Direct construction of xanthene and benzophenone derivatives via Br?nsted acid controlled Diels-Alder reaction of 3-vinylchromones and arynes

Article abstract of DOI:10.1016/j.tet.2016.11.028

A Br?nsted acid controlled Diels-Alder reaction of 3-vinylchromones with arynes has been developed. By employing different kinds and amounts of acid, 9-aryl-9H-xanthen-9-ols or ortho-hydroxybenzophenones could be controllably furnished in good yields in an atom- and step-economic manner.

Full text of DOI:10.1016/j.tet.2016.11.028

Accepted Manuscript
Direct construction of xanthene and benzophenone derivatives via Brønsted acid
controlled Diels-Alder reaction of 3-vinylchromones and arynes
Xu-Jiao Huang, Yuan Tao, Yue-Kun Li, Xin-Yan Wu, Feng Sha
PII:
S0040-4020(16)31172-3
10.1016/j.tet.2016.11.028
TET 28242
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 5 September 2016
Revised Date: 5 November 2016
Accepted Date: 8 November 2016
Please cite this article as: Huang X-J, Tao Y, Li Y-K, Wu X-Y, Sha F, Direct construction of xanthene
and benzophenone derivatives via Brønsted acid controlled Diels-Alder reaction of 3-vinylchromones
and arynes, Tetrahedron (2016), doi: 10.1016/j.tet.2016.11.028.
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ACCEPTED MANUSCRIPT
Graphical Abstract
Direct Construction of Xanthene and
Benzophenone Derivatives via Brønsted Acid
Controlled Diels-Alder Reaction of 3-
Vinylchromones and Arynes
Leave this area blank for abstract info.
Xu-Jiao Huang, Yuan Tao, Yue-Kun Li, Xin-Yan Wu,* and Feng Sha*

ACCEPTED MANUSCRIPT
Tetrahedron
journal homepage: www.elsevier.com
Direct Construction of Xanthene and Benzophenone Derivatives via Brønsted
Acid Controlled Diels-Alder Reaction of 3-Vinylchromones and Arynes
Xu-Jiao Huang, Yuan Tao, Yue-Kun Li, Xin-Yan Wu,* and Feng Sha*
Key Laboratory for Advanced Materials and Institute of Fine Chemicals, East China University of Science and Technology, Shanghai 200237, PR China
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
A Brønsted acid controlled Diels-Alder reaction of 3-vinylchromones with arynes has been
developed. By employing different kinds and amounts of acid, 9-aryl-9H-xanthen-9-ols or
ortho-hydroxybenzophenones could be controllably furnished in good yields in an atom- and
step-economic manner.
Available online
2016 Elsevier Ltd. All rights reserved
.
Keywords:
Arynes
3-Vinylchromones
Diels-Alder reaction
9-Xanthenols
2-Hydroxybenzophenones
1. Introduction
Previous Diels-Alder reaction involve 3-vinylchromone
R
O
R
O
O
Arynes are highly reactive intermediates and particular
building blocks in organic synthesis.1 Due to their low-lying
LUMO and unique structural properties, arynes can serve as
dienophiles in cycloaddition reactions to generate useful
polycyclic and ring-fused compounds.2 Especially, C-O, C-N
bonds could be constructed for the assembly of heterocyclic
compounds. Increasing number of synthetic strategies have been
developed to approach natural products and medicines by using
arynes to generate key cyclic intermediates.3
Silva
2005
+
NMe
O
O
O
O
O
NMe
O
EWG
-pyrrolidine
O
O
O
EWG
EWG
O
+
-MeOH
Bodwell
2008
O
N
H
OMe
OMe
OMe
MeO
OMe
O
O
Me
MeO
O
O
Me
O
O
Me
Many research groups, such as Suzuki group,4 Biju group,1c,2d-
MeO
MeO
-H2
Abozeid
2014
f,2h,5
and Larock group2c,6,9b,9d have reported the annulation
+
CO2Me
CO2Me
CO2Me
H
MeO2C
CO2Me
CO2Me
reactions of arynes to synthesize cyclic compounds. In 2009, our
group reported a three-component reaction of arynes, isocynides,
and terminal alkynes to generate polysubstituted pyridines and
isoquinolines in good yields.7 Recently, we introduced
vinylindoles and vinylpyrroles as dienes to react with arynes to
furnish benzocarbazoles and benzoindoles successfully.8
However, as revealed in the survey of reported literatures,9 the
formation of C-O bond via the oxa-Diels-Alder reaction of arynes
is quite difficult and still remains challenging.
This work:
R2
O
O
O
O
O
R1
R1
R1
+
R2
R2
R3
OH
R3
R3
R3
acid
R1
R1
OH
O
R3
R1
+
HO
R3
R2
OH
R3
R2
R2
R3
O
In the past decade, only a few research groups employed
substituted 3-vinylchromones in Diels-Alder reactions to
construct cyclic compounds. In 2005, Silva and coworkers
developed a Diels-Alder reaction of 3-vinylchromones with
reactive dienophile N-methylmaleimide.10 Then, Bodwell and
coworkers developed an inverse-electron-demand Diels-Alder
reaction of 3-vinylchromones with 1-(2,2-dimethoxyvinyl)
pyrrolidine.11 Sequently, in 2014, Abozeid and coworkers
O
Scheme 1. Related Diels-Alder reactions of 3-
vinylchromones.
reported another Diels-Alder reaction of 3-vinylchromone with
dimethyl acetylenedicarboxylate, furnishing biologically active
xanthone derivatives.12 In these elegant strategies, 3-
vinylchromones have been demonstrated to be able to work as

2
Tetrahedron
ACCEPTED MANUSCRIPT
Table 1. Optimization of the Reaction Conditions.a
normal dienes for the Diels-Alder reactions. To the best of our
knowledge, 3-vinylchromones functioning as oxa-1,3-dienes for
the oxa-Diels-Alde reaction have never been reported. Based on
our previous studies on arynes,7-8,13 herein, we wish to disclose
new routes of 3-vinylchromones with arynes via Diels-Alder
reactions to afford normal Diels-Alder annulations as well as
oxa-Diels-Alder annulations (Scheme 1).
Yield (%)b
2. Results and discussion
F- source
(equiv of 2a)
Acid
(equiv)
Entry
Initially, the reaction of ethyl (E)-3-(4-oxo-4H-chromen-3-
yl)acrylate 1a (1.0 equiv) and 2-(trimethylsilyl)phenyl triflate 2a
(3.0 equiv) was conducted in the presence of CsF (6.0 equiv) in
CH3CN at room temperature under a nitrogen atmosphere (Table
1, entry 1). The product ethyl 3-(9-hydroxy-9H-xanthen-9-yl)-1-
naphthoate 3a was isolated in 21% yield. Also, trace ammout of
9-phenoxy-9H-xanthene 4a and ortho-hydroxyl benzophenone
5a, and 10% of ortho-phenoxyl benzophenone 6a were obtained.
Surprisingly, when the reaction was conducted by using KF/18-
C-6 as the F- source in THF, the yield of 3a was enhanced to 41%
(entry 2). Changing the amount of benzyne precursor 2a from 3.0
equiv to 2.0 or 4.0 equiv did not improve the yield of 3a (entries
3-4). Considering that acid may promote the polarization process
of 1a to form oxa-1,3-diene (Scheme 1),14 we proposed to add
acid with low nucleophilic property to achieve better yield of 3a.
Trials with different amount of trifluoroacetic acid (TFA) were
then carried out (entries 5-8). The results indicated that the
application of TFA had improvement on the yields of both 3a
and 6a. Particularly, a highest yield of 3a was achieved by
proceeding the reaction with 1.1 equiv of TFA (54% yield, entry
7). Moreover, TfOH and p-TsOH.H2O were examined (entries 9-
10), and TfOH gave a better result of 3a in 65% yield. Several
Lewis acids were then screened to facilitate the polarization of 1a.
Unfotunately, none of the Lewis acid provided better results than
TfOH (entries 11-16). BF3·OEt2 was investigated and delivered
3a in 56% yield (entry 11). By using Y(OTf)3 or Yb(OTf)3, the
yields of 3a and 4a were low, although the yield of 6a was
decreased (entries 12-13). Reaction with Fe(OTf)3, FeCl3 or
ZnCl2 gave none of the products 3-6 (entries 14-16). On the other
hand, compared with 6a, compound 5a bearing a free hydroxyl
group is of greater potential utility in organic chemistry. It is
interesting that 5a was observed as the major product instead of
3a by increasing the amount of TFA to 2.0 equiv (53% yield,
entry 17). Pleasingly, increasing the amount of TFA to 2.5 equiv
led to the sole product 5a, and the yield was dramatically
improved to 94% (entry 18). However, further increasing the
amount of TFA to 3.0 or 3.5 equiv would slightly reduce the
yield of 5a (entries 19-20).
3a
4a
5a
6a
1c
2
CsF (3.0)
-
-
-
-
21
41
30
34
50
50
54
46
65
40
56
23
22
-
trace
10
trace
trace
trace
trace
trace
trace
trace
trace
trace
trace
trace
-
10
13
12
21
20
30
27
36
24
32
28
-
KF/18-C-6 (3.0)
KF/18-C-6 (2.0)
KF/18-C-6 (4.0)
3
trace
trace
trace
trace
trace
trace
trace
trace
trace
30
4
5
KF/18-C-6 (3.0) TFA (0.1)
KF/18-C-6 (3.0) TFA (0.55)
KF/18-C-6 (3.0) TFA (1.1)
KF/18-C-6 (3.0) TFA (1.5)
KF/18-C-6 (3.0) TfOH (1.1)
KF/18-C-6 (3.0) TsOHd(1.1)
KF/18-C-6 (3.0) BF3e (1.1)
6
7
8
9
10
11
12
13
14
15
16
17
18
19
f
KF/18-C-6 (3.0) Y(OTf)3
f
KF/18-C-6 (3.0) Yb(OTf)3
26
-
-
f
KF/18-C-6 (3.0) Fe(OTf)3
-
-
-
f
KF/18-C-6 (3.0) FeCl3
-
-
-
-
f
KF/18-C-6 (3.0) ZnCl2
-
-
-
-
KF/18-C-6 (3.0) TFA (2.0)
KF/18-C-6 (3.0) TFA (2.5)
KF/18-C-6 (3.0) TFA (3.0)
KF/18-C-6 (3.0) TFA (3.5)
17
-
trace
-
53
20
-
94
-
-
93
-
20
-
-
88
-
a
Unless otherwise specified, the reactions were conducted under a nitrogen
atmosphere using 1.0 equiv of 1a (0.3 mmol), 2a, 2.0 equiv of F- source
(based on 2a) and acid (based on 1a) in 3.0 mL of THF at room temperature
for 24 hours.
b Yield of isolated product based on 1a.
c The reaction was conducted in 3 mL of CH3CN.
d TsOH = p-TsOH.H2O.
e BF3 = BF3.Et2O
f 1.1 equiv of Lewis acid was used.
17-18 vs entries 14-16 and 19). However, the reaction of
substrate 1m bearing a methoxyl group gave lower yield (47%
yield, entry 13). The structure of the product 3d was further
established by the X-ray diffraction studies (Fig. 1).19
Considering the naphthalenyl moiety might better stabilize the
resonated intermediate oxa-1,3-diene (Scheme 1) than phenyl
moiety, 3-vinylbenzochromones 1t and 1u were synthesized and
examined in this reaction (Scheme 2). As expected, they were
well compatible and delivered the corresponding products 3t
(72% yield) and 3u (80% yield) with high selectivity. No
byproduct 4 or 5 was detected in the above process, and only
trace amount of 6t and 6u were detected. Moreover, substituted
aryne precursor 2b was then investigated to furnish 3v in 68%
yield as the sole product (Scheme 2).
Due to the frequent occurrence of the xanthene core in
biologically active molecules15-17 and phosphine ligands,18 we
then went on to examine the scope of the oxa-Diels-Alder
reaction with the optimized reaction conditions (Table 1, entry 9).
As illustrated in Table 2,
vinylchromones 1 were investigated, furnishing corresponding
9H-xanthen-9-ols smoothly in moderate-to-good yields.
a variety of substituted 3-
3
Employment of 1a-e bearing the carbonyl group (ester or acyl
group) could be conducted successfully, giving the corresponding
products 3a-e in 53-71% yields (entries 1-5). Cyano group could
also be introduced, with product 3f isolated in 46% yield (entry
6). Pleasingly, aryl substituted 3-vinylchromones (1g-k) were
readily accommodated in the reaction as well, giving products
3g-k in 60-78% yields (entries 7-11). Moreover, similar behavior
was observed for substrates 1 with either electron-donating or -
withdrawing group on the chromone ring (entries 12-19).
Generally, the electron-donating group substituted substrate 1
was more reactive in the oxa-Diels-Alder reaction (entries12 and
Inspired by the above results, we further focused on the
application scope to approach ortho-hydroxyl benzophenone 5,
which has been found as the core skeleton of many important
biologically active compounds,20 natural products,21 and
cosmetics.22 As summarized in Table 3, by following the
optimized conditions (Table 1, entry 18), all the reactions

Table 2. Reaction of substrates 1 with benzyne precursor 2a
ACCEPTED MANUSCRIPT
to afford products 3 and 6.a
Yield (%)b
Entry
R1
R2
3
6
1
CO2Et
H (1a)
65 (3a)
62 (3b)
53 (3c)
71 (3d)
60 (3e)
46 (3f)
78 (3g)
72 (3h)
62 (3i)
60 (3j)
65 (3k)
62 (3l)
47 (3m)
57 (3n)
52 (3o)
45 (3p)
60 (3q)
58 (3r)
55 (3s)
24 (6a)
25 (6b)
25 (6c)
27 (6d)
25 (6e)
30 (6f)
15 (6g)
24 (6h)
30 (6i)
35 (6j)
28 (6k)
24 (6l)
32 (6m)
17 (6n)
28 (6o)
21 (6p)
32 (6q)
35 (6r)
34 (6s)
2
CO2Bn
H (1b)
t
Scheme
2.
oxa-Diels-Alder
reaction
of
3-vinyl
3
CO2 Bu
H (1c)
benzochromones with arynes
4
COMe
COPh
H (1d)
Table 3. Reaction of substrates 1 with benzyne precursor 2a
to afford product 5.a
5
H (1e)
6
CN
H (1f)
7
Ph
H (1g)
8
4-MeOC6H4
4-BrC6H4
4-NO2C6H4
2-naphthyl
CO2Et
H (1h)
9
H (1i)
Entry
1
R1
R2
Yield (%)b
94 (5a)
84 (5b)
93 (5c)
94 (5d)
89 (5e)
67 (5f)
86 (5g)
87 (5h)
88 (5i)
83 (5j)
90 (5k)
93 (5l)
89 (5m)
82 (5n)
81 (5o)
70 (5p)
64 (5q)
92 (5r)
93 (5s)
82 (5t)
93 (5u)
82 (5v)
10
11
12
13c
14
15
16
17
18
19
H (1j)
CO2Et
CO2Bn
H (1a)
H (1k)
2
H (1b)
6-Me (1l)
6-MeO (1m)
6-F (1n)
6-Cl (1o)
6-Br (1p)
7-Me (1q)
7-MeO (1r)
7-Br (1s)
t
3
CO2 Bu
H (1c)
CO2Et
4
COMe
COPh
H (1d)
CO2Et
5
H (1e)
CO2Et
6
CN
H (1f)
CO2Et
7
Ph
H (1g)
CO2Et
8
4-MeOC6H4
4-BrC6H4
4-NO2C6H4
2-naphthyl
CO2Et
CO2Et
CO2Et
CO2Et
CO2Et
CO2Et
CO2Et
CO2Et
CO2Et
CO2Et
CO2Et
H (1h)
CO2Et
9
H (1i)
CO2Et
10
11
12
13
14
15
16
17
18
19
20
21
22
H (1j)
a
Unless otherwise specified, the reactions were conducted under a nitrogen
H (1k)
atmosphere using 1 (0.3 mmol), 2a (0.9 mmol), KF (1.8 mmol), 18-C-6 (1.8
mmol) and TfOH (0.33 mmol) in 3.0 mL of THF at room temperature for 24
hours.
5-MeO (1v)
6-Me (1l)
6-MeO (1m)
6-F (1n)
6-Cl (1o)
6-Br (1p)
7-Me (1q)
7-MeO (1r)
7-Br (1s)
4H-benzo[h] (1t)
1H-benzo[f] (1u)
b Yield of isolated product based on 1.
c The reaction was conducted for 48 hours.
a
The reactions were conducted using 1 (0.3 mmol), 2a (0.9 mmol), KF (1.8
mmol), 18-C-6 (1.8 mmol) and TFA (0.75 mmol) in 3.0 mL of THF at room
temperature for 24 hours under a nitrogen atmosphere.
b Yield of isolated product based on 1.
reaction (67% yield, entry 6). Importantly, different substitution
patterns on the aryl ring attached to the vinyl moiety were also
well tolerated, and the substitutents had little effect on the yields
(entries 7-11). In addition, a variety of substituted chromones 1v
and 1l-s were employed and the reactions proceeded smoothly
(entries 12-20). It was interesting to observe that the electron-rich
substituents usually led to higher yields (entries 12-14 and 18-19)
in comparison with the electron-deficient ones (entries 15-17 and
20). Interestingly, 3-vinylbenzochromones 1t and 1u could react
with aryne precursor 2a smoothly, and the products 5u and 5v
Fig. 1 X-ray crystal structure of 9H-xanthen-9-ol 3d
exhibited exclusive selectivity and provided the corresponding
products 5a-v in good-to-excellent yields (64-94%). Substrate 1c
bearing a tert-butyl substituent afforded the desired product 5c in
93% yield (entry 3). Benzoyl and acetyl substituted substrates 1d
and 1e showed excellent reactivity, delivering 5d and 5e in 94%
and 89% yield, respectively (entries 4 and 5). 3-Vinylchromone
1f with a cyano substituent could also be applied smoothly in the

