Construction of 3-Sulfonyl Naphthalenes via Tandem Reaction of 1,4-Diyn-3-yl Esters with Sodium Sulfinates

Article abstract of DOI:10.1021/acs.joc.1c00038

Polysubstituted 3-sulfonyl naphthalenes were constructed in good to high yields by AlCl3-mediated tandem reaction of 1,4-diyn-3-yl esters and sodium sulfinates. This reaction proceeded under mild reaction conditions and tolerated a variety of functional groups. Moreover, the mechanistic studies indicated that the initial formation of allene under DBU from 1,4-diyn-3-yl ester and a sequence of nucleophilic addition of sodium sulfinate, the formation of allene, and intramolecular cyclization might be involved.

Full text of DOI:10.1021/acs.joc.1c00038

pubs.acs.org/joc
Article
Construction of 3‑Sulfonyl Naphthalenes via Tandem Reaction of
1,4-Diyn-3-yl Esters with Sodium Sulfinates
Ziyi Guo, Yiming Zhao, Yu Wang, Meihua Xie,* and Jitan Zhang*
Cite This: J. Org. Chem. 2021, 86, 6247−6258
Read Online
sı
*
Metrics & More
Article Recommendations
Supporting Information
ACCESS
ABSTRACT: Polysubstituted 3-sulfonyl naphthalenes were con-
structed in good to high yields by AlCl3-mediated tandem reaction
of 1,4-diyn-3-yl esters and sodium sulfinates. This reaction
proceeded under mild reaction conditions and tolerated a variety
of functional groups. Moreover, the mechanistic studies indicated
that the initial formation of allene under DBU from 1,4-diyn-3-yl
ester and a sequence of nucleophilic addition of sodium sulfinate,
the formation of allene, and intramolecular cyclization might be involved.
active compounds.11 However, to the best of our knowledge,
approaches to access sulfonyl naphthalenes remain highly
limited and only rare examples have been explored. In 2016,
Deng and co-workers reported the synthesis of α-sulfonyl
naphthalene by cross-coupling reaction of 2-naphthols with
sodium sulfonates (Scheme 1, eq a).12 In the same year, Jiang
and co-workers developed a radical cyclization of 1,5-enynes
and sulfonyl hydrazides to prepare α-sulfonyl naphthalene
(Scheme 1, eq b).13 Subsequently, a radical cyclization of
homopropargyl alcohols and sulfonyl hydrazides to give β-
arylsulfonyl naphthalenes was disclosed by Yan and Zhu,
respectively (Scheme 1, eq c).14 Recently, Li and co-workers
delivered the synthesis of α-sulfonyl naphthalene via Ru(II)-
catalyzed annulation of nitrones with α-diazo sulfonyl ketones
(Scheme 1, eq d).15 1,4-Diyn-3-yl esters are potential synthons
due to the presence of carbon−carbon triple bonds and the
ester group. However, the synthetic transformation of 1,4-diyn-
3-yl esters is less developed.16 To avoid the high reaction
temperature, over-stoichiometric amounts of oxidants, or
transition-metal catalysts which were always necessary in the
aforementioned transformations, and continuing our ongoing
research interest in the synthesis of sulfur-contained com-
pounds17 by employing stable and readily available sulfur
sources, such as sodium sulfonates,18 we wish to report herein
a convenient and atom-economic synthesis of polysubstituted
β-sulfonyl naphthalenes through AlCl3-mediated tandem
reaction of 1,4-diyn-3-yl esters and sodium sulfinates at room
temperature.
INTRODUCTION
■
Naphthalenes are prevalent in a large number of bioactive
natural products, pharmaceutical compounds, agrochemicals,
and functional materials.1 Naphthalene derivatives are also
valuable precursors of unusual aromatic architectures and
chiral catalysts.2 Therefore, the development of a novel and
efficient method to access naphthalenes, especially function-
alized naphthalenes, has attracted continuous attention in
organic synthesis.3 Generally, the Diels−Alder reaction and
sequential aromatization represent the typical strategy.4
Besides, transition-metal promoted annulation reaction of o-
alkynyl(oxo)benzenes with alkenes/alkynes5 and intramolecu-
lar cyclization of o-(alkynyl)styrenes6 are also powerful tools
for the synthesis of various naphthalene derivatives. Recently,
access to naphthalenes via transition-metal catalyzed C−H
activation/annulation has provided a straightforward manner
for this synthetic topic.7 Despite these significant advances, the
development of more efficient strategies to access naphthalenes
bearing functional groups, such as heteroatoms, would be in
great demand.
Owing to the distinctive structure and electronic features of
sulfonyl groups, organosulfones have versatile applications in
biochemistry, medicinal chemistry, materials chemistry, as well
as in synthetic chemistry.8 For example, organosulfones can be
used as drug candidates for cancer, HIV, and Parkinson’s
disease.8d,e,i On the other hand, sulfonyl functionality can be
transformed into important building blocks via Smile
rearrangement, Julia olefination, and reductive cleavage of
the sulfone group.8b,f−h Given their importance, incorporating
the sulfonyl group into small molecules has attracted
considerable attention of organic chemists.9 Aryl sulfones are
of particular interest in organic chemistry and their synthesis
has been extensively explored.10 Among them, sulfonyl
naphthalene is an important kind of aryl sulfone compound,
which are versatile precursors of various naphthalene
derivatives and the core substructure of some biologically
Received: January 6, 2021
Published: April 20, 2021
https://doi.org/10.1021/acs.joc.1c00038
© 2021 American Chemical Society
J. Org. Chem. 2021, 86, 6247−6258
6247

