.2 Hz, 3H); C
NMR (150 MHz, CDCl3): δ (ppm) 169.0, 140.7, 138.2, 137.8, 136.7, 133.4, 131.9,
131.2, 130.2, 128.7, 128.4, 128.2, 128.0, 127.9, 127.7, 127.4, 127.1, 126.8, 126.6,
60.8, 13.4; IR (KBr, cmꢀ1):1726, 1491, 1446, 1420, 1384, 1301, 1264, 1227, 1184,
1152, 1131, 1107, 1039, 1015, 891, 855, 815, 796, 756, 701, 604, 578; HRMS (ESI):
m/z [M+Na]+ calcd for C25H20NaO2: 375.1356; found: 375.1358.
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methyl 6,7ꢀdimethoxyꢀ1,3ꢀdiphenylꢀ2ꢀnaphthoate (7c): Yield 84% (167.4 mg);
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white solid; m.p. 142–144 °C; H NMR (600 MHz, CDCl3): δ (ppm) 7.72 (s, 1H),
7.49 (d, J = 7.8 Hz, 2H), 7.46 (d, J = 7.2 Hz, 2H), 7.44–7.37 (m, 5H), 7.35 (t, J = 7.8
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Hz, 1H), 7.17 (s, 1H), 6.86 (s, 1H), 4.01 (s, 3H), 3.74 (s, 3H), 3.29 (s, 3H); C NMR
(100 MHz, CDCl3): δ (ppm) 169.6, 150.2, 149.7, 140.7, 138.1, 136.7, 135.1, 130.0,
129.7, 129.5, 128.4, 128.1, 127.9, 127.5, 127.1, 126.7, 106.2, 105.3, 56.0, 55.7, 51.6;
IR (KBr, cmꢀ1):1732, 1624, 1501, 1466, 1429, 1311, 1244, 1220, 1188, 1144, 1113,
1037, 1012, 899, 816, 752, 703, 621, 569; HRMS (ESI): m/z [M+Na]+ calcd for
C26H22NaO4: 421.1410; found: 421.1414.
methyl 1,3ꢀdiphenylanthraceneꢀ2ꢀcarboxylate (7d): Yield 56% (108.8 mg); yellow
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solid; m.p. 130–131 °C; H NMR (600 MHz, CDCl3): δ (ppm) 8.49 (s, 1H), 8.15 (s,
1H), 8.04 (s, 1H), 8.01 (d, J = 8.4 Hz, 1H), 7.84 (d, J = 8.4 Hz, 1H), 7.57–7.55 (m,
2H), 7.52 (t, J = 7.2 Hz, 2H), 7.50 (d, J = 7.2 Hz, 3H), 7.48–7.42 (m, 3H), 7.41–7.37
(m, 1H), 3.3 (s, 3H); 13C NMR (150 MHz, CDCl3): δ (ppm) 169.7, 140.7, 138.6,
137.9, 136.0, 132.3, 132.0, 131.4, 131.3, 130.2, 129.6, 128.7, 128.6, 128.5, 128.4,
128.1, 127.9, 127.8, 127.5, 126.6, 126.4, 126.3, 125.7, 51.7; IR (KBr, cmꢀ1):1729,
1638, 1411, 1385, 1301, 1184, 1150, 1126, 1044, 1015, 957, 816, 757, 691, 620, 567;
HRMS (ESI): m/z [M+H]+ calcd for C28H21O2: 389.1536; found: 389.1538.
methyl 1ꢀ(4ꢀmethoxyphenyl)ꢀ3ꢀphenylꢀ2ꢀnaphthoate (7e): Yield 79% (145.5 mg);
yellow solid; m.p. 144–145 °C; 1H NMR (600 MHz, CDCl3): δ (ppm) 7.89 (d, J = 8.4
Hz, 1H), 7.85 (s, 1H), 7.64 (d, J = 8.5 Hz, 1H), 7.55–7.50 (m, 3H), 7.42 (t, J = 7.2 Hz,
3H), 7.36 (t, J = 7.2 Hz, 1H), 7.33 (d, J = 7.8 Hz, 2H), 7.00 (d, J = 7.8 Hz, 2H), 3.87
(s, 3H), 3.33 (s, 3H); 13C NMR (100 MHz, CDCl3): δ (ppm) 169.5, 158.9, 140.5,
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137.8, 136.4, 133.3, 131.9, 131.3, 131.1, 129.7, 128.4, 128.1, 128.1, 127.9, 127.3,
126.9, 126.7, 126.4, 113.4, 55.3, 51.8; IR (KBr, cmꢀ1):1732, 1607, 1513, 1493, 1435,
1384, 1288, 1249, 1183, 1152, 1133, 1109, 1039, 995, 965, 894, 860, 841, 795, 753,
704, 605, 578; HRMS (ESI): m/z [M+Na]+ calcd for C25H20NaO3: 391.1305; found:
391.1308.