4
Tetrahedron
ACCEPTED MANUSCRIPT
were isolated in 93% and 82% yield, respectively (entries 21
and 22).
To expand the scope of this cycloaddition methodology,
several substituted aryne precursors (2b-d) were investigated
(Scheme 3). The reaction of 4,5-dimethoxybenzyne precursor 2b
and
1a
furnished
the
corresponding
product
2-
naphthalenylphenylmethanone 5w in 67% yield (Scheme 3, eq 1).
To disclose the regioselectivity, nonsymmetric arynes (derived
from precursor 2c and 2d) were applied. As expected, the
reaction of 2c with 1a afforded regioisomers 5xa and 5xb in a 5:4
ratio (Scheme 3, eq 2). Unexpectedly, the reaction of 3-methoxyl
aryne precursor 2d exhibited excellent regioselectivity to
generate the sole regioisomer 5y (Scheme 3, eq 3). It may be
rationalized by the higher steric hindrance of the methoxyl group
than that of the methyl group. Also, the ester group of substrate
1a is bulkier than the ether group, leading to the final product 5y.
On the other hand, the electronic effect may be another reason
leading to the different regioselectivity. As demonstrated in Fig.
2, one of the most stable resonance forms of aryne and 3-
vinylchromone 1a are depicted as A and B.23 Due to the electron
distribution, the addition with the ether and the methoxyl group
on the same side is favored. The structure of products 5xa and 5y
were confirmed by the NOESY studies.
Scheme 4. Proposed mechanism.
3. Conclusion
In summary, a controllable strategy to achieve 9-xanthenols
and 2-hydroxybenzophenones in step and atom economic
manners has been developed. By utilizing the Brønsted acid
TfOH, 9-(2-naphthalenyl)-9H-xanthen-9-ols were generated
smoothly through an oxa-Diels-Alder reaction of arynes and 3-
vinylchromones. On the other hand, in the presence of TFA, 2-
hydroxyphenyl-2-naphthalenylmethanones could be constructed
in good-to-excellent yields via a Diels-Alder reaction. Due to the
high formation efficiency of furnishing xanthene and 2-hydroxyl
benzophenone skeletons, transition-metal-free strategy, wide
scope of substrates and promising utilization of the products, this
methodology may be of great potential use in synthetic
chemistry.
4. Experimental section
4.1 General methods
Anhydrous solvents were freshly distilled prior to use: THF
was distilled from sodium-benzophenone; CH3CN was distilled
from P2O5; Petroleum ether refers to the fraction with a boiling
1
point in the range of 60-90 °C. H NMR and 13C NMR spectra
were measured on a 400 MHz spectrometer (1H 400 MHz, 13C
100 MHz), using CDCl3 or d6-DMSO as the solvent at room
temperature. Chemical shifts are expressed in ppm, and J values
are given in Hz. Melting points are uncorrected. High-resolution
mass spectra (HRMS) were recorded on a Waters Micromass
GCT instrument with electron spray ionization (ESI) or electron
ionization (EI) resource. IR spectra were measured on a FT-IR
spectrometer.
Scheme 3. Effect of steric hindrance.
4.2 General Procedure for the Synthesis of Products 3 and 6
Under nitrogen atmosphere, 3-vinylchromones 1 (0.3 mmol),
KF (104.6 mg, 1.8 mmol) and 18-C-6 (1.8 mmol, 475.7 mg) were
added to a 25 mL of Schlenk tube equipped with a stirrer bar.
Then anhydrous THF (3.0 mL), trifluoromethanesulfonic acid
(TfOH) (0.33 mmol, 49.6 mg) and aryne precursor 2 (0.9 mmol)
were added. The reaction mixture was then stirred at room
temperature. After 24 hours, the mixture was poured into water
(20 mL), and the water layer was extracted with CH2Cl2 (5 mL ×
3). The organic layer were combined and dried over Na2SO4.
After filtration and evaporation, the residue was purified by silica
gel chromatography (petroleum ether/ethyl acetate 50:1) to afford
3 and 6.
Fig 2. The electronic effect of the reaction of 1a and 2d.
A plausible mechanism of the reaction of arynes and 3-
vinylchromones is shown in Scheme 4. In the presence of 2.5
equiv of TFA, 3-vinylchromone 1a reacts with benzyne
generated in situ from precursor 2a in the presence of fluorine
anions and affords the ring-opened Diels-Alder adduct 5a. On the
other hand, in the presence of 1.1 equiv of TfOH, substrate 1a is
more likely to polarise into oxa-1,3-diene C and processes
through oxa-Diels-Alder reaction and Diels-Alder reaction
successively with benzyne to furnish product 3a.
4.2.1 Ethyl 3-(9-hydroxy-9H-xanthen-9-yl)-1-naphthoate (3a).
The reaction of 1a (0.3 mmol, 73.3 mg), 2a (0.9 mmol, 268.6
mg), KF (1.8 mmol, 104.6 mg), 18-C-6 (1.8 mmol, 475.7 mg)
and TfOH (0.33 mmol, 49.5 mg) in THF (3 mL) afforded 77.3
mg (65%) of 3a. Pale yellow solid, mp 173.9-174.5 oC; 1H NMR
(400 MHz, CDCl3): δ 8.76 (d, J = 8.4 Hz, 1H), 8.21 (d, J = 0.4
Hz, 1H), 8.02 (d, J = 2.0 Hz, 1H), 7.86 (d, J = 7.6 Hz, 1H), 7.57-

4.2.6 3-(9-Hydroxy-9H-xanthen-9-yl)-1-naphthonitrile (3f). The
7.48 (m, 2H), 7.32-7.28 (m, 4H), 7.23-7.21 (Am,C2HC)E, 7P.0T4-E7.D00 MANUSCRIPT
(m, 2H), 4.36 (q, J = 7.2 Hz, 2H), 2.88 (s, 1H), 1.36 (t, J = 7.2 Hz,
3H); 13C NMR (100 MHz, CDCl3): δ 167.6, 149.8, 143.8, 133.4,
130.1, 129.5, 129.4, 129.1, 129.0, 129.0, 127.7, 127.7, 126.4,
126.3, 125.6, 123.7, 116.5, 70.4, 61.1, 14.3; IR (neat): ν 3476,
2924, 2858, 1715, 1693, 1600, 1448, 1241, 1192, 1154, 1041,
1027 cm-1; HRMS calcd for C26H21O4 [M + H]+ 397.1440, found
397.1437.
reaction of 1f (0.3 mmol, 59.2 mg), 2a (0.9 mmol, 268.6 mg), KF
(1.8 mmol, 104.6 mg), 18-C-6 (1.8 mmol, 475.7 mg) and TfOH
(0.33 mmol, 49.5 mg) in THF (3 mL) afforded 48.2 mg (46%) of
o
1
3f. Pale yellow solid, mp 195.0-196.8 C; H NMR (400 MHz,
d6-DMSO): δ 8.34 (s, 1H), 8.15 (d, J = 8.0 Hz, 1H), 8.04 (d, J =
8.4 Hz, 1H), 7.88 (s, 1H), 7.77 (t, J = 7.6 Hz, 1H), 7.70 (t, J = 7.6
Hz, 1H), 7.39-7.29 (m, 6H), 7.19 (s, 1H), 7.11-7.09 (m, 2H); 13C
NMR (100 MHz, d6-DMSO): δ 149.3, 146.8, 132.2, 132.2, 131.6,
130.2, 129.5, 129.2, 129.2, 129.1, 128.1, 127.0, 123.9, 123.6,
117.4, 116.2, 108.9, 68.6; IR (neat): ν 3443, 2923, 2225, 1642,
1477, 1449, 1315, 1241, 1041 cm-1; HRMS (EI) calcd for
C24H15NO2 349.1103, found 349.1104.
4.2.2 Benzyl 3-(9-hydroxy-9H-xanthen-9-yl)-1-naphthoate (3b).
The reaction of 1b (0.3 mmol, 91.9 mg), 2a (0.9 mmol, 268.6
mg), KF (1.8 mmol, 104.6 mg), 18-C-6 (1.8 mmol, 475.7 mg)
and TfOH (0.33 mmol, 49.5 mg) in THF (3 mL) afforded 85.3
mg (62%) of 3b. Pale yellow solid, mp 180.6-182.2 oC; 1H NMR
(400 MHz, CDCl3): δ 8.79 (d, J = 8.4 Hz, 1H), 8.27 (d, J = 1.6
Hz, 1H), 8.07 (d, J = 2.0 Hz, 1H), 7.89-7.87 (m, 1H), 7.57-7.49
(m, 2H), 7.36-7.33 (m, 7H), 7.31-7.28 (m, 2H), 7.23-7.21 (m,
2H), 7.05-7.01 (m, 2H), 5.34 (s, 2H), 2.87 (s, 1H); 13C NMR (100
MHz, CDCl3): δ 167.1, 149.8, 144.0, 136.1, 133.4, 130.1, 129.6,
129.4, 129.4, 129.1, 129.1, 128.5, 128.0, 127.8, 127.7, 127.1,
126.5, 126.3, 125.6, 123.7, 116.6, 70.4, 66.5; IR (neat): ν 3450,
2921, 2849, 1714, 1601, 1450, 1292, 1241, 1190, 1148, 1014 cm-
1; HRMS calcd for C31H23O4 [M + H]+ 459.1596, found 459.1591.
4.2.7 9-(4-Phenylnaphthalen-2-yl)-9H-xanthen-9-ol (3g). The
reaction of 1g (0.3 mmol, 74.5 mg), 2a (0.9 mmol, 268.6 mg),
KF (1.8 mmol, 104.6 mg), 18-C-6 (1.8 mmol, 475.7 mg) and
TfOH (0.33 mmol, 49.5 mg) in THF (3 mL) afforded 93.7 mg
o
1
(78%) of 3g. Pale yellow solid, mp 180.0-181.6 C; H NMR
(400 MHz, CDCl3): δ 8.18 (d, J = 0.8 Hz, 1H), 7.92 (d, J = 8.0
Hz, 1H), 7.83 (d, J = 8.0 Hz, 1H), 7.50-7.46 (m, 1H), 7.41-7.26
(m, 10H), 7.21-7.17 (m, 3H) ,7.04-7.00 (m, 2H), 2.75 (s, 1H); 13
C
NMR (100 MHz, CDCl3): δ 149.8, 144.4, 140.4, 140.1, 133.2,
130.5, 130.1, 129.3, 129.2, 128.8, 128.1, 127.2, 126.6, 126.4,
126.2, 126.1, 125.7, 123.9, 123.5, 116.5, 70.6; IR (neat): ν 3450,
2922, 2850, 1597, 1481, 1443, 1316, 1241, 1035 cm-1; HRMS
calcd for C29H21O2 [M + H]+ 401.1542, found 401.1547.
4.2.3 tert-Butyl 3-(9-hydroxy-9H-xanthen-9-yl)-1-naphthoate (3c).
The reaction of 1c (0.3 mmol, 81.7 mg), 2a (0.9 mmol, 268.6
mg), KF (1.8 mmol, 104.6 mg), 18-C-6 (1.8 mmol, 475.7 mg)
and TfOH (0.33 mmol, 49.5 mg) in THF (3 mL) afforded 67.5
mg (53%) of 3c. Pale yellow solid, mp 187.4-188.7 oC; 1H NMR
(400 MHz, CDCl3): δ 8.70 (d, J = 8.4 Hz, 1H), 8.16 (d, J = 1.2
Hz, 1H), 7.94 (d, J = 2.0 Hz, 1H), 7.85 (d, J = 7.6 Hz, 1H), 7.56-
7.47 (m, 2H), 7.36-7.28 (m, 4H), 7.23-7.21 (m, 2H), 7.05-7.02
(m, 2H), 2.82 (s, 1H), 1.58 (s, 9H); 13C NMR (100 MHz, CDCl3):
δ 167.1, 149.8, 143.9, 133.4, 129.9, 129.5, 129.3, 129.0, 129.0,
128.9, 128.7, 127.4, 126.4, 126.3, 125.6, 123.7, 116.5, 81.7, 70.4,
28.2; IR (neat): ν 3467, 2976, 2922, 1704, 1475, 1450, 1310,
1292, 1245, 1148, 1008 cm-1; HRMS calcd for C28H25O4 [M + H]+
425.1753, found 425.1739.
4.2.8 9-(4-(4-Methoxyphenyl)naphthalen-2-yl)-9H-xanthen-9-ol
(3h). The reaction of 1h (0.3 mmol, 83.5 mg), 2a (0.9 mmol,
268.6 mg), KF (1.8 mmol, 104.6 mg), 18-C-6 (1.8 mmol, 475.7
mg) and TfOH (0.33 mmol, 49.5 mg) in THF (3 mL) afforded
o
1
93.0 mg (72%) of 3h. Pale yellow solid, mp 184.2-185.7 C; H
NMR (400 MHz, CDCl3): δ 8.16 (d, J = 1.2 Hz, 1H), 7.92 (d, J =
8.0 Hz, 1H), 7.86 (d, J = 8.0 Hz, 1H), 7.50-7.46 (m, 1H), 7.42-
7.37 (m, 3H), 7.31-7.23 (m, 4H), 7.20-7.18 (m, 2H), 7.14 (d, J =
2.0 Hz, 1H), 7.05-7.01 (m, 2H), 6.93-6.91 (m, 2H), 3.81 (s, 3H),
2.78 (s, 1H); 13C NMR (100 MHz, CDCl3): δ 158.9, 149.8, 144.4,
139.8, 133.2, 132.8, 131.1, 130.7, 129.3, 129.2, 128.8, 126.6,
126.4, 126.1, 126.0, 125.8, 123.6, 123.5, 116.5, 113.6, 70.6, 55.3;
IR (neat): ν 3460, 2922, 2849, 1604, 1447, 1241, 1179, 1032 cm-1;
HRMS calcd for C30H23O3 [M + H]+ 431.1647, found 431.1643.
4.2.4 1-(3-(9-Hydroxy-9H-xanthen-9-yl)naphthalen-1-yl)ethan-1-
one (3d). The reaction of 1d (0.3 mmol, 64.3 mg), 2a (0.9 mmol,
268.6 mg), KF (1.8 mmol, 104.6 mg), 18-C-6 (1.8 mmol, 475.7
mg) and TfOH (0.33 mmol, 49.5 mg) in THF (3 mL) afforded
o
1
78.0 mg (71%) of 3d. Pale yellow solid, mp 214.0-215.9 C; H
NMR (400 MHz, d6-DMSO): δ 8.47 (d, J = 8.4 Hz, 1H), 8.03 (s,
1H), 7.97-7.94 (m, 2H), 7.59-7.52 (m, 2H), 7.41-7.28 (m, 6H),
7.12-7.08 (m, 3H), 2.57 (s, 3H); 13C NMR (100 MHz, d6-DMSO):
δ 202.1, 149.5, 146.0, 135.6, 133.3, 129.3, 129.2, 129.1, 128.7,
128.2, 128.1, 127.8, 127.1, 127.0, 125.4, 123.8, 116.4, 69.0, 30.2;
IR (neat): ν 3450, 2922, 2853, 1666, 1601, 1570, 1477, 1446,
1316, 1292, 1241, 1014 cm-1; HRMS calcd for C25H19O3 [M +
H]+ 367.1334, found 367.1336.
4.2.9
9-(4-(4-Bromophenyl)naphthalen-2-yl)-9H-xanthen-9-ol
(3i). The reaction of 1i (0.3 mmol, 98.2 mg), 2a (0.9 mmol, 268.6
mg), KF (1.8 mmol, 104.6 mg), 18-C-6 (1.8 mmol, 475.7 mg)
and TfOH (0.33 mmol, 49.5 mg) in THF (3 mL) afforded 89.2
o
1
mg (62%) of 3i. Pale yellow solid, mp 227.5-228.8 C; H NMR
(400 MHz, CDCl3): δ 8.16 (d, J = 0.8 Hz, 1H), 7.91 (d, J = 8.0
Hz, 1H), 7.76 (d, J = 8.8 Hz, 1H), 7.51-7.46 (m, 3H), 7.41-7.36
(m, 3H), 7.30-7.26 (m, 2H), 7.22-7.18 (m, 4H), 7.15 (d, J = 0.8
Hz, 1H), 7.04-7.00 (m, 2H), 2.80 (s, 1H); 13C NMR (100 MHz,
CDCl3): δ 149.7, 144.5, 139.3, 138.8, 133.2, 131.7, 131.3, 130.2,
129.3, 129.2, 128.9, 126.6, 126.4, 126.3, 126.2, 125.4, 124.3,
123.6, 121.4, 116.5, 70.6; IR (neat): ν 3446, 2925, 1649, 1447,
1237, 1010 cm-1; HRMS calcd for C29H2079BrO2 [M + H]+
479.0647, found 479.0648.
4.2.5 (3-(9-Hydroxy-9H-xanthen-9-yl)naphthalen-1-yl)(phenyl)
methanone (3e). The reaction of 1e (0.3 mmol, 82.9 mg), 2a (0.9
mmol, 268.6 mg), KF (1.8 mmol, 104.6 mg), 18-C-6 (1.8 mmol,
475.7 mg) and TfOH (0.33 mmol, 49.5 mg) in THF (3 mL)
afforded 77.1 mg (60%) of 3e. Pale yellow solid, mp 199.1-199.8
1
oC; H NMR (400 MHz, CDCl3): δ 8.32 (s, 1H), 8.08 (d, J = 8.4
4.2.10
9-(4-(4-Nitrophenyl)naphthalen-2-yl)-9H-xanthen-9-ol
Hz, 1H), 7.94 (d, J = 8.0 Hz, 1H), 7.64-7.62 (m, 2H), 7.53-7.48
(m, 3H), 7.35-7.33 (m, 3H), 7.30-7.27 (m, 4H), 7.15-7.13 (m,
2H), 7.06-7.02 (m, 2H), 2.93 (s, 1H); 13C NMR (100 MHz,
CDCl3): δ 197.2, 149.7, 143.6, 137.8, 135.5, 133.3, 133.1, 130.4,
129.7, 129.4, 129.1, 129.0, 128.2, 128.0, 127.4, 127.2, 126.8,
126.2, 125.3, 123.6, 116.6, 70.4; IR (neat): ν 3446, 2922, 2853,
1656, 1601, 1477, 1450, 1316, 1289, 1248, 1025 cm-1; HRMS
calcd for C30H21O3 [M + H]+ 429.1491, found 429.1492.
(3j). The reaction of 1j (0.3 mmol, 88.0 mg), 2a (0.9 mmol, 268.6
mg), KF (1.8 mmol, 104.6 mg), 18-C-6 (1.8 mmol, 475.7 mg)
and TfOH (0.33 mmol, 49.5 mg) in THF (3 mL) afforded 80.2
mg (60%) of 3j. Pale yellow solid, mp 147.1-148.6 C; H NMR
(400 MHz, CDCl3): δ 8.22-8.20 (m, 3H), 7.93 (d, J = 8.0 Hz, 1H),
7.69 (d, J = 8.0 Hz, 1H), 7.50-7.37 (m, 6H), 7.29-7.27 (m, 2H),
7.20-7.18 (m, 3H), 7.05-7.01 (m, 2H), 2.89 (s, 1H); 13C NMR
(100 MHz, CDCl3): δ 149.7, 147.3, 147.0, 144.7, 137.7, 133.3,
130.9, 129.8, 129.3, 129.1, 129.1, 126.8, 126.5, 126.5, 126.3,
o
1