The Journal of Organic Chemistry
pubs.acs.org/joc
Article
a
Scheme 1. Strategies for the Synthesis of Sulfonyl
Naphthalenes
Table 1. Optimization of the Reaction Conditions
2a
yield
b
entry
base
catalyst
solvent
DMSO
(equiv)
(%)
1
2
3
4
5
6
7
8
9
10
11
12
13
−
−
−
1
1
1
1
1
1
1
1
1
1
1
1
n.r.
30
52
35
30
18
43
40
0
55
35
49
37
61
68
67
82
DBU
DBU
Et3N
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
AlCl3
AlCl3
AlCl3
AlCl3
FeCl3
ZnCl2
DABCO
K2CO3
DBU
DBU
DBU
DBU
DBU
DBU
DBU
DBU
DBU
DBU
DBU
Cu(OTf)2 DMSO
c
AlCl3
AlCl3
AlCl3
AlCl3
AlCl3
AlCl3
AlCl3
AlCl3
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
d
e
f
1
14
15
16
17
1.4
1.5
1.6
1.5
RESULTS AND DISCUSSION
■
DMSO/DCM
(1:1)
Our initial effort focused on identifying the optimal reaction
conditions by selecting 1,5-diphenylpenta-1,4-diyn-3-yl ben-
zoate (1a) and sodium 4-methylbenzenesulfinate (2a) as the
model substrates. The results are summarized in Table 1. First,
the mixture of 1,5-diphenylpenta-1,4-diyn-3-yl benzoate and
sodium 4-methylbenzenesulfinate in DMSO was stirred at
room temperature for 15 h, but no reaction took place by
recovering 1a completely (Table 1, entry 1). To our delight, 1-
benzyl-3-tosylnaphthalen-2-yl benzoate (3aa) can be isolated
in 30% yield when 1.0 equiv DBU was added (Table 1, entry
2). By combining use of DBU and AlCl3, a better result was
obtained to give 3aa in 52% yield (Table 1, entry 3). Then,
other bases (such as Et3N, DABCO, and K2CO3) and Lewis
acids (such as FeCl3, ZnCl2, and Cu(OTf)2) were tested,
respectively, but they were less effective (Table 1, entries 4−6
and entries 7−9). While an increase in the loading of DBU or
AlCl3 had no apparent effect on the yield of 3aa (Table 1,
entries 10 and 12), a depressing yield was obtained when the
usage of DBU or AlCl3 decreased (Table 1, entries 11 and 13).
Gratifyingly, increasing the amount of 2a to 1.5 equiv resulted
in 68% yield of 3aa (Table 1, entries 14−16). Moreover, the
yield of 3aa was further improved to 82% when the solvent
combination of DMSO/DCM (v/v = 1:1) was used (Table 1,
entry 17). Several other solvent systems, such as DMSO/THF,
DMSO/MeCN, DMF/DCM, THF/DCM, MeCN/DCM,
were also screened and no enhancement of yields was
observed (Table 1, entries 18−22). Only a trace amount of
3aa was detected when the reaction was conducted at 0 °C,
while 3aa was isolated in 71% yield at 40 °C (Table 1, entries
23 and 24).
18
19
DBU
DBU
AlCl3
AlCl3
DMSO/THF
(1:1)
DMSO/MeCN
(1:1)
DMF/DCM (1:1)
THF/DCM (1:1)
MeCN/DCM
(1:1)
DMSO/DCM
(1:1)
DMSO/DCM
(1:1)
1.5
1.5
28
23
20
21
22
DBU
DBU
DBU
AlCl3
AlCl3
AlCl3
1.5
1.5
1.5
45
30
28
g
23
DBU
DBU
AlCl3
AlCl3
1.5
1.5
trace
71
h
24
a
Reaction conditions unless specified otherwise: 1a (0.2 mmol), 2a,
base (1.0 equiv) catalyzed by 50 mol % of catalyst in 2 mL of solvent
at room temperature. n.r.: no reaction. With 1.5 equiv of DBU.
With 0.5 equiv of DBU. With 70 mol % of AlCl3. With 30 mol % of
AlCl3. The reaction was run at 0 °C. The reaction was run at 40 °C.
b
c
d
e
f
g
h
Aryl sulfinates proved to be suitable substrates, and both
electron-donating and electron-withdrawing substituents on
aromatic rings could be tolerated (3aa−3ae). In particular,
sodium naphthalene-2-sulfinate and heteroaryl sulfinates (such
as sodium thiophene-2-sulfinate and sodium pyridine-3-
sulfinate) also furnished the desired products in good yields
(3af−3ah). However, only moderate yields were obtained
when alkyl sulfinates were concerned (3ai and 3aj). Sodium 4-
nitrobenzenesulfinate and sodium trifluoromethylsulfinate
showed difficulty for producing the desired products (3ak−
3al) under the optimal reaction conditions, which may be due
to their poor nucleophilicity.
Next, the substrate scope with respect to 1,4-diyn-3-yl esters
1 was probed (Table 3). The results demonstrated that the
reaction is general and a wide range of 1,5-diaryl-1,4-diyn-3-yl
esters were found to be compatible with the reaction
conditions. At first, the reaction of sodium p-toluenesulfinate
with 1,5-diphenyl-1,4-diyn-3-yl esters containing various
acyloxy groups was tested, and the corresponding products
With the optimized reaction conditions in hand (Table 1,
entry 17), we moved to investigate the scope and generality of
the reaction. First, the reaction of 1,5-diphenylpenta-1,4-diyn-
3-yl benzoate (1a) with different sodium sulfinates 2 was
tested (Table 2). It was noticed that both aryl sulfinates (2a−
2h) and alkyl sulfinates (2i and 2j) can react with 1a smoothly
to give the corresponding products in moderate to good yields.
6248
https://doi.org/10.1021/acs.joc.1c00038
J. Org. Chem. 2021, 86, 6247−6258