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ethyl 1ꢀ(4ꢀmethoxyphenyl)ꢀ3ꢀphenylꢀ2ꢀnaphthoate (7f): Yield 70% (133.9 mg);
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white solid; m.p. 122–123 °C; H NMR (600 MHz, CDCl3): δ (ppm) 7.88 (d, J = 8.4
Hz, 1H), 7.85 (s, 1H), 7.63 (d, J = 8.4 Hz, 1H), 7.53–7.51 (m, 3H), 7.41 (t, J = 7.2 Hz,
3H), 7.37 (d, J = 7.2 Hz, 1H), 7.34 (d, J = 8.4 Hz, 2H), 7.00 (d, J = 8.4 Hz, 2H), 3.87
(s, 3H), 3.82 (q, J = 7.2 Hz, 2H), 0.80 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz,
CDCl3): δ (ppm) 168.8, 158.9, 140.5, 137.7, 136.5, 133.2, 132.1, 131.4, 131.2, 129.8,
128.6, 128.1, 128.0, 127.9, 127.2, 126.8, 126.7, 126.3, 113.3, 60.8, 55.3, 13.7; IR
(KBr, cmꢀ1):1729, 1638, 1608, 1513, 1493, 1422, 1384, 1289, 1245, 1226, 1182, 1151,
1130, 1110, 1039, 1015, 887, 839, 816, 753, 702, 605, 577; HRMS (ESI): m/z
[M+H]+ calcd for C26H23O3: 383.1642; found: 383.1646.
methyl 6,7ꢀdimethoxyꢀ1ꢀ(4ꢀmethoxyphenyl)ꢀ3ꢀphenylꢀ2ꢀnaphthoate (7g): Yield 78%
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(167.1 mg); yellow solid; m.p. 175–177 °C; H NMR (600 MHz, CDCl3): δ (ppm)
7.70 (s, 1H), 7.49 (d, J = 7.2 Hz, 2H), 7.41 (t, J = 7.2 Hz, 2H), 7.36 (d, J = 7.2 Hz,
1H), 7.34 (d, J = 8.4 Hz, 2H), 7.17 (s, 1H), 7.00 (d, J = 9.0 Hz, 2H), 6.90 (s, 1H), 4.02
(s, 3H), 3.89 (s, 3H), 3.77 (s, 3H), 3.33 (s, 3H); 13C NMR (100 MHz, CDCl3): δ (ppm)
169.8, 158.7, 150.2, 149.7, 140.8, 136.4, 135.0, 130.9, 130.2, 130.2, 129.5, 128.4,
128.1, 127.0, 126.5, 113.4, 106.2, 105.3, 56.0, 55.8, 55.3, 51.7; IR (KBr, cmꢀ1):2362,
2339, 1737, 1623, 1504, 1465, 1428, 1290, 1245, 1221, 1182, 1148, 1112, 1039, 1013,
898, 850, 815, 763, 688, 570; HRMS (ESI): m/z [M+H]+ calcd for C27H25O5:
429.1697; found: 429.1698.
methyl 1ꢀ(4ꢀmethoxyphenyl)ꢀ3ꢀphenylanthraceneꢀ2ꢀcarboxylate (7h): Yield 65%
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(136.0 mg); yellow solid; m.p. 182–184 °C; H NMR (600 MHz, CDCl3): δ (ppm)
8.46 (s, 1H), 8.19 (s, 1H), 8.01–7.99 (m, 2H), 7.85 (d, J = 9.0 Hz, 1H), 7.55 (d, J = 7.2
Hz, 2H), 7.48 (t, J = 7.2 Hz, 1H), 7.44 (t, J = 7.2 Hz, 2H), 7.41 (d, J = 8.4 Hz, 2H),
7.38 (t, J = 7.8 Hz, 1H), 7.06 (d, J = 8.4 Hz, 2H), 3.92 (s, 3H), 3.36 (s, 3H); 13C NMR
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(100 MHz, CDCl3): δ (ppm) 169.5, 159.0, 140.6, 138.1, 135.9, 132.1, 131.8, 131.5,
131.2, 131.2, 129.9, 129.8, 128.6, 128.4, 128.2, 128.2, 127.7, 127.3, 126.4, 126.3,
126.1, 125.5, 113.5, 55.3, 51.8; IR (KBr, cmꢀ1):1730, 1637, 1504, 1425, 1385, 1288,
1224, 1183, 1149, 1126, 1043, 1015, 957, 898, 816, 753, 689, 621, 570; HRMS (ESI):
m/z [M+H]+ calcd for C29H23O3: 419.1642; found: 419.1642.