6
Tetrahedron
125.2, 124.8, 123.6, 123.4, 116.5, 70.5; IR (neat): ν 3541, 2923,
1476, 1454, 1260, 1192, 1150, 1039 cm-1; HRMS calcd for
ACCEPTED MANUSCRIPT
2853, 1601, 1516, 1473, 1450, 1241 cm-1; HRMS (EI) calcd for
C29H19NO4 445.1314, found 445.1318.
C26H20FO4 [M + H]+ 415.1346, found 415.1344.
4.2.15 Ethyl 3-(2-chloro-9-hydroxy-9H-xanthen-9-yl)-1-
4.2.11 9-([1,2'-Binaphthalen]-3-yl)-9H-xanthen-9-ol (3k). The
reaction of 1k (0.3 mmol, 89.5 mg), 2a (0.9 mmol, 268.6 mg),
KF (1.8 mmol, 104.6 mg), 18-C-6 (1.8 mmol, 475.7 mg) and
TfOH (0.33 mmol, 49.5 mg) in THF (3 mL) afforded 87.8 mg
naphthoate (3o). The reaction of 1o (0.3 mmol, 83.6 mg), 2a (0.9
mmol, 268.6 mg), KF (1.8 mmol, 104.6 mg), 18-C-6 (1.8 mmol,
475.7 mg) and TfOH (0.33 mmol, 49.5 mg) in THF (3 mL)
afforded 67.2 mg (52%) of 3o. Pale yellow solid, mp 165.9-166.5
oC; 1H NMR (400 MHz, CDCl3): δ 8.76 (d, J = 8.4 Hz, 1H), 8.20
(d, J = 1.2 Hz, 1H), 7.97 (d, J = 2.0 Hz, 1H), 7.88 (d, J = 8.0 Hz,
1H), 7.60-7.51 (m, 2H), 7.33-7.30 (m, 3H), 7.27-7.23 (m, 2H),
7.20-7.16 (m, 1H), 7.06-7.03 (m, 1H), 4.38 (q, J = 7.2 Hz, 2H),
2.93 (s, 1H), 1.38 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz,
CDCl3): δ 167.5, 149.5, 148.3, 143.3, 133.4, 130.1, 129.6, 129.6,
129.6, 129.4, 129.1, 129.0, 128.7, 128.7, 128.4, 127.9, 127.9,
126.6, 125.8, 125.6, 124.0, 118.2, 116.6, 70.2, 61.2, 14.3; IR
(neat): ν 3440, 2922, 2854, 1703, 1472, 1455, 1274, 1264, 1195,
1022 cm-1; HRMS calcd for C26H1935ClO4Na [M + Na]+ 453.0870,
found 453.0867.
o
1
(65%) of 3k. Pale yellow solid, mp 182.1-183.7 C; H NMR
(400 MHz, CDCl3): δ 8.19 (s, 1H), 7.95 (d, J = 8.0 Hz, 1H), 7.87-
7.84 (m, 3H), 7.82-7.79 (m, 1H), 7.50-7.46 (m, 5H), 7.43-7.39
(m, 3H), 7.31-7.27 (m, 3H), 7.23-7.19 (m, 2H), 7.07-7.03 (m,
2H), 2.81 (s, 1H); 13C NMR (100 MHz, CDCl3): δ 149.8, 144.5,
140.1, 138.0, 133.3, 133.2, 132.5, 130.6, 129.3, 129.2, 128.9,
128.7, 128.4, 128.0, 127.6, 127.5, 126.7, 126.6, 126.3, 126.2,
126.2, 126.0, 125.8, 124.1, 123.6, 116.5, 70.7; IR (neat): ν 3457,
2922, 1639, 1444, 1295, 1241, 1011 cm-1; HRMS calcd for
C33H23O2 [M + H]+ 451.1698, found 451.1701.
4.2.12
Ethyl
3-(9-hydroxy-2-methyl-9H-xanthen-9-yl)-1-
naphthoate (3l). The reaction of 1l (0.3 mmol, 77.5 mg), 2a (0.9
mmol, 268.6 mg), KF (1.8 mmol, 104.6 mg), 18-C-6 (1.8 mmol,
475.7 mg) and TfOH (0.33 mmol, 49.5 mg) in THF (3 mL)
afforded 76.4 mg (62%) of 3l. Pale yellow solid, mp 166.0-167.8
oC; 1H NMR (400 MHz, CDCl3): δ 8.75 (d, J = 8.4 Hz, 1H), 8.22
(d, J = 1.6 Hz, 1H), 8.01 (d, J = 2.0 Hz, 1H), 7.87-7.86 (m, 1H),
7.57-7.48 (m, 2H), 7.30-7.24 (m, 2H), 7.19-7.17 (m, 1H), 7.09-
7.07 (m, 3H), 7.01-6.97 (m, 1H), 4.36 (q, J = 7.2 Hz, 2H), 2.93 (s,
1H), 2.18 (s, 3H), 1.35 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz,
CDCl3): δ 167.6, 149.8, 147.7, 144.0, 133.4, 133.1, 130.3, 130.0,
129.4, 129.2, 129.2, 129.0, 129.0, 129.0, 127.7, 127.6, 126.4,
126.3, 125.8, 125.6, 123.4, 116.5, 116.3, 70.4, 61.1, 20.7, 14.2;
IR (neat): ν 3450, 2922, 2850, 1705, 1453, 1278, 1256, 1017 cm-1;
HRMS calcd for C27H23O4 [M + H]+ 411.1596, found 411.1601.
4.2.16
Ethyl
3-(2-bromo-9-hydroxy-9H-xanthen-9-yl)-1-
naphthoate (3p). The reaction of 1p (0.3 mmol, 96.9 mg), 2a (0.9
mmol, 268.6 mg), KF (1.8 mmol, 104.6 mg), 18-C-6 (1.8 mmol,
475.7 mg) and TfOH (0.33 mmol, 49.5 mg) in THF (3 mL)
afforded 64.2 mg (45%) of 3p. Pale yellow solid, mp 165.5-166.2
oC; 1H NMR (400 MHz, CDCl3): δ 8.75 (d, J = 8.4 Hz, 1H), 8.19
(d, J = 1.2 Hz, 1H), 7.97 (d, J = 7.6 Hz, 1H), 7.87 (d, J = 7.6 Hz,
1H), 7.59-7.50 (m, 2H), 7.45 (d, J = 2.4 Hz, 1H), 7.38-7.36 (m,
1H), 7.31-7.27 (m, 2H), 7.20-7.18 (m, 1H), 7.10-7.07 (d, J = 1.2
Hz, 1H), 7.04-7.00 (m, 1H), 4.36 (q, J = 7.2 Hz, 2H), 3.06 (s, 1H),
1.36 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3): δ 167.5,
149.4, 148.8, 143.3, 133.4, 132.4, 131.7, 130.1, 129.6, 129.4,
129.1, 129.0, 128.7, 128.3, 127.9, 127.9, 126.6, 125.9, 125.6,
124.0, 118.5, 116.6, 115.8, 70.1, 61.9, 14.2; IR (neat): ν 3449,
2922, 2850, 1700, 1472, 1452, 1264, 1236, 1192, 1025 cm-1;
HRMS calcd for C26H2079BrO4 [M + H]+ 475.0545, found
475.0549.
4.2.13
Ethyl
3-(9-hydroxy-2-methoxy-9H-xanthen-9-yl)-1-
naphthoate (3m). The reaction of 1m (0.3 mmol, 82.3 mg), 2a
(0.9 mmol, 268.6 mg), KF (1.8 mmol, 104.6 mg), 18-C-6 (1.8
mmol, 475.7 mg) and TfOH (0.33 mmol, 49.5 mg) in THF (3 mL)
afforded 60.1 mg (47%) of 3m. Pale yellow solid, mp 162.6-
162.7 oC; 1H NMR (400 MHz, CDCl3): δ 8.76 (d, J = 8.4 Hz, 1H),
8.18 (d, J = 1.2 Hz, 1H), 8.04 (d, J = 2.0 Hz, 1H), 7.86 (d, J = 8.0
Hz, 1H), 7.57-7.48 (m, 2H), 7.34-7.24 (m, 2H), 7.19-7.14 (m,
2H), 7.03-6.99 (m, 1H), 6.89-6.86 (m, 1H), 6.81 (d, J = 3.2 Hz,
1H), 4.36 (q, J = 7.2 Hz, 2H), 3.62 (s, 3H), 2.95 (s, 1H), 1.37 (t, J
= 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3): δ 167.6, 155.5,
149.9, 144.1, 143.8, 133.4, 130.1, 129.3, 129.2, 129.0, 129.0,
128.8, 127.7, 127.7, 126.7, 126.4, 125.8, 125.6, 123.4, 117.5,
116.6, 116.5, 111.9, 70.7, 61.1, 55.6, 14.3; IR (neat): ν 3456,
2917, 2849, 1712, 1478, 1450, 1289, 1224, 1193, 1155, 1035 cm-
1; HRMS calcd for C27H22O5Na [M + Na]+ 449.1365, found
449.1371.
4.2.17
Ethyl
3-(9-hydroxy-3-methyl-9H-xanthen-9-yl)-1-
naphthoate (3q). The reaction of 1q (0.3 mmol, 77.5 mg), 2a (0.9
mmol, 268.6 mg), KF (1.8 mmol, 104.6 mg), 18-C-6 (1.8 mmol,
475.7 mg) and TfOH (0.33 mmol, 49.5 mg) in THF (3 mL)
afforded 73.9 mg (60%) of 3q. Pale yellow solid, mp 112.2-113.0
oC; 1H NMR (400 MHz, CDCl3): δ 8.67 (d, J = 8.4 Hz, 1H), 8.13
(s, 1H), 7.94 (s, 1H), 7.77 (d, J = 8.0 Hz, 1H), 7.48-7.39 (m, 2H),
7.21-7.14 (m, 2H), 7.11-7.07 (m, 2H), 6.93-6.90 (m, 2H), 6.74 (d,
J = 8.0 Hz, 1H), 4.27 (q, J = 7.2 Hz, 2H), 2.81 (s, 1H), 2.25 (s,
3H), 1.27 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3): δ
167.6, 149.9, 149.6, 144.0, 139.6, 133.4, 130.0, 129.5, 129.3,
129.2, 129.1, 129.0, 128.9, 127.7, 127.6, 126.4, 126.4, 125.6,
124.8, 123.5, 123.4, 116.6, 116.5, 70.3, 61.0, 21.1, 14.2; IR
(neat): ν 3476, 2924, 2853, 1712, 1603, 1454, 1288, 1243, 1191,
1154, 1033 cm-1; HRMS (EI) calcd for C27H22O4 410.1518, found
410.1515.
4.2.14
Ethyl
3-(2-fluoro-9-hydroxy-9H-xanthen-9-yl)-1-
naphthoate (3n). The reaction of 1n (0.3 mmol, 78.7 mg), 2a (0.9
mmol, 268.6 mg), KF (1.8 mmol, 104.6 mg), 18-C-6 (1.8 mmol,
475.7 mg) and TfOH (0.33 mmol, 49.5 mg) in THF (3 mL)
afforded 70.9 mg (57%) of 3n. Pale yellow solid, mp 160.8-161.6
4.2.18
Ethyl
3-(9-hydroxy-3-methoxy-9H-xanthen-9-yl)-1-
naphthoate (3r). The reaction of 1r (0.3 mmol, 82.3 mg), 2a (0.9
mmol, 268.6 mg), KF (1.8 mmol, 104.6 mg), 18-C-6 (1.8 mmol,
475.7 mg) and TfOH (0.33 mmol, 49.5 mg) in THF (3 mL)
1
oC; H NMR (400 MHz, d6-DMSO): δ 8.63 (d, J = 8.4 Hz, 1H),
1
8.22 (d, J = 1.2 Hz, 1H), 8.05 (d, J = 7.6 Hz, 1H), 7.89 (d, J = 1.6
Hz, 1H), 7.66-7.57 (m, 2H), 7.39-7.36 (m, 3H), 7.31-7.29 (m,
1H), 7.27 (s, 1H), 7.25-7.21 (m, 1H), 7.14-7.09 (m, 2H), 4.35 (q,
J = 7.2 Hz, 2H), 1.31 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz,
d6-DMSO): δ 166.9, 158.1 (d, JC-F = 237.7 Hz), 149.3, 145.8 (d,
JC-F = 1.5 Hz), 145.3, 133.2, 129.4, 129.3, 129.2, 128.9, 128.8,
128.8, 128.1, 128.0, 127.6, 127.0, 126.7, 125.1, 124.0, 118.3 (d,
afforded 74.2 mg (58%) of 3r. Pale yellow oil; H NMR (400
MHz, CDCl3): δ 8.77 (d, J = 8.0 Hz, 1H), 8.24 (s, 1H), 8.00 (d, J
= 1.6 Hz, 1H), 7.87 (d, J = 8.0 Hz, 1H), 7.59-7.50 (m, 3H), 7.30-
7.28 (m, 2H), 7.22-7.16 (m, 2H), 7.04-7.00 (m, 1H), 6.73 (d, J =
2.4 Hz, 1H), 6.63-6.60 (m, 1H), 4.37 (q, J = 7.2 Hz, 2H), 3.81 (s,
3H), 1.37 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3): δ
167.6, 160.3, 150.8, 149.9, 144.0, 133.4, 130.2, 130.0, 129.5,
129.3, 129.2, 129.0, 127.7, 127.6, 126.5, 126.4, 125.6, 123.7,
118.7, 116.5, 114.3, 111.4, 100.4, 70.3, 61.1, 55.4, 14.3; IR
JC-F = 8.1 Hz), 116.6 (d, JC-F = 23.4 Hz), 116.3, 114.3 (d, JC-F
=
23.3 Hz), 69.0, 61.3, 14.2; IR (neat): ν 3456, 2919, 2850, 1704,

128.3, 127.6, 127.0, 126.6, 126.2, 125.9, 125.1, 123.9, 123.4,
(neat): ν 3389, 3007, 2949, 1713, 1558, 1520, A12C98C, 1E22P1T, 1E07D7, MANUSCRIPT
1029 cm-1; HRMS (EI) calcd for C27H22O5 426.1467, found
426.1470.
122.9, 122.2, 119.8, 117.2, 70.6, 60.9, 20.7, 20.0, 19.7, 19.1, 14.3;
IR (neat): ν 3460, 2921, 1705, 1456, 1378, 1248, 1175, 1107,
1022 cm-1; HRMS (EI) calcd for C34H30O4 502.2144, found
502.2139.
4.2.19
Ethyl
3-(3-bromo-9-hydroxy-9H-xanthen-9-yl)-1-
naphthoate (3s). The reaction of 1s (0.3 mmol, 96.9 mg), 2a (0.9
mmol, 268.6 mg), KF (1.8 mmol, 104.6 mg), 18-C-6 (1.8 mmol,
475.7 mg) and TfOH (0.33 mmol, 49.5 mg) in THF (3 mL)
afforded 78.4 mg (55%) of 3s. Pale yellow solid, mp 135.6-136.7
oC; 1H NMR (400 MHz, CDCl3): δ 8.74 (d, J = 8.4 Hz, 1H), 8.18
(d, J = 1.6 Hz, 1H), 7.97 (d, J = 2.0 Hz, 1H), 7.86 (d, J = 8.8 Hz,
1H), 7.58-7.49 (m, 2H), 7.38 (d, J = 2.0 Hz, 1H), 7.31-7.28 (m,
2H), 7.20-7.11 (m, 3H), 7.05-7.01 (m, 1H), 4.36 (q, J = 7.2 Hz,
2H), 3.02 (s, 1H), 1.36 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz,
CDCl3): δ 167.5, 150.3, 149.4, 143.4, 133.4, 130.7, 130.1, 129.5,
129.5, 129.1, 129.0, 128.7, 127.9, 127.8, 126.9, 126.5, 126.1,
125.6, 125.6, 124.1, 122.4, 119.6, 116.6, 70.1, 61.1, 14.3; IR
(neat): ν 3458, 2925, 2854, 1713, 1595, 1473, 1455, 1407, 1290,
1240, 1194, 1155, 1033 cm-1; HRMS (EI) calcd for C26H1979BrO4
474.0467, found 474.0466.
4.2.23 Ethyl 3-(2-phenoxybenzoyl)-1-naphthoate (6a). The
reaction of 1a (0.3 mmol, 73.3 mg), 2a (0.9 mmol, 268.6 mg),
KF (1.8 mmol, 104.6 mg), 18-C-6 (1.8 mmol, 475.7 mg) and
TfOH (0.33 mmol, 49.5 mg) in THF (3 mL) afforded 28.5 mg
(24%) of 6a. Pale yellow oil; 1H NMR (400 MHz, CDCl3): δ 8.92
(d, J = 8.4 Hz, 1H), 8.66 (d, J = 1.6 Hz, 1H), 8.44 (s, 1H), 7.88 (d,
J = 8.0 Hz, 1H), 7.68-7.64 (m, 1H), 7.61 (dd, J1 = 7.6 Hz, J2 =
2.0 Hz, 1H), 7.53-7.44 (m, 2H), 7.25-7.16 (m, 3H), 7.00-6.96 (m,
2H), 6.84-6.82 (m, 2H), 4.47 (q, J = 7.2 Hz, 2H), 1.43 (t, J = 7.2
Hz, 3H); 13C NMR (100 MHz, CDCl3): δ 194.7, 167.0, 156.1,
155.1, 136.2, 133.6, 133.2, 133.0, 132.4, 130.4, 130.2, 130.2,
130.1, 129.6, 129.1, 127.8, 126.9, 125.9, 123.7, 123.4, 119.0,
118.4, 61.2, 14.3; IR (neat): ν 2987, 2922, 1710, 1660, 1473,
1446, 1278, 1232 cm-1; HRMS (EI) calcd for C26H20O4 396.1362,
found 396.1367.
4.2.20
Ethyl
3-(7-hydroxy-7H-benzo[c]xanthen-7-yl)-1-
naphthoate (3t). The reaction of 1t (0.3 mmol, 88.3 mg), 2a (0.9
mmol, 268.6 mg), KF (1.8 mmol, 104.6 mg), 18-C-6 (1.8 mmol,
475.7 mg) and TfOH (0.33 mmol, 49.5 mg) in THF (3 mL)
afforded 96.4 mg (72%) of 3t. Pale yellow solid, mp 192.9-193.5
4.2.24 Benzyl 3-(2-phenoxybenzoyl)-1-naphthoate (6b). The
reaction of 1b (0.3 mmol, 91.9 mg), 2a (0.9 mmol, 268.6 mg),
KF (1.8 mmol, 104.6 mg), 18-C-6 (1.8 mmol, 475.7 mg) and
TfOH (0.33 mmol, 49.5 mg) in THF (3 mL) afforded 34.4 mg
(25%) of 6b. Pale yellow oil; 1H NMR (400 MHz, CDCl3): δ 8.94
(d, J = 8.4 Hz, 1H), 8.68 (d, J = 1.6 Hz, 1H), 8.47 (s, 1H), 7.92 (d,
J = 8.4 Hz, 1H), 7.71-7.67 (m, 1H), 7.62-7.46 (m, 5H), 7.40-7.34
(m, 3H), 7.28-7.24 (m, 1H), 7.17-7.13 (m, 2H), 7.00-6.95 (m,
2H), 6.77-6.76 (m, 2H), 5.45 (s, 2H); 13C NMR (100 MHz,
CDCl3): δ 194.7, 166.7, 156.0, 155.2, 136.3, 135.8, 133.6, 133.3,
133.0, 132.4, 130.5, 130.3, 130.2, 130.2, 129.7, 129.7, 128.6,
128.3, 128.2, 127.3, 126.9, 125.9, 123.8, 123.4, 119.0, 118.3,
66.9; IR (neat): ν 3058, 3038, 2956, 2921, 2848, 1721, 1666,
1450, 1378, 1230, 1005 cm-1; HRMS calcd for C31H23O4 [M +
H]+ 459.1596, found 459.1592.
1
oC; H NMR (400 MHz, d6-DMSO): δ 8.64 (d, J = 8.4 Hz, 1H),
8.56 (d, J = 8.4 Hz, 1H), 8.33 (s, 1H), 8.06 (d, J = 7.6 Hz, 1H),
7.96-7.95 (m, 1H), 7.92 (d, J = 8.0 Hz, 1H), 7.73-7.69 (m, 1H),
7.65-7.58 (m, 4H), 7.54 (d, J = 7.6 Hz, 1H), 7.44-7.40 (m, 1H),
7.38-7.34 (m, 2H), 7.20 (s, 1H), 7.17-7.13 (m, 1H), 4.31 (q, J =
7.2 Hz, 2H), 1.26 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz, d6-
DMSO): δ 166.9, 149.0, 145.8, 144.0, 133.2, 133.2, 129.5, 129.3,
129.2, 129.1, 129.0, 128.4, 127.9, 127.7, 127.3, 127.3, 127.2,
126.8, 126.6, 126.0, 125.0, 124.0, 123.1, 122.9, 121.6, 120.9,
116.4, 68.8, 61.0, 14.1; IR (neat): ν 3509, 2931, 2850, 1694, 1635,
1455, 1375, 1249, 1156, 1023 cm-1; HRMS (EI) calcd for
C30H22O4 446.1518, found 446.1516.
4.2.25 tert-Butyl 3-(2-phenoxybenzoyl)-1-naphthoate (6c). The
reaction of 1c (0.3 mmol, 81.7 mg), 2a (0.9 mmol, 268.6 mg), KF
(1.8 mmol, 104.6 mg), 18-C-6 (1.8 mmol, 475.7 mg) and TfOH
(0.33 mmol, 49.5 mg) in THF (3 mL) afforded 31.8 mg (25%) of
4.2.21
Ethyl 3-(12-hydroxy-12H-benzo[a]xanthen-12-yl)-1-
naphthoate (3u). The reaction of 1u (0.3 mmol, 88.3 mg), 2a (0.9
mmol, 268.6 mg), KF (1.8 mmol, 104.6 mg), 18-C-6 (1.8 mmol,
475.7 mg) and TfOH (0.33 mmol, 49.5 mg) in THF (3 mL)
afforded 107.2 mg (80%) of 3u. Pale yellow solid, mp 213.9-
215.1 oC; 1H NMR (400 MHz, d6-DMSO): δ 8.62 (d, J = 8.4 Hz,
1H), 8.55 (d, J = 8.4 Hz, 1H), 8.31 (s, 1H), 8.06 (d, J = 7.6 Hz,
1H), 7.95-7.91 (m, 2H), 7.73-7.69 (m, 1H), 7.66-7.52 (m, 5H),
7.44-7.40 (m, 1H), 7.36-7.32 (m, 2H), 7.19-7.12 (m, 2H), 4.31 (q,
J = 7.2 Hz, 2H), 1.26 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz,
d6-DMSO): δ 166.8, 149.0, 145.7, 143.9, 133.2, 133.1, 129.4,
129.2, 129.0, 129.0, 128.9, 128.3, 127.8, 127.7, 127.3, 127.2,
127.2, 126.7, 126.6, 125.9, 125.0, 123.9, 123.1, 122.9, 121.6,
120.9, 116.4, 68.8, 61.0, 14.1; IR (neat): ν 3500, 2918, 2847,
1694, 1377, 1274, 1259, 1022 cm-1; HRMS calcd for C30H23O4
[M + H]+ 447.1596, found 447.1599.
1
6c. Pale yellow oil; H NMR (400 MHz, CDCl3): δ 8.86 (d, J =
8.8 Hz, 1H), 8.54 (d, J = 1.6 Hz, 1H), 8.41 (s, 1H), 7.91 (d, J =
8.0 Hz, 1H), 7.70-7.66 (m, 1H), 7.62-7.47 (m, 3H), 7.23-7.19 (m,
3H), 7.04-6.97 (m, 2H), 6.85-6.83 (m, 2H), 1.66 (s, 9H); 13C
NMR (100 MHz, CDCl3): δ 194.9, 166.5, 156.1, 155.2, 135.9,
133.6, 133.2, 133.0, 132.3, 132.3, 130.4, 130.3, 130.2, 129.9,
129.7, 128.7, 126.8, 125.9, 123.8, 123.3, 119.1, 118.3, 82.0, 28.3;
IR (neat): ν 2968, 2919, 2841, 1710, 1654, 1598, 1471, 1358,
1235, 1136, 1002 cm-1; HRMS calcd for C28H25O4 [M + H]+
425.1753, found 425.1750.
4.2.26 1-(3-(2-Phenoxybenzoyl)naphthalen-1-yl)ethan-1-one (6d).
The reaction of 1d (0.3 mmol, 64.3 mg), 2a (0.9 mmol, 268.6
mg), KF (1.8 mmol, 104.6 mg), 18-C-6 (1.8 mmol, 475.7 mg)
and TfOH (0.33 mmol, 49.5 mg) in THF (3 mL) afforded 29.7
mg (27%) of 6d. Pale yellow oil; 1H NMR (400 MHz, CDCl3): δ
8.77 (d, J = 8.4 Hz, 1H), 8.44 (d, J = 1.6 Hz, 1H), 8.36 (s, 1H),
7.90 (d, J = 8.0 Hz, 1H), 7.72-7.68 (m, 1H), 7.62 (dd, J1 = 7.6 Hz,
J2 = 2.0 Hz, 1H), 7.59-7.51 (m, 2H), 7.30-7.28 (m, 1H), 7.21-
7.17 (m, 2H), 7.05-6.98 (m, 2H), 6.78-7.76 (m, 2H), 2.76 (s, 3H);
13C NMR (100 MHz, CDCl3): δ 201.4, 194.7, 156.3, 154.9, 136.7,
135.5, 133.4, 133.1, 132.5, 132.2, 130.5, 130.5, 130.4, 130.4,
130.1, 129.7, 127.3, 127.1, 126.2, 123.6, 119.0, 118.6, 29.9; IR
(neat): ν 3067, 2922, 2848, 1672, 1601, 1471, 1443, 1231 cm-1;
HRMS calcd for C25H19O3 [M + H]+ 367.1334, found 367.1333.
4.2.22 Ethyl 3-(12-hydroxy-9,10-dimethyl-12H-benzo[a]xanthen-
12-yl)-6,7-dimethyl-1- naphthoate (3v). The reaction of 1u (0.3
mmol, 88.3 mg), 2b (0.9 mmol, 293.8 mg), KF (1.8 mmol, 104.6
mg), 18-C-6 (1.8 mmol, 475.7 mg) and TfOH (0.33 mmol, 49.5
mg) in THF (3 mL) afforded 102.5 mg (68%) of 3v. Pale yellow
1
oil; H NMR (400 MHz, CDCl3): δ 8.57-8.55 (m, 2H), 8.13 (s,
1H), 8.01 (s, 1H), 7.78 (d, J = 8.0 Hz, 1H), 7.64-7.54 (m, 3H),
7.43 (d, J = 8.8 Hz, 1H), 7.26 (d, J = 7.6 Hz, 1H), 7.20 (s, 1H),
7.05 (s, 1H), 4.36 (q, J = 7.2 Hz, 2H), 2.77 (s, 1H), 2.44 (s, 3H),
2.40 (s, 3H), 2.30 (s, 3H), 2.11 (s, 3H), 1.34 (t, J = 7.2 Hz, 3H);
13C NMR (100 MHz, CDCl3): δ 167.9, 147.6, 145.0, 143.2, 138.3,
137.7, 136.1, 133.8, 132.5, 132.4, 129.6, 129.1, 129.0, 128.5,