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methyl 8ꢀmethoxyꢀ1,3ꢀdiphenylꢀ2ꢀnaphthoate (7i): Yield 48% (88.4 mg); yellow oil;
1H NMR (600 MHz, CDCl3): δ (ppm) 7.81 (s, 1H), 7.49 (t, J = 8.4 Hz, 3H), , 7.44 (t, J
= 7.8 Hz, 1H), 7.40 (t, J = 7.8 Hz, 2H), 7.35 (t, J = 6.6 Hz, 2H), 7.31 (s, 4H), 6.77 (d,
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J = 7.8 Hz, 1H), 3.40 (s, 3H), 3.21 (s, 3H); C NMR (150 MHz, CDCl3): δ (ppm)
169.6, 157.2, 141.7, 140.3, 136.6, 136.5, 135.4, 133.2, 128.9, 128.6, 128.5, 128.2,
127.5, 126.4, 126.2, 122.5, 121.0, 106.9, 55.5, 51.5; IR (KBr, cmꢀ1):1727, 1563, 1435,
1266, 1251, 1119, 1108, 772, 758, 702; HRMS (ESI): C25H21O3: m/z [M+H]+ calcd
for: 369.1485; found: 369.1486.
methyl
6ꢀmethylꢀ1,3ꢀdiphenylꢀ2ꢀnaphthoate
(7j)/methyl
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7ꢀmethylꢀ1,3ꢀdiphenylꢀ2ꢀnaphthoate (7j'): Yield 59% (103.9 mg); yellow oil; H
NMR (600 MHz, CDCl3): δ (ppm) 7.82 (s, 1H), 7.80–7.78 (m, 2H), 7.66 (s, 1H),
7.51–7. 48 (m, 6H), 7.47–7.43 (m, 5H), 7.43–7.40 (m, 9H), 7.37–7.35 (m, 5H),
7.25–7.22 (m, 2H), 3.29 (s, 6H), 2.50 (s, 3H), 2.39 (s, 3H); 13C NMR (150 MHz,
CDCl3): δ (ppm) 169.7, 140.7, 140.7, 138.2, 137.9, 137.6, 137.0, 136.6, 136.5, 135.6,
133.7, 131.8, 131.7, 131.2, 130.9, 130.1, 130.0, 129.4, 129.3, 128.9, 128.5, 128.5,
128.5, 128.5, 128.3, 128.2, 127.9, 127.9, 127.8, 127.6, 127.4, 127.3, 127.0, 126.6,
125.6, 51.6, 21.9, 21.6; IR (KBr, cmꢀ1):1729, 1568, 1429, 1266, 1108, 774, 701;
HRMS (ESI): m/z [M+H]+ calcd for C25H21O2: 353.1536; found: 353.1535.
2ꢀ(2ꢀbenzoylphenyl)acetonitrile (8): Yield 83% (91.0 mg); oil; 1H NMR (600 MHz,
CDCl3): δ (ppm) 8.46 (s, 1H), 7.79 (d, J = 7.2 Hz, 2H), 7.65 (d, J = 7.2 Hz, 1H), 7.61
(t, J = 7.2 Hz, 1H), 7.57 (t, J = 7.8 Hz, 1H), 7.49–7.46 (m, 3H), 7.41 (t, J = 7.8 Hz,
13
1H), 3.99 (s, 2H); C NMR (150 MHz, CDCl3): δ (ppm) 197.0, 137.1, 136.6, 133.4,
131.6, 130.6, 130.2, 130.1, 129.8, 128.5, 127.4, 117.7, 21.8; IR (KBr, cmꢀ1):1713,
1667, 1493, 1433, 1384, 1329, 1285, 1186, 1151, 1125, 1044, 1016, 954, 816, 781,
756, 727, 689, 622, 570; HRMS (ESI): m/z [M+H]+ calcd for C15H12NO: 222.0913;
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found: 222.0915.
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6
7
8
2ꢀ(2ꢀbenzoylphenyl)ꢀ1ꢀphenylethanꢀ1ꢀone (9): Yield 77% (115.7 mg); yellow solid;
m.p. 50–51 °C; 1H NMR (600 MHz, CDCl3): δ (ppm) 9.06 (d, J = 9.0 Hz, 1H), 8.27 (s,
1H), 7.78 (d, J = 8.4 Hz, 1H), 7.70 (t, J = 8.4, 1H), 7.59 (d, J = 7.2 Hz, 2H), 7.52 (t, J
= 7.8 Hz, 1H), 7.43 (t, J = 7.2 Hz, 1H), 7.30–7.27 (m, 2H), 7.26–7.22 (m, 4H), 4.01 (s,
2H); 13C NMR (150 MHz, CDCl3): δ (ppm) 198.0, 167.4, 143.1, 137.4, 136.8, 135.8,
133.0, 132.6, 132.0, 130.5, 129.7, 128.6, 128.5, 128.1, 127.9, 127.5, 127.0, 126.6,
125.9, 52.4; IR (KBr, cmꢀ1):1732, 1665, 1598, 1493, 1431, 1384, 1340, 1286, 1231,
1184, 1151, 1130, 1113, 1044, 1018, 951, 882, 841, 816, 753, 702, 629, 571, 533;
HRMS (ESI): m/z [M+Na]+ calcd for C21H16NaO2: 323.1043; found: 323.1043.
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Supporting Information
Crystallographic data, and copies of 1H and 13C NMR spectra of compounds 4aꢀ4l,
5aꢀ5l and 7aꢀ7j. This material is available free of charge via the Internet at
http://pubs.acs.org.
Acknowledgments
We are grateful to the National Natural Science Foundation of China (Grants
21472056, 21772051), and the Doctoral Scientific Research Startup Foundation of
Yangtze University (No. 801090010135) for financial support. This work was also
supported by the Yangtze Youth Talents Fund (No. 2016cqn25).
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