8
Tetrahedron
ACCEPTED MANUSCRIPT
4.2.27
(4-Benzoylnaphthalen-2-yl)(2-phenoxyphenyl)
3H), 7.32-7.30 (m, 2H), 7.25-7.17 (m, 3H) ,7.02-6.99 (m, 2H),
methanone (6e). The reaction of 1e (0.3 mmol, 82.9 mg), 2a (0.9
mmol, 268.6 mg), KF (1.8 mmol, 104.6 mg), 18-C-6 (1.8 mmol,
475.7 mg) and TfOH (0.33 mmol, 49.5 mg) in THF (3 mL)
6.82-6.80 (m, 2H); 13C NMR (100 MHz, CDCl3): δ 195.4, 156.4,
154.9, 139.2, 138.8, 134.3, 133.6, 132.9, 132.2, 131.9, 131.6,
131.5, 130.8, 130.4, 130.1, 129.6, 128.8, 126.6, 125.7, 125.7,
123.6, 123.4, 121.8, 118.8, 118.7; IR (neat): ν 3056, 2918, 2846,
1657, 1592, 1477, 1439, 1229, 1011 cm-1; HRMS calcd for
C29H2079BrO2 [M + H]+ 479.0647, found 479.0641.
1
afforded 32.1 mg (25%) of 6e. Pale yellow oil; H NMR (400
MHz, CDCl3): δ 8.35 (s, 1H), 8.00-7.97 (m, 1H), 7.96 (d, J = 1.2
Hz, 1H), 7.91-7.88 (m, 1H), 7.77-7.75 (m, 2H), 7.55-7.48 (m,
4H), 7.44-7.35 (m, 3H), 7.20-7.16 (m, 1H), 7.14-7.10 (m, 2H),
6.95-6.91 (m, 2H), 6.72-6.70 (m, 2H); 13C NMR (100 MHz,
CDCl3): δ 197.3, 194.8, 156.4, 154.9, 137.7, 136.7, 134.6, 133.6,
133.5, 133.1, 133.0, 132.8, 132.5, 130.6, 130.5, 130.4, 130.1,
129.7, 128.5, 127.2, 126.4, 125.8, 123.6, 123.6, 118.9, 118.7; IR
(neat): ν 3048, 2960, 2912, 2845, 1657, 1597, 1481, 1446, 1257,
1092, 1022 cm-1; HRMS (EI) calcd for C30H20O3 428.1412, found
428.1416.
4.2.32
(4-(4-Nitrophenyl)naphthalen-2-yl)(2-phenoxyphenyl)
methanone (6j). The reaction of 1j (0.3 mmol, 88.0 mg), 2a (0.9
mmol, 268.6 mg), KF (1.8 mmol, 104.6 mg), 18-C-6 (1.8 mmol,
475.7 mg) and TfOH (0.33 mmol, 49.5 mg) in THF (3 mL)
afforded 46.8 mg (35%) of 6j. Pale yellow solid, mp 163.0-164.2
1
oC; H NMR (400 MHz, CDCl3): δ 8.36-8.33 (m, 3H), 7.99-7.98
(m, 1H), 7.90 (s, 1H), 7.77-7.76 (m, 1H), 7.64-7.57 (m, 5H), 7.50
(t, J = 7.2 Hz, 1H), 7.27 (t, J = 7.2 Hz, 1H), 7.21-7.18 (m, 2H),
7.03-7.01 (m, 2H), 6.80 (d, J = 7.6 Hz, 2H); 13C NMR (100 MHz,
CDCl3): δ 195.1, 156.3, 154.9, 147.3, 146.8, 138.0, 134.3, 133.1,
132.9, 132.7, 132.4, 130.9, 130.6, 130.4, 130.3, 129.6, 129.2,
126.9, 125.9, 125.2, 123.6, 123.6,123.5, 118.8, 118.7; IR (neat): ν
2923, 2853, 1662, 1596, 1516, 1481, 1448, 1346, 1237 cm-1;
HRMS (EI) calcd for C29H19NO4 445.1314, found 445.1317.
4.2.28 3-(2-Phenoxybenzoyl)-1-naphthonitrile (6f). The reaction
of 1f (0.3 mmol, 59.2 mg), 2a (0.9 mmol, 268.6 mg), KF (1.8
mmol, 104.6 mg), 18-C-6 (1.8 mmol, 475.7 mg) and TfOH (0.33
mmol, 49.5 mg) in THF (3 mL) afforded 31.4 mg (30%) of 6f.
o
1
White solid, mp 192.0-193.3 C; H NMR (400 MHz, CDCl3): δ
8.52 (s, 1H), 8.34 (s, 1H), 8.26 (d, J = 8.4 Hz, 1H), 8.00 (d, J =
8.4 Hz, 1H), 7.80 (t, J = 7.6 Hz, 1H), 7.69-7.63 (m, 2H), 7.54 (t,
J = 8.0 Hz, 1H), 7.30 (t, J = 7.6 Hz, 1H), 7.23-7.20 (m, 2H),
7.05-7.00 (m, 2H), 6.77 (d, J = 8.0 Hz, 2H); 13C NMR (100 MHz,
CDCl3): δ 193.6, 155.9, 155.0, 135.8, 134.4, 133.9, 133.0, 132.2,
132.1, 130.9, 130.6, 130.3, 129.8, 129.6, 128.3, 125.2, 123.9,
123.7, 118.7, 118.7, 117.1, 110.6; IR (neat): ν 3436, 2924, 2360,
2334, 1667, 1597, 1479, 1448, 1299, 1235, 1041 cm-1; HRMS
(EI) calcd for C24H15NO2 349.1103, found 349.1104.
4.2.33
[1,2'-Binaphthalen]-3-yl(2-phenoxyphenyl)methanone
(6k). The reaction of 1k (0.3 mmol, 89.5 mg), 2a (0.9 mmol,
268.6 mg), KF (1.8 mmol, 104.6 mg), 18-C-6 (1.8 mmol, 475.7
mg) and TfOH (0.33 mmol, 49.5 mg) in THF (3 mL) afforded
1
37.8 mg (28%) of 6k. Pale yellow oil; H NMR (400 MHz,
CDCl3): δ 8.35 (s, 1H), 7.99 (d, J = 2.0 Hz, 1H), 7.97-7.86 (m,
6H), 7.63 (dd, J1 = 7.6 Hz, J2 = 2.0 Hz, 1H), 7.57 (dd, J1 = 8.4 Hz,
J2 = 1.6 Hz, 1H), 7.54-7.43 (m, 5H), 7.24-7.17 (m, 3H), 7.03-
6.97 (m, 2H), 6.85-6.83 (m, 2H); 13C NMR (100 MHz, CDCl3): δ
195.6, 156.4, 155.0, 140.5, 137.5, 134.5, 134.1, 133.3, 132.9,
132.6, 132.1, 131.6, 130.9, 130.4, 130.0, 129.6, 128.8, 128.6,
128.1, 128.0, 127.7, 127.7, 126.5, 126.4, 126.2, 126.2, 126.1,
123.6, 123.3, 118.9, 118.7; IR (neat): ν 3050, 2918, 2853, 1660,
1596, 1478, 1447, 1303, 1235 cm-1; HRMS calcd for C33H23O2
[M + H]+ 451.1698, found 451.1694.
4.2.29 (2-Phenoxyphenyl)(4-phenylnaphthalen-2-yl) methanone
(6g). The reaction of 1g (0.3 mmol, 74.5 mg), 2a (0.9 mmol,
268.6 mg), KF (1.8 mmol, 104.6 mg), 18-C-6 (1.8 mmol, 475.7
mg) and TfOH (0.33 mmol, 49.5 mg) in THF (3 mL) afforded
1
18.0 mg (15%) of 6g. Pale yellow oil; H NMR (400 MHz,
CDCl3): δ 8.31 (s, 1H), 7.96-7.93 (m, 1H), 7.89 (d, J = 2.0 Hz,
1H), 7.61 (dd, J1 = 7.6 Hz, J2 = 2.0 Hz, 1H), 7.53-7.43 (m, 8H),
7.24-7.18 (m, 4H), 7.03-6.98 (m, 2H), 6.84-6.82 (m, 2H); 13C
NMR (100 MHz, CDCl3): δ 195.6, 156.4, 155.0, 140.5, 140.0,
134.3, 134.0, 132.9, 132.1, 131.6, 130.4, 130.0, 130.0, 129.6,
128.6, 128.3, 127.5, 126.5, 126.1, 125.8, 123.6, 123.3, 120.4,
118.9, 118.7; IR (neat): ν 2957, 2915, 2848, 1650, 1594, 1467,
1435, 1270, 1111 cm-1; HRMS calcd for C29H21O2 [M + H]+
401.1542, found 401.1544.
4.2.34 Ethyl 3-(5-methyl-2-phenoxybenzoyl)-1-naphthoate (6l).
The reaction of 1l (0.3 mmol, 77.5 mg), 2a (0.9 mmol, 268.6 mg),
KF (1.8 mmol, 104.6 mg), 18-C-6 (1.8 mmol, 475.7 mg) and
TfOH (0.33 mmol, 49.5 mg) in THF (3 mL) afforded 29.6 mg
(24%) of 6l. Pale yellow oil; 1H NMR (400 MHz, CDCl3): δ 8.92
(d, J = 8.4 Hz, 1H), 8.60 (d, J = 1.6 Hz, 1H), 8.42 (s, 1H), 7.91 (d,
J = 8.4 Hz, 1H), 7.72-7.67 (m, 1H), 7.58-7.54 (m, 1H), 7.42 (d, J
= 1.2 Hz, 1H), 7.31 (dd, J1 = 8.0 Hz, J2 = 2.0 Hz, 1H), 7.18-7.16
(m, 2H), 6.99-6.95 (m, 1H), 6.92 (d, J = 8.4 Hz, 1H), 6.77-6.75
(m, 2H), 4.47 (q, J = 7.2 Hz, 2H), 2.41 (s, 3H), 1.45 (t, J = 7.2 Hz,
3H); 13C NMR (100 MHz, CDCl3): δ 194.9, 167.1, 156.6, 152.7,
136.3, 133.7, 133.4, 133.2, 133.1, 133.0, 130.7, 130.3, 130.2,
130.1, 129.6, 129.2, 127.8, 126.8, 125.9, 123.3, 119.0, 118.4,
61.3, 20.6, 14.3; IR (neat): ν 3050, 2922, 2842, 1718, 1660, 1592,
1477, 1232, 1183, 1037 cm-1; HRMS calcd for C27H23O4 [M +
H]+ 411.1596, found 411.1598.
4.2.30 (4-(4-Methoxyphenyl)naphthalen-2-yl)(2-phenoxyphenyl)
methanone (6h). The reaction of 1h (0.3 mmol, 83.5 mg), 2a (0.9
mmol, 268.6 mg), KF (1.8 mmol, 104.6 mg), 18-C-6 (1.8 mmol,
475.7 mg) and TfOH (0.33 mmol, 49.5 mg) in THF (3 mL)
1
afforded 31.0 mg (24%) of 6h. Pale yellow oil; H NMR (400
MHz, CDCl3): δ 8.28 (s, 1H), 7.94-7.90 (m, 2H), 7.87 (d, J = 2.0
Hz, 1H), 7.60 (dd, J1 = 7.6 Hz, J2 = 2.0 Hz, 1H), 7.52-7.44 (m,
3H), 7.39-7.37 (m, 2H), 7.26-7.18 (m, 3H), 7.03-6.98 (m, 4H),
6.84-6.82 (m, 2H), 3.88 (s, 3H); 13C NMR (100 MHz, CDCl3): δ
195.6, 159.1, 156.5, 155.0, 140.2, 134.3, 134.2, 132.9, 132.3,
132.0, 131.4, 131.3, 131.0, 130.3, 130.0, 129.6, 128.5, 126.4,
126.1, 125.8, 123.5, 123.3, 118.9, 118.7, 113.7, 55.3; IR (neat): ν
2924, 2842, 1652, 1591, 1466, 1385, 1277, 1250, 1030 cm-1;
HRMS calcd for C30H23O3 [M + H]+ 431.1647, found 431.1650.
4.2.35 Ethyl 3-(5-methoxy-2-phenoxybenzoyl)-1-naphthoate (6m).
The reaction of 1m (0.3 mmol, 82.3 mg), 2a (0.9 mmol, 268.6
mg), KF (1.8 mmol, 104.6 mg), 18-C-6 (1.8 mmol, 475.7 mg)
and TfOH (0.33 mmol, 49.5 mg) in THF (3 mL) afforded 40.9
mg (32%) of 6m. Pale yellow oil; 1H NMR (400 MHz, CDCl3): δ
8.92 (d, J = 8.4 Hz, 1H), 8.60 (d, J = 1.6 Hz, 1H), 8.40 (s, 1H),
7.90 (d, J = 8.0 Hz, 1H), 7.70-7.68 (m, 1H), 7.57-7.54 (m ,1H),
7.16-7.12 (m, 3H), 7.10-7.07 (m, 1H) , 7.02 (d, J = 8.8 Hz, 1H),
6.95-6.91 (m, 1H), 6.71-6.89 (m, 2H), 4.47 (q, J = 7.2 Hz, 2H),
3.86 (s, 3H), 1.45 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz,
CDCl3): δ 194.4, 167.0, 157.4, 155.8, 147.9, 136.4, 133.4, 133.3,
132.9, 131.6, 130.2, 130.1, 129.5, 129.0, 127.8, 126.9, 125.9,
4.2.31
(4-(4-Bromophenyl)naphthalen-2-yl)(2-phenoxyphenyl)
methanone (6i). The reaction of 1i (0.3 mmol, 98.2 mg), 2a (0.9
mmol, 268.6 mg), KF (1.8 mmol, 104.6 mg), 18-C-6 (1.8 mmol,
475.7 mg) and TfOH (0.33 mmol, 49.5 mg) in THF (3 mL)
1
afforded 43.1 mg (30%) of 6i. Pale yellow oil; H NMR (400
MHz, CDCl3): δ 8.31 (s, 1H), 7.95-7.93 (m, 1H), 7.86 (d, J = 2.4
Hz, 1H), 7.83-7.81 (m, 1H), 7.61-7.59 (m, 3H), 7.54-7.46 (m,

1487, 1304, 1240, 1230, 1155 cm-1; HRMS (EI) calcd for
C27H22O4 410.1518, found 410.1515.
122.9, 121.3, 118.7, 117.6, 114.3, 61.3, 55.8,A14C.3C; IER P(nTeaEt)D: ν MANUSCRIPT
2957, 2919, 2852, 1714, 1661, 1591, 1470, 1270, 1217, 1034 cm-
1; HRMS calcd for C27H23O5 [M + H]+ 427.1545, found 427.1548.
4.2.40 Ethyl 3-(4-methoxy-2-phenoxybenzoyl)-1-naphthoate (6r).
The reaction of 1r (0.3 mmol, 82.3 mg), 2a (0.9 mmol, 268.6
mg), KF (1.8 mmol, 104.6 mg), 18-C-6 (1.8 mmol, 475.7 mg)
and TfOH (0.33 mmol, 49.5 mg) in THF (3 mL) afforded 44.8
4.2.36 Ethyl 3-(5-fluoro-2-phenoxybenzoyl)-1-naphthoate (6n).
The reaction of 1n (0.3 mmol, 78.7 mg), 2a (0.9 mmol, 268.6
mg), KF (1.8 mmol, 104.6 mg), 18-C-6 (1.8 mmol, 475.7 mg)
and TfOH (0.33 mmol, 49.5 mg) in THF (3 mL) afforded 21.1
mg (17%) of 6n. Pale yellow oil; 1H NMR (400 MHz, CDCl3): δ
8.92 (d, J = 8.8 Hz, 1H), 8.61 (d, J = 1.6 Hz, 1H), 8.42 (s, 1H),
7.92 (d, J = 8.0 Hz, 1H), 7.73-7.69 (m, 1H), 7.59-7.55 (m, 1H),
7.33 (dd, J1 = 8.0 Hz, J2 = 3.2 Hz, 1H), 7.24-7.17 (m, 3H), 7.01-
6.98 (m, 2H), 6.78-6.76 (m, 2H), 4.47 (q, J = 7.2 Hz, 2H), 1.45 (t,
1
mg (35%) of 6r. Pale yellow oil; H NMR (400 MHz, CDCl3): δ
8.82 (d, J = 8.4 Hz, 1H), 8.49 (s, 1H), 8.34 (s, 1H), 7.82 (d, J =
8.0 Hz, 1H), 7.59-7.56 (m, 2H), 7.45 (t, J = 7.6 Hz, 1H), 7.12-
7.08 (m, 2H), 6.91 (t, J = 7.2 Hz, 1H), 6.71-6.69 (m, 3H), 6.38 (s,
1H), 4.38 (q, J = 7.2 Hz, 2H), 3.71 (s, 3H), 1.36 (t, J = 7.2 Hz,
3H); 13C NMR (100 MHz, CDCl3): δ 193.9, 167.1, 163.5, 157.2,
155.8, 135.7, 134.6, 133.0, 133.0, 132.8, 130.0, 129.8, 129.7,
129.5, 127.5, 126.7, 125.9, 123.8, 122.6, 118.9, 108.8, 104.3,
61.2, 55.6, 14.3; IR (neat): ν 2989, 2932, 1722, 1665, 1577, 1465,
1265, 1200 cm-1; HRMS (EI) calcd for C27H22O5 426.1467, found
426.1469.
J = 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3): δ 193.2 (d, JC-F
1.5 Hz), 166.9, 158.4 (d, JC-F = 243.5 Hz), 156.5, 150.8 (d, JC-F
=
=
2.1 Hz), 136.4, 133.4, 133.0, 132.9, 131.7 (d, JC-F = 6.6 Hz),
130.3, 130.2, 129.7, 128.9, 128.0, 127.0, 126.0, 123.7, 129.6 (d,
JC-F = 7.3 Hz), 119.1 (d, JC-F = 23.4 Hz), 118.4, 116.8 (d, JC-F
=
24.8 Hz), 61.3, 14.3; IR (neat): ν 3069, 2985, 2927, 2849, 2254,
1716, 1663, 1585, 1482, 1242, 1029 cm-1; HRMS calcd for
C26H20FO4 [M + H]+ 415.1346, found 415.1347.
4.2.41 Ethyl 3-(4-bromo-2-phenoxybenzoyl)-1-naphthoate (6s).
The reaction of 1s (0.3 mmol, 96.9 mg), 2a (0.9 mmol, 268.6 mg),
KF (1.8 mmol, 104.6 mg), 18-C-6 (1.8 mmol, 475.7 mg) and
TfOH (0.33 mmol, 49.5 mg) in THF (3 mL) afforded 48.5 mg
(34%) of 6s. Pale yellow oil; 1H NMR (400 MHz, CDCl3): δ 8.92
(d, J = 8.4 Hz, 1H), 8.62 (d, J = 1.6 Hz, 1H), 8.44 (s, 1H), 7.94 (d,
J = 8.0 Hz, 1H), 7.73-7.69 (m, 1H), 7.59-7.56 (m, 1H), 7.49 (d, J
= 8.4 Hz, 1H), 7.39 (dd, J1 = 8.4 Hz, J2 = 1.6 Hz, 1H), 7.27-7.23
(m, 2H), 7.09-7.07 (m, 2H), 6.87-6.85 (m, 2H), 4.47 (q, J = 7.2
Hz, 2H), 1.46 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3): δ
193.8, 167.0, 156.1, 155.1, 136.1, 133.4, 133.3, 133.0, 131.7,
130.2, 130.2, 129.9, 129.0, 128.7, 128.0, 127.0, 126.4, 126.1,
126.0, 124.6, 120.9, 119.5, 61.3, 14.3; IR (neat): ν 2923, 1715,
1666, 1588, 1473, 1393, 1303, 1233, 1153, 1026 cm-1; HRMS
(EI) calcd for C26H1979BrO4 474.0467, found 474.0461.
4.2.37 Ethyl 3-(5-chloro-2-phenoxybenzoyl)-1-naphthoate (6o).
The reaction of 1o (0.3 mmol, 83.6 mg), 2a (0.9 mmol, 268.6
mg), KF (1.8 mmol, 104.6 mg), 18-C-6 (1.8 mmol, 475.7 mg)
and TfOH (0.33 mmol, 49.5 mg) in THF (3 mL) afforded 36.2
1
mg (28%) of 6o. Pale yellow oil; H NMR (400 MHz, CDCl3): δ
8.92 (d, J = 8.4 Hz, 1H), 8.61 (d, J = 2.0 Hz, 1H), 8.44 (s, 1H),
7.95 (d, J = 8.0 Hz, 1H), 7.74-7.70 (m, 1H), 7.61-7.57 (m, 2H),
7.45 (dd, J1 = 8.8 Hz, J2 = 2.4 Hz, 1H), 7.24-7.20 (m, 2H), 7.06-
7.03 (m, 1H), 6.92 (d, J = 8.8 Hz, 1H), 6.83-6.81 (m, 2H), 4.49 (q,
J = 7.2 Hz, 2H), 1.45 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz,
CDCl3): δ 193.3, 167.0, 155.8, 153.8, 136.3, 133.4, 133.1, 133.0,
132.2, 131.5, 130.4, 130.3, 130.1, 129.8, 129.0, 128.6, 128.1,
127.1, 126.0, 124.2, 119.6, 119.1, 61.4, 14.4; IR (neat): ν 3040,
1710, 1662, 1464, 1296, 1229, 1188, 1148, 1020 cm-1; HRMS
calcd for C26H2035ClO4 [M + H]+ 431.1050, found 431.1049.
4.3 General Procedure for the Synthesis of Products 5
Under nitrogen atmosphere, 3-vinylchromones 1 (0.3 mmol),
KF (104.6 mg, 1.8 mmol) and 18-C-6 (1.8 mmol, 475.7 mg) were
added to a 25 mL of Schlenk tube equipped with a stirrer bar.
Then anhydrous THF (3.0 mL), trifluoroacetic acid (TFA) (0.75
mmol, 85.5 mg) and aryne precursor 2 (0.9 mmol) were added.
The reaction mixture was then stirred at room temperature. After
24 hours, the mixture was poured into water (20 mL), and then
the water layer was extracted with CH2Cl2 (5 mL × 3). The
organic layer were combined and dried over Na2SO4. After
filtration and evaporation, the residue was purified by silica gel
chromatography (petroleum ether/ethyl acetate 30:1) to afford 5.
4.2.38 Ethyl 3-(5-bromo-2-phenoxybenzoyl)-1-naphthoate (6p).
The reaction of 1p (0.3 mmol, 96.9 mg), 2a (0.9 mmol, 268.6
mg), KF (1.8 mmol, 104.6 mg), 18-C-6 (1.8 mmol, 475.7 mg)
and TfOH (0.33 mmol, 49.5 mg) in THF (3 mL) afforded 29.9
mg (21%) of 6p. Pale yellow oil; 1H NMR (400 MHz, CDCl3): δ
8.92 (d, J = 8.4 Hz, 1H), 8.62 (d, J = 1.6 Hz, 1H), 8.44 (s, 1H),
7.94 (d, J = 8.0 Hz, 1H), 7.73 (d, J = 2.4 Hz, 1H), 7.71-7.69 (m,
1H), 7.59-7.55 (m, 2H), 7.24-7.20 (m, 2H), 7.06-7.02 (m, 1H),
6.86-6.82 (m, 3H), 4.47 (q, J = 7.2 Hz, 2H), 1.45 (t, J = 7.2 Hz,
3H); 13C NMR (100 MHz, CDCl3): δ 193.1, 166.9, 155.5, 154.4,
136.3, 135.1, 133.3, 133.1, 133.0, 132.9, 131.8, 130.3, 130.2,
129.8, 128.9, 128.0, 127.0, 126.0, 124.2, 119.8, 119.1, 115.8,
61.3, 14.3; IR (neat): ν 2922, 2851, 1724, 1653, 1594, 1470, 1238,
1150, 1027 cm-1; HRMS (EI) calcd for C26H1979BrO4 474.0467,
found 474.0466.
4.3.1 Ethyl 3-(2-hydroxybenzoyl)-1-naphthoate (5a). The reaction
of 1a (0.3 mmol, 73.3 mg), 2a (0.9 mmol, 268.6 mg), KF (1.8
mmol, 104.6 mg), 18-C-6 (1.8 mmol, 475.7 mg) and TFA (0.75
mmol, 85.5 mg) in THF (3 mL) afforded 90.3 mg (94%) of 5a.
Pale yellow solid, mp 81.4-83.3 oC; 1H NMR (400 MHz, CDCl3):
δ 11.96 (s, 1H), 8.99 (d, J = 8.4 Hz, 1H), 8.48 (d, J = 1.6 Hz, 1H),
8.33 (s, 1H), 7.98 (d, J = 8.0 Hz, 1H), 7.77-7.73 (m, 1H), 7.65-
7.62 (m, 2H), 7.58-7.53 (m, 1H), 7.12 (dd, J1 = 8.4 Hz, J2 = 0.8
Hz, 1H), 6.94-6.90 (m, 1H), 4.50 (q, J = 7.2 Hz, 2H), 1.46 (t, J =
7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3): δ 200.4, 166.8, 163.3,
136.6, 134.8, 133.8, 133.4, 132.8, 132.6, 129.9, 129.8, 129.3,
128.2, 127.3, 126.0, 119.1, 118.9, 118.6, 61.5, 14.3; IR (neat): ν
3415, 2984, 1717, 1626, 1482, 1445, 1242, 1147, 1026 cm-1;
HRMS calcd for C20H17O4 [M + H]+ 321.1127, found 321.1131.
4.2.39 Ethyl 3-(4-methyl-2-phenoxybenzoyl)-1-naphthoate (6q).
The reaction of 1q (0.3 mmol, 77.5 mg), 2a (0.9 mmol, 268.6
mg), KF (1.8 mmol, 104.6 mg), 18-C-6 (1.8 mmol, 475.7 mg)
and TfOH (0.33 mmol, 49.5 mg) in THF (3 mL) afforded 39.4
mg (32%) of 6q. Pale yellow oil; 1H NMR (400 MHz, CDCl3): δ
8.91 (d, J = 8.4 Hz, 1H), 8.62 (s, 1H), 8.43 (s, 1H), 7.92 (d, J =
8.0 Hz, 1H), 7.69 (t, J = 8.0 Hz, 1H), 7.57-7.53 (m, 2H), 7.22-
7.18 (m, 2H), 7.08 (d, J = 7.6 Hz, 1H), 7.02-7.00 (m, 1H), 6.81-
6.79 (m, 3H), 4.47 (q, J = 7.2 Hz, 2H), 2.39 (s, 3H), 1.45 (t, J =
7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3): δ 194.6, 167.1, 156.2,
155.2, 143.7, 136.1, 134.0, 133.1, 133.0, 130.7, 130.1, 129.9,
129.6, 129.3, 127.7, 127.5, 126.8, 125.9, 124.3, 123.6, 119.1,
118.8, 61.2, 21.6, 14.3; IR (neat): ν 2970, 2859, 1716, 1663, 1612,
4.3.2 Benzyl 3-(2-hydroxybenzoyl)-1-naphthoate (5b). The
reaction of 1b (0.3 mmol, 91.9 mg), 2a (0.9 mmol, 268.6 mg),
KF (1.8 mmol, 104.6 mg), 18-C-6 (1.8 mmol, 475.7 mg) and
TFA (0.75 mmol, 85.5 mg) in THF (3 mL) afforded 96.4 mg
o
(84%) of 5b. Yellow solid, mp 122.9-123.6 C; 1H NMR (400

10
Tetrahedron
ACCEPTED MANUSCRIPT
MHz, CDCl3): δ 11.93 (s, 1H), 9.01 (d, J = 8.4 Hz, 1H), 8.52
4.3.7
(2-Hydroxyphenyl)(4-phenylnaphthalen-2-yl)methanone
(d, J = 1.6 Hz, 1H), 8.33 (s, 1H), 7.98 (d, J = 8.0 Hz, 1H), 7.76-
7.72 (m, 1H), 7.65-7.61 (m, 2H), 7.57-7.53 (m, 1H), 7.50-7.48
(m, 2H), 7.41-7.35 (m, 3H), 7.11 (d, J = 8.4 Hz, 1H), 6.92-6.88
(m, 1H), 5.48 (s, 2H); 13C NMR (100 MHz, CDCl3): δ 200.2,
166.5, 163.3, 136.6, 135.7, 135.0, 133.8, 133.3, 132.8, 132.7,
130.1, 129.8, 129.6, 128.7, 128.4, 128.3, 127.7, 127.3, 126.0,
119.0, 118.9, 118.6, 67.1; IR (neat): ν 3415, 1718, 1627, 1486,
1449, 1276, 1240, 1211, 1149, 1005 cm-1; HRMS calcd for
C25H19O4 [M + H]+ 383.1283, found 383.1289.
(5g). The reaction of 1g (0.3 mmol, 74.5 mg), 2a (0.9 mmol,
268.6 mg), KF (1.8 mmol, 104.6 mg), 18-C-6 (1.8 mmol, 475.7
mg) and TFA (0.75 mmol, 85.5 mg) in THF (3 mL) afforded 83.7
mg (86%) of 5g. Pale yellow oil; 1H NMR (400 MHz, CDCl3): δ
12.07 (s, 1H), 8.15 (d, J = 0.8 Hz, 1H), 7.98-7.94 (m, 2H), 7.74-
7.71 (m, 2H), 7.56-7.43 (m, 8H), 7.09 (dd, J1 = 8.4 Hz, J2 = 1.2
Hz, 1H), 6.90-6.85 (m, 1H); 13C NMR (100 MHz, CDCl3): δ
201.3, 163.2, 140.9, 139.6, 136.3, 134.5, 133.6, 133.1, 132.6,
129.9, 129.5, 128.4, 128.4, 128.3, 127.7, 126.8, 126.1, 126.0,
119.3, 118.7, 118.4; IR (neat): ν 3210, 2918, 1625, 1603, 1482,
1391, 1241, 1159 cm-1; HRMS calcd for C23H17O2 [M + H]+
325.1229, found 325.1230.
4.3.3 tert-Butyl 3-(2-hydroxybenzoyl)-1-naphthoate (5c). The
reaction of 1c (0.3 mmol, 81.7 mg), 2a (0.9 mmol, 268.6 mg), KF
(1.8 mmol, 104.6 mg), 18-C-6 (1.8 mmol, 475.7 mg) and TFA
(0.75 mmol, 85.5 mg) in THF (3 mL) afforded 97.2 mg (93%) of
4.3.8
(2-Hydroxyphenyl)(4-(4-methoxyphenyl)naphthalen-2-
5c. Pale yellow solid, mp 112.8-112.9 C; 1H NMR (400 MHz,
yl)methanone (5h). The reaction of 1h (0.3 mmol, 83.5 mg), 2a
(0.9 mmol, 268.6 mg), KF (1.8 mmol, 104.6 mg), 18-C-6 (1.8
mmol, 475.7 mg) and TFA (0.75 mmol, 85.5 mg) in THF (3 mL)
afforded 92.5 mg (87%) of 5h. Yellow solid, mp 143.4-143.8 oC;
1H NMR (400 MHz, CDCl3): δ 12.07 (s, 1H), 8.15 (d, J = 0.8 Hz,
1H), 8.01-7.98 (m, 2H), 7.74 (dd, J1 = 8.0 Hz, J2 = 1.2 Hz, 1H),
7.71 (d, J = 2.0 Hz, 1H), 7.58-7.50 (m, 3H), 7.46-7.44 (m, 2H),
7.10 (dd, J1 = 8.4 Hz, J2 = 0.8 Hz, 1H), 7.07-7.02 (m, 2H), 6.92-
6.88 (m, 1H), 3.89 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 201.4,
163.2, 159.3, 140.6, 136.3, 134.6, 133.7, 133.4, 132.7, 132.0,
131.1, 129.6, 129.5, 128.2, 126.8, 126.2, 126.0, 119.4, 118.7,
118.4, 113.9, 55.3; IR (neat): ν 3419, 3050, 1626, 1609, 1514,
1483, 1395, 1248, 1159, 1030 cm-1; HRMS calcd for C24H19O3
[M + H]+ 355.1334, found 355.1332.
o
CDCl3): δ 11.98 (s, 1H), 8.91 (d, J = 8.4 Hz, 1H), 8.36 (d, J = 1.6
Hz, 1H), 8.29 (s, 1H), 7.97 (d, J = 8.0 Hz, 1H), 7.75-7.71 (m, 1H),
7.65-7.60 (m, 2H), 7.57-7.53 (m, 1H), 7.11 (d, J = 8.0 Hz, 1H),
6.93-6.89 (m, 1H), 1.68 (s, 9H); 13C NMR (100 MHz, CDCl3): δ
200.5, 166.3, 163.3, 136.6, 134.2, 133.7, 133.4, 132.7, 132.5,
130.1, 129.7, 129.7, 128.8, 127.1, 126.0, 119.1, 118.9, 118.6,
82.2, 28.3; IR (neat): ν 3240, 2976, 1712, 1627, 1482, 1449, 1366,
1283, 1246, 1147, 1010 cm-1; HRMS calcd for C22H21O4 [M +
H]+ 349.1440, found 349.1444.
4.3.4 1-(3-(2-Hydroxybenzoyl)naphthalen-1-yl)ethanone (5d).
The reaction of 1d (0.3 mmol, 64.3 mg), 2a (0.9 mmol, 268.6
mg), KF (1.8 mmol, 104.6 mg), 18-C-6 (1.8 mmol, 475.7 mg)
and TFA (0.75 mmol, 85.5 mg) in THF (3 mL) afforded 81.9 mg
o
1
(94%) of 5d. Pale yellow solid, mp 115.5-116.9 C; H NMR
(400 MHz, CDCl3): δ 11.90 (s, 1H), 8.78 (d, J = 8.4 Hz, 1H),
8.30 (s, 1H), 8.23 (d, J = 1.6 Hz, 1H), 7.97 (d, J = 8.0 Hz, 1H),
7.76-7.71 (m, 1H), 7.65-7.62 (m, 2H), 7.59-7.54 (m, 1H), 7.13 (d,
J = 8.4 Hz, 1H), 6.95-6.91 (m, 1H), 2.79 (s, 3H); 13C NMR (100
MHz, CDCl3): δ 201.2, 200.2, 163.2, 136.7, 136.0, 134.8, 133.5,
133.2, 132.8, 131.4, 130.3, 129.7, 127.7, 127.5, 126.1, 119.0,
118.9, 118.7, 30.0; IR (neat): ν 3054, 1682, 1625, 1487, 1453,
1350, 1275, 1239, 1213 cm-1; HRMS calcd for C19H14O3Na [M +
Na]+ 313.0841, found 313.0837.
4.3.9
(4-(4-Bromophenyl)naphthalen-2-yl)(2-hydroxyphenyl)
methanone (5i). The reaction of 1i (0.3 mmol, 98.2 mg), 2a (0.9
mmol, 268.6 mg), KF (1.8 mmol, 104.6 mg), 18-C-6 (1.8 mmol,
475.7 mg) and TFA (0.75 mmol, 85.5 mg) in THF (3 mL)
afforded 106.5 mg (88%) of 5i. Yellow solid, mp 113.3-114.1 oC;
1H NMR (400 MHz, CDCl3): δ 11.91 (s, 1H), 8.04 (s, 1H), 7.86
(d, J = 8.0 Hz, 1H), 7.78 (d, J = 7.2 Hz, 1H), 7.60-7.57 (m, 2H),
7.50-7.37 (m, 5H), 7.26-7.24 (m, 1H), 6.98 (d, J = 8.4 Hz, 1H),
6.81-6.75 (m, 2H); 13C NMR (100 MHz, CDCl3): δ 200.9, 163.2,
139.5, 138.4, 136.3, 134.4, 133.4, 132.8, 132.5, 131.5, 131.5,
130.3, 129.6, 128.5, 126.9, 126.0, 125.6, 121.9, 119.2, 118.7,
118.4 cm-1; IR (neat): ν 3054, 2924, 1625, 1484, 1448, 1394,
1309, 1241, 1213, 1158, 1008 cm-1; HRMS (EI) calcd for
C23H1579BrO2 402.0255, found 402.0259.
4.3.5
(4-Benzoylnaphthalen-2-yl)(2-hydroxyphenyl)methanone
(5e). The reaction of 1e (0.3 mmol, 82.9 mg), 2a (0.9 mmol,
268.6 mg), KF (1.8 mmol, 104.6 mg), 18-C-6 (1.8 mmol, 475.7
mg) and TFA (0.75 mmol, 85.5 mg) in THF (3 mL) afforded 94.1
mg (89%) of 5e. Pale yellow solid, mp 100.0-101.4 oC; 1H NMR
(400 MHz, CDCl3): δ 11.91 (s, 1H), 8.39 (s, 1H), 8.15-8.13 (m,
1H), 8.05-8.02 (m, 1H), 7.91-7.86 (m, 3H), 7.68-7.60 (m, 4H),
7.55-7.46 (m, 3H), 7.09 (d, J = 8.0 Hz, 1H), 6.92-6.88 (m, 1H);
13C NMR (100 MHz, CDCl3): δ 200.4, 197.0, 163.2, 137.6, 137.0,
136.6, 133.7, 133.4, 133.0, 132.7, 132.3, 130.4, 129.8, 129.7,
129.5, 128.6, 127.6, 126.6, 125.8, 119.0, 118.9, 118.6; IR (neat):
ν 3059, 1662, 1625, 1478, 1445, 1304, 1280, 1155 cm-1; HRMS
calcd for C24H16O3Na [M + Na]+ 375.0997, found 375.0992.
4.3.10
(2-Hydroxyphenyl)(4-(4-nitrophenyl)naphthalen-2-
yl)methanone (5j). The reaction of 1j (0.3 mmol, 88.0 mg), 2a
(0.9 mmol, 268.6 mg), KF (1.8 mmol, 104.6 mg), 18-C-6 (1.8
mmol, 475.7 mg) and TFA (0.75 mmol, 85.5 mg) in THF (3 mL)
afforded 92.0 mg (83%) of 5j. Pale yellow solid, mp 185.7-186.0
oC; 1H NMR (400 MHz, CDCl3): δ 11.96 (s, 1H), 8.40-8.38 (m,
2H), 8.25 (s, 1H), 8.06-8.04 (m, 1H), 7.87-7.84 (m, 1H), 7.75-
7.71 (m, 4H), 7.67-7.61 (m, 2H), 7.58-7.54 (m, 1H), 7.12 (d, J =
8.0 Hz, 1H), 6.95-6.91 (m, 1H); 13C NMR (100 MHz, CDCl3): δ
200.8, 163.3, 147.5, 146.5, 138.6, 136.6, 134.5, 133.4, 132.6,
132.4, 131.2, 130.9, 129.9, 129.1, 127.3, 126.3, 125.3, 123.7,
119.2, 118.9, 118.6; IR (neat): ν 3424, 1624, 1602, 1518, 1395,
1348, 1240, 1155 cm-1; HRMS calcd for C23H16NO4 [M + H]+
370.1079, found 370.1081.
4.3.11 [1,2'-Binaphthalen]-3-yl(2-hydroxyphenyl)methanone (5k).
The reaction of 1k (0.3 mmol, 89.5 mg), 2a (0.9 mmol, 268.6
mg), KF (1.8 mmol, 104.6 mg), 18-C-6 (1.8 mmol, 475.7 mg)
and TFA (0.75 mmol, 85.5 mg) in THF (3 mL) afforded 101.1
mg (90%) of 5k. Pale yellow solid, mp 151.9-152.8 oC; 1H NMR
(400 MHz, CDCl3): δ 11.97 (s, 1H), 8.04 (s, 1H), 7.85-7.72 (m,
5H), 7.68 (s, 1H), 7.61 (d, J = 8.0 Hz, 1H), 7.48 (d, J = 8.0 Hz,
1H), 7.42-7.34 (m, 5H), 6.96 (d, J = 8.4 Hz, 1H), 6.78-6.72 (m,
2H); 13C NMR (100 MHz, CDCl3): δ 201.2, 163.2, 140.8, 137.1,
4.3.6 3-(2-Hydroxybenzoyl)-1-naphthonitrile (5f). The reaction of
1f (0.3 mmol, 59.2 mg), 2a (0.9 mmol, 268.6 mg), KF (1.8 mmol,
104.6 mg), 18-C-6 (1.8 mmol, 475.7 mg) and TFA (0.75 mmol,
85.5 mg) in THF (3 mL) afforded 54.9 mg (67%) of 5f. Pale
yellow solid, mp 147.1-148.5 C; 1H NMR (400 MHz, CDCl3): δ
o
11.77 (s, 1H), 8.41 (s, 1H), 8.33 (d, J = 8.4 Hz, 1H), 8.21 (d, J =
1.6 Hz, 1H), 8.05 (d, J = 8.0 Hz, 1H), 7.87-7.83 (m, 1H), 7.77-
7.72 (m, 1H), 7.60-7.55 (m, 2H), 7.15-7.11 (m, 1H), 6.97-6.92
(m, 1H); 13C NMR (100 MHz, CDCl3): δ 198.8, 163.3, 137.0,
134.8, 134.4, 133.3, 133.0, 132.0, 131.9, 130.8, 129.9, 128.7,
125.2, 119.1, 118.8, 118.7, 116.9, 111.0; IR (neat): ν 1625, 1604,
1307, 1274, 1244, 1209, 1152 cm-1; HRMS (EI) calcd for
C18H11NO2 273.0790, found 273.0788.

136.3, 134.6, 133.6, 133.3, 133.2, 132.6, 132.6, 130.0, 129.5,
mg), KF (1.8 mmol, 104.6 mg), 18-C-6 (1.8 mmol, 475.7 mg)
and TFA (0.75 mmol, 85.5 mg) in THF (3 mL) afforded 74.5 mg
(70%) of 5p. Yellow solid, mp 62.5-63.9 oC; 1H NMR (400 MHz,
CDCl3): δ 11.82 (s, 1H), 9.00 (d, J = 8.4 Hz, 1H), 8.46 (d, J = 1.6
Hz, 1H), 8.32 (s, 1H), 8.01 (d, J = 8.4 Hz, 1H), 7.79-7.74 (m, 1H),
7.68-7.63 (m, 1H), 7.60 (d, J = 2.4 Hz, 1H), 7.49 (dd, J1 = 8.8 Hz,
J2 = 2.4 Hz, 1H), 7.08 (d, J = 8.8 Hz, 1H), 4.50 (q, J = 7.2 Hz,
2H), 1.47 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3): δ
199.3, 166.6, 161.7, 136.4, 134.8, 133.1, 132.8, 132.8, 132.1,
130.2, 129.9, 129.0, 128.5, 127.4, 126.0, 123.6, 120.3, 119.7,
61.5, 14.3; IR (neat): ν 2980, 1718, 1630, 1599, 1467, 1326, 1276,
1245, 1201, 1153, 1026 cm-1; HRMS calcd for C20H1635ClO4 [M
+ H]+ 355.0737, found 355.0729.
ACCEPTED MANUSCRIPT
129.4, 128.8, 128.4, 128.0, 127.8, 127.7, 126.8, 126.4, 126.3,
126.3, 126.1, 119.3, 118.7, 118.4; IR (neat): ν 3053, 2925, 1842,
1624, 1601, 1447, 1241, 1212, 1157 cm-1; HRMS (EI) calcd for
C27H18O2 374.1307, found 374.1306.
4.3.12 Ethyl 3-(2-hydroxy-6-methoxybenzoyl)-1-naphthoate (5l).
The reaction of 1v (0.3 mmol, 82.3 mg), 2a (0.9 mmol, 268.6
mg), KF (1.8 mmol, 104.6 mg), 18-C-6 (1.8 mmol, 475.7 mg)
and TFA (0.75 mmol, 85.5 mg) in THF (3 mL) afforded 97.8 mg
1
(93%) of 5l. Pale yellow oil; H NMR (400 MHz, CDCl3): δ
10.90 (s, 1H), 8.94 (d, J = 8.4 Hz, 1H), 8.38-8.33 (m, 2H), 7.96
(d, J = 8.4 Hz, 1H), 7.71 (d, J = 8.0 Hz, 1H), 7.58 (d, J = 7.6 Hz,
1H), 7.44 (d, J = 8.4 Hz, 1H), 6.73 (d, J = 8.0 Hz, 1H), 6.46 (d, J
= 8.0 Hz, 1H), 4.47 (q, J = 7.2 Hz, 2H), 3.48 (s, 3H), 1.44 (t, J =
7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3): δ 198.5, 167.1, 162.4,
160.1, 136.7, 136.1, 134.0, 133.0, 132.6, 129.9, 129.6, 129.6,
126.9, 126.7, 125.8, 111.3, 110.6, 102.2, 61.2, 55.3, 14.3; IR
(neat): ν 3415, 2971, 1716, 1621, 1458, 1304, 1245, 1089, 1030
cm-1; HRMS calcd for C21H19O5 [M + H]+ 351.1232, found
351.1236.
4.3.13 Ethyl 3-(2-hydroxy-5-methylbenzoyl)-1-naphthoate (5m).
The reaction of 1l (0.3 mmol, 77.5 mg), 2a (0.9 mmol, 268.6 mg),
KF (1.8 mmol, 104.6 mg), 18-C-6 (1.8 mmol, 475.7 mg) and
TFA (0.75 mmol, 85.5 mg) in THF (3 mL) afforded 89.3 mg
(89%) of 5m. Yellow oil; 1H NMR (400 MHz, CDCl3): δ 11.77 (s,
1H), 9.00 (d, J = 8.4 Hz, 1H), 8.47 (d, J = 1.6 Hz, 1H), 8.31 (s,
1H), 7.99 (d, J = 8.0 Hz, 1H), 7.77-7.72 (m, 1H), 7.65-7.61 (m,
1H), 7.40-7.34 (m, 2H), 7.02 (d, J = 8.4 Hz, 1H), 4.50 (q, J = 7.2
Hz, 2H), 2.25 (s, 3H), 1.46 (t, J = 7.2 Hz, 3H); 13C NMR (100
MHz, CDCl3): δ 200.3, 166.8, 161.2, 137.6, 134.6, 133.9, 133.0,
132.8, 132.5, 129.8, 129.8, 129.3, 128.1, 128.0, 127.2, 125.9,
118.7, 118.3, 61.4, 20.4, 14.3; IR (neat): ν 3320, 2976, 1718,
1632, 1605, 1482, 1279, 1244, 1198, 1145, 1026 cm-1; HRMS
calcd for C21H19O4 [M + H]+ 335.1283, found 335.1287.
4.3.14 Ethyl 3-(2-hydroxy-5-methoxybenzoyl)-1-naphthoate (5n).
The reaction of 1m (0.3 mmol, 82.3 mg), 2a (0.9 mmol, 268.6
mg), KF (1.8 mmol, 104.6 mg), 18-C-6 (1.8 mmol, 475.7 mg)
and TFA (0.75 mmol, 85.5 mg) in THF (3 mL) afforded 86.2 mg
(82%) of 5n. Yellow solid, mp 92.8-93.9 oC; 1H NMR (400 MHz,
CDCl3): δ 11.54 (s, 1H), 8.98 (d, J = 8.4 Hz, 1H), 8.50 (d, J = 1.6
Hz, 1H), 8.36 (s, 1H), 7.98 (d, J = 8.0 Hz, 1H), 7.76-7.72 (m, 1H),
7.65-7.60 (m, 1H), 7.20-7.16 (m, 1H), 7.09-7.04 (m, 2H), 4.50 (q,
J = 7.2 Hz, 2H), 3.67 (s, 3H), 1.46 (t, J = 7.2 Hz, 3H); 13C NMR
(100 MHz, CDCl3): δ 199.7, 166.7, 157.6, 151.6, 134.7, 133.7,
132.8, 132.6, 129.9, 129.8, 129.2, 128.1, 127.3, 125.9, 124.6,
119.5, 118.5, 115.5, 61.4, 55.8, 14.3; IR (neat): ν 2984, 1717,
1607, 1484, 1325, 1275, 1246, 1201, 1146, 1041 cm-1; HRMS
calcd for C21H19O5 [M + H]+ 351.1232, found 351.1234.
4.3.15 Ethyl 3-(5-fluoro-2-hydroxybenzoyl)-1-naphthoate (5o).
The reaction of 1n (0.3 mmol, 78.7 mg), 2a (0.9 mmol, 268.6
mg), KF (1.8 mmol, 104.6 mg), 18-C-6 (1.8 mmol, 475.7 mg)
and TFA (0.75 mmol, 85.5 mg) in THF (3 mL) afforded 82.2 mg
(81%) of 5o. Yellow solid, mp 81.4-82.4 oC; 1H NMR (400 MHz,
CDCl3): δ 11.67 (s, 1H), 8.99 (d, J = 8.4 Hz, 1H), 8.46 (d, J = 1.6
Hz, 1H), 8.32 (s, 1H), 8.00 (d, J = 8.0 Hz, 1H), 7.78-7.73 (m, 1H),
7.67-7.62 (m, 1H), 7.34-7.26 (m, 2H), 7.09 (dd, J1 = 8.8 Hz, J2 =
4.4 Hz, 1H), 4.50 (q, J = 7.2 Hz, 2H), 1.47 (t, J = 7.2 Hz, 3H);
13C NMR (100 MHz, CDCl3): δ 199.3 (d, JC-F = 2.9 Hz), 166.6,
159.4, 154.6 (d, JC-F = 237.7 Hz), 134.7, 133.2, 132.7, 130.2,
4.3.17 Ethyl 3-(5-bromo-2-hydroxybenzoyl)-1-naphthoate (5q).
The reaction of 1p (0.3 mmol, 96.9 mg), 2a (0.9 mmol, 268.6
mg), KF (1.8 mmol, 104.6 mg), 18-C-6 (1.8 mmol, 475.7 mg)
and TFA (0.75 mmol, 85.5 mg) in THF (3 mL) afforded 76.6 mg
o
1
(64%) of 5q. Yellow solid, mp 100.8-101.5 C; H NMR (400
MHz, CDCl3): δ 11.84 (s, 1H), 9.00 (d, J = 8.4 Hz, 1H), 8.46 (d,
J = 1.6 Hz, 1H), 8.32 (s, 1H), 8.01 (d, J = 8.0 Hz, 1H), 7.79-7.74
(m, 2H), 7.68-7.60 (m, 2H), 7.03 (d, J = 8.8 Hz, 1H), 4.50 (q, J =
7.2 Hz, 2H), 1.47 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz,
CDCl3): δ 199.2, 166.6, 162.1, 139.2, 135.1, 134.8, 134.8, 133.0,
132.8, 130.2, 129.9, 129.1, 128.4, 127.4, 126.0, 120.6, 120.3,
110.5, 61.5, 14.3; IR (neat): ν 2976, 1718, 1627, 1466, 1321,
1275, 1245, 1201, 1152, 1030 cm-1; HRMS calcd for
C20H1679BrO4 [M + H]+ 399.0232, found 399.0235.
4.3.18 Ethyl 3-(2-hydroxy-4-methylbenzoyl)-1-naphthoate (5r).
The reaction of 1q (0.3 mmol, 77.5 mg), 2a (0.9 mmol, 268.6
mg), KF (1.8 mmol, 104.6 mg), 18-C-6 (1.8 mmol, 475.7 mg)
and TFA (0.75 mmol, 85.5 mg) in THF (3 mL) afforded 92.3 mg
o
1
(92%) of 5r. Pale yellow solid, mp 84.4-86.3 C; H NMR (400
MHz, CDCl3): δ 11.96 (s, 1H), 8.89 (d, J = 8.4 Hz, 1H), 8.37 (s,
1H), 8.20 (s, 1H), 7.87 (d, J = 8.0 Hz, 1H), 7.66-7.62 (m, 1H),
7.55-7.51 (m, 1H), 7.41 (d, J = 8.0 Hz, 1H), 6.83 (s, 1H), 6.62 (d,
J = 8.0 Hz, 1H), 4.40 (q, J = 7.2 Hz, 2H), 2.30 (s, 3H), 1.37 (t, J
= 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3): δ 199.8, 166.8,
163.5, 148.4, 134.6, 134.0, 133.3, 132.8, 132.5, 129.8, 129.7,
129.3, 128.1, 127.2, 126.0, 120.2, 118.6, 116.8, 61.4, 22.0, 14.3;
IR (neat): ν 2981, 1716, 1631, 1503, 1304, 1242, 1159 cm-1;
HRMS (EI) calcd for C21H18O4 334.1205, found 334.1207.
4.3.19 Ethyl 3-(2-hydroxy-4-methoxybenzoyl)-1-naphthoate (5s).
The reaction of 1r (0.3 mmol, 82.3 mg), 2a (0.9 mmol, 268.6
mg), KF (1.8 mmol, 104.6 mg), 18-C-6 (1.8 mmol, 475.7 mg)
and TFA (0.75 mmol, 85.5 mg) in THF (3 mL) afforded 97.8 mg
(93%) of 5s. Pale yellow solid, mp 130.8-131.1 oC; 1H NMR (400
MHz, CDCl3): δ 12.62 (s, 1H), 8.98 (d, J = 8.4 Hz, 1H), 8.44 (d,
J = 1.6 Hz, 1H), 8.27 (s, 1H), 7.97 (d, J = 8.0 Hz, 1H), 7.75-7.71
(m, 1H), 7.64-7.60 (m, 1H), 7.54 (d, J = 9.2 Hz, 1H), 6.56 (d, J =
2.4 Hz, 1H), 6.45 (dd, J1 = 8.8 Hz, J2 = 2.4 Hz, 1H), 4.50 (q, J =
7.2 Hz, 2H), 3.88 (s, 3H), 1.46 (t, J = 7.2 Hz, 3H); 13C NMR (100
MHz, CDCl3): δ 198.6, 166.8, 166.4, 166.4, 135.0, 134.2, 134.1,
132.8, 132.4, 129.7, 129.6, 129.3, 128.1, 127.2, 125.9, 113.1,
107.7, 101.2, 61.4, 55.6, 14.3; IR (neat): ν 2984, 2826, 1715,
1624, 1507, 1362, 1244, 1154, 1132, 1026 cm-1; HRMS (EI)
calcd for C21H18O5 350.1154, found 350.1156.
4.3.20 Ethyl 3-(4-bromo-2-hydroxybenzoyl)-1-naphthoate (5t).
The reaction of 1s (0.3 mmol, 96.9 mg), 2a (0.9 mmol, 268.6 mg),
KF (1.8 mmol, 104.6 mg), 18-C-6 (1.8 mmol, 475.7 mg) and
TFA (0.75 mmol, 85.5 mg) in THF (3 mL) afforded 98.2 mg
(82%) of 5t. Pale yellow solid, mp 115.6-116.7 oC; 1H NMR (400
MHz, CDCl3): δ 12.05 (s, 1H), 8.99 (d, J = 8.4 Hz, 1H), 8.44 (s,
1H), 8.30 (s, 1H), 7.99 (d, J = 8.0 Hz, 1H), 7.78-7.74 (m, 1H),
7.67-7.63 (m, 1H), 7.50 (d, J = 8.8 Hz, 1H), 7.33 (s, 1H), 7.07 (d,
J = 8.4 Hz, 1H), 4.50 (q, J = 7.2 Hz, 2H), 1.47 (t, J = 7.2 Hz,
3H); 13C NMR (100 MHz, CDCl3): δ 199.8, 166.7, 163.6, 134.7,
129.9, 129.0, 128.5, 127.4, 126.0, 124.3, 124.1, 120.0 (d, JC-F
=
7.3 Hz), 118.6 (d, JC-F = 5.8 Hz), 118.0 (d, JC-F = 23.3 Hz), 61.5,
14.3; IR (neat): ν 2984, 1718, 1615, 1480, 1325, 1271, 1245,
1192, 1142, 1030 cm-1; HRMS calcd for C20H16FO4 [M + H]+
339.1033, found 339.1030.
4.3.16 Ethyl 3-(5-chloro-2-hydroxybenzoyl)-1-naphthoate (5p).
The reaction of 1o (0.3 mmol, 83.6 mg), 2a (0.9 mmol, 268.6

12
Tetrahedron
ACCEPTED MANUSCRIPT
134.2, 133.4, 132.8, 132.7, 131.3, 130.2, 129.8, 129.0, 128.4,
and TFA (0.75 mmol, 85.5 mg) in THF (3 mL) afforded 40.1 mg
127.4, 126.0, 122.5, 121.8, 118.0, 61.5, 14.3; IR (neat): ν 3424,
2980, 1717, 1620, 1482, 1288, 1275, 1245, 1207, 1151, 1030 cm-
1; HRMS calcd for C20H1679BrO4 [M + H]+ 399.0232, found
399.0229.
4.3.21 Ethyl 3-(1-hydroxy-2-naphthoyl)-1-naphthoate (5u). The
reaction of 1t (0.3 mmol, 88.3 mg), 2a (0.9 mmol, 268.6 mg), KF
(1.8 mmol, 104.6 mg), 18-C-6 (1.8 mmol, 475.7 mg) and TFA
(0.75 mmol, 85.5 mg) in THF (3 mL) afforded 103.3 mg (93%)
(40%) of 5xb. Pale yellow oil; 1H NMR (400 MHz, CDCl3): δ
11.93 (s, 1H), 8.23 (s, 1H), 7.88 (d, J = 1.6 Hz, 1H), 7.84-7.81 (m,
1H), 7.65-7.63 (m, 1H), 7.56-7.50 (m, 3H), 7.10 (d, J = 8.4 Hz,
1H), 6.92-6.88 (m, 1H), 4.49 (q, J = 7.2 Hz, 2H), 2.67 (s, 3H),
1.44 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3): δ 200.0,
170.7, 163.2, 136.5, 134.1, 133.4, 133.4, 133.3, 133.3, 133.2,
132.1, 130.2, 128.5, 127.2, 126.1, 119.1, 118.9, 118.5, 62.0, 21.7,
14.1; IR (neat): ν 3424, 2976, 1725, 1626, 1482, 1277, 1242,
1211, 1186, 1026 cm-1; HRMS calcd for C21H18O4Na [M + Na]+
357.1103, found 357.1107.
o
1
of 5u. Yellow solid, mp 115.4-116.7 C; H NMR (400 MHz,
CDCl3): δ 13.88 (s, 1H), 9.01 (d, J = 8.8 Hz, 1H), 8.55 (d, J = 8.4
Hz, 1H), 8.52 (s, 1H), 8.37 (s, 1H), 8.00 (d, J = 8.0 Hz, 1H),
7.80-7.73 (m, 2H), 7.70-7.57 (m, 4H), 7.26 (d, J = 8.8 Hz, 1H),
4.50 (q, J = 7.2 Hz, 2H), 1.46 (t, J = 7.2 Hz, 3H); 13C NMR (100
MHz, CDCl3): δ 200.0, 166.8, 164.1, 137.4, 134.6, 134.1, 132.9,
132.5, 130.5, 129.8, 129.8, 129.4, 128.1, 127.5, 127.2, 126.9,
126.1, 126.0, 125.3, 124.5, 118.2, 112.5, 61.4, 14.3. IR (neat): ν
2925, 2852, 1716, 1627, 1603, 1570, 1462, 1293, 1243, 1191,
1041 cm-1; HRMS (EI) calcd for C24H18O4 370.1205, found
370.1201.
4.3.22 3-(2-Hydroxy-1-naphthoyl)-1-naphthoate (5v). The
reaction of 1u (0.3 mmol, 88.3 mg), 2a (0.9 mmol, 268.6 mg),
KF (1.8 mmol, 104.6 mg), 18-C-6 (1.8 mmol, 475.7 mg) and
TFA (0.75 mmol, 85.5 mg) in THF (3 mL) afforded 91.1 mg
(82%) of 5v. Yellow oil; 1H NMR (400 MHz, CDCl3): δ 13.88 (s,
1H), 9.01 (d, J = 8.8 Hz, 1H), 8.57-8.52 (m, 2H), 8.37 (s, 1H),
8.00 (d, J = 8.4 Hz, 1H), 7.80-7.73 (m, 2H), 7.70-7.62 (m, 2H),
7.61-7.56 (m, 2H), 7.27 (d, J = 8.0 Hz, 1H), 4.50 (q, J = 7.2 Hz,
2H), 1.46 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3): δ
200.1, 166.9, 164.1, 137.4, 134.6, 134.1, 132.9, 132.5, 130.6,
129.8, 129.8, 129.4, 128.1, 127.5, 127.2, 127.0, 126.1, 126.0,
125.3, 124.5, 118.2, 112.6, 61.4, 14.3; IR (neat): ν 3063, 2955,
1715, 1599, 1466, 1420, 1248, 1212, 1143, 1057 cm-1; HRMS
calcd for C24H19O4 [M + H]+ 371.1283, found 371.1290.
4.3.26 Ethyl 3-(2-hydroxybenzoyl)-5-methoxy-1-naphthoate (5y).
The reaction of 1a (0.3 mmol, 73.3 mg), 2d (0.9 mmol, 295.6
mg), KF (1.8 mmol, 104.6 mg), 18-C-6 (1.8 mmol, 475.7 mg)
and TFA (0.75 mmol, 85.5 mg) in THF (3 mL) afforded 33.6 mg
1
(32%) of 5y. Pale yellow oil; H NMR (400 MHz, CDCl3): δ
12.01 (s, 1H), 8.83 (d, J = 0.8 Hz, 1H), 8.52-8.47 (m, 2H), 7.67-
7.62 (m, 2H), 7.57-7.52 (m, 1H), 7.13-7.10 (m, 1H), 6.96-6.90
(m, 2H), 4.49 (q, J = 7.2 Hz, 2H), 4.00 (s, 3H), 1.45 (t, J = 7.2 Hz,
3H); 13C NMR (100 MHz, CDCl3): δ 200.5, 167.0, 163.3, 156.4,
136.4, 133.6, 133.5, 132.8, 130.4, 129.7, 129.1, 127.9, 125.1,
119.2, 118.9, 118.5, 117.8, 105.1, 61.4, 55.7, 14.3; IR (neat): ν
2976, 1711, 1625, 1599, 1458, 1308, 1254, 1036 cm-1; HRMS
calcd for C21H18O5Na [M + Na]+ 373.1052, found 373.1057.
Acknowledgments
We are grateful for the financial support from National Natural
Science Foundation of China (Project No. 21102043) and the
Fundamental Research Funds for the Central Universities.
References and notes
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4.3.23 Ethyl 3-(2-hydroxybenzoyl)-6,7-dimethyl-1-naphthoate
(5w). The reaction of 1a (0.3 mmol, 73.3 mg), 2b (0.9 mmol,
293.8 mg), KF (1.8 mmol, 104.6 mg), 18-C-6 (1.8 mmol, 475.7
mg) and TFA (0.75 mmol, 85.5 mg) in THF (3 mL) afforded 70.0
o
mg (67%) of 5w. White solid, mp 117.1-117.3 C; 1H NMR (400
MHz, CDCl3): δ 11.98 (s, 1H), 8.75 (s, 1H), 8.40 (d, J = 1.6 Hz,
1H), 8.21 (s, 1H), 7.71 (s, 1H), 7.64 (dd, J1 = 8.0 Hz, J2 = 1.6 Hz,
1H), 7.57-7.52 (m, 1H), 7.11 (d, J = 8.4 Hz, 1H), 6.93-6.88 (m,
1H), 4.49 (q, J = 7.2 Hz, 2H), 2.52 (s, 3H), 2.46 (s, 3H), 1.46 (t, J
= 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3): δ 200.5, 167.0,
163.2, 140.7, 137.3, 136.4, 134.1, 133.4, 132.8, 131.7, 131.6,
129.2, 128.6, 127.1, 125.4, 119.2, 118.8, 118.5, 61.3, 21.0, 20.0,
14.3; IR (neat): ν 3415, 2980, 1716, 1625, 1483, 1305, 1239,
1217, 1176 cm-1; HRMS calcd for C22H21O4 [M + H]+ 349.1440,
found 349.1441.
4.3.24 Ethyl 3-(2-hydroxybenzoyl)-5-methyl-1-naphthoate (5xa).
The reaction of 1a (0.3 mmol, 73.3 mg), 2c (0.9 mmol, 281.2
mg), KF (1.8 mmol, 104.6 mg), 18-C-6 (1.8 mmol, 475.7 mg)
and TFA (0.75 mmol, 85.5 mg) in THF (3 mL) afforded 50.1 mg
1
(50%) of 5xa. Pale yellow oil; H NMR (400 MHz, CDCl3): δ
12.00 (s, 1H), 8.79 (d, J = 8.4 Hz, 1H), 8.52 (s, 1H), 8.42 (d, J =
1.6 Hz, 1H), 7.64-7.58 (m, 2H), 7.57-7.52 (m, 1H), 7.45 (d, J =
7.2 Hz, 1H), 7.13-7.10 (m, 1H), 6.93-6.88 (m, 1H), 4.50 (q, J =
7.2 Hz, 2H), 2.73 (s, 3H), 1.45 (t, J = 7.2 Hz, 3H); 13C NMR (100
MHz, CDCl3): δ 200.6, 167.1, 163.3, 136.5, 136.0, 133.4, 133.4,
132.8, 132.1, 130.6, 129.5, 128.8, 128.6, 128.1, 124.1, 119.1,
118.8, 118.6, 61.4, 19.8, 14.3; IR (neat): ν 3428, 2922, 1719,
1627, 1478, 1445, 1269, 1241, 1088 cm-1; HRMS calcd for
C21H18O4Na [M + Na]+ 357.1103, found 357.1105.
4.3.25 Ethyl 3-(2-hydroxybenzoyl)-8-methyl-1-naphthoate (5xb).
The reaction of 1a (0.3 mmol, 73.3 mg), 2c (0.9 mmol, 281.2
mg), KF (1.8 mmol, 104.6 mg), 18-C-6 (1.8 mmol, 475.7 mg)

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