The Journal of Organic Chemistry
pubs.acs.org/joc
Article
a
Table 2. Substrate Scope of Sodium Sulfinate
a
Reaction conditions: 1a (0.2 mmol), 2 (0.3 mmol), AlCl3 (50 mol %), DMSO/DCM (1:1) (2.0 mL), rt, isolated yield.
3ba−3ma were obtained in 62−89% yields. R2 in 1,4-diyn-3-yl
esters 1 can be different aryls, such as substituted phenyl, 1-
naphthyl, and 2-furyl, or different alkyls, such as methyl,
cyclopropyl, prop-1-en-2-yl, and t-butyl. We then explored the
reaction of sodium p-toluenesulfinate with different 1,5-diaryl-
1,4-diyn-3-yl benzoates. In general, 1,5-diaryl-1,4-diyn-3-yl
benzoates with either an electron-donating or withdrawing
group on the benzene ring were able to generate the
corresponding products 3na−3sa in 65−85% yields. Various
functional groups, such as methyl, methoxy, fluoro, chloro, and
bromo, were compatible with the reaction conditions. The
electronic properties of the substituents on the benzene ring of
1,5-diaryl-1,4-diyn-3-yl benzoates did not have a significant
influence on the reaction efficiency. However, it should be
pointed out that a mixture of two regioisomers (3sa/3sa′, 3ta/
3ta′, and 3ua/3ua′) were obtained in the case of unsym-
metrical 1,4-diyn-3-yl benzoates (1s−1u), where the major
products were formed via the cyclization of electron-deficient
arene, probably due to the higher stability and nucleophilic
addition reactivity of allene Int-I bearing an electron-deficient
aryl group. Unfortunately, the reaction is messy and no desired
product was isolated when an alkyl (such as cyclopropyl, t-
butyl, or n-pentyl) attached to the triple bond of 1,4-diyn-3-
ester 1 or the acyloxy group in substrate 1 was replaced by
ethoxy, methoxy, OTMS, or chloro. The results may be due to
the instability of the in situ generated allene intermediates.
To explore the potential applications of the method, a gram-
scale synthesis of 3aa and its further transformation were
conducted. The desired product 3aa could be afforded in 78%
yield (1.92 g) when 5 mmol 1,4-diyne-3-yl ester 1a was
subjected to the standard reaction conditions (Scheme 2, eq
a). The Pd-catalyzed coupling reaction of 3aa and phenyl-
magnesium bromide proceeded smoothly and the sulfonyl
group in 3aa can be easily converted into phenyl (Scheme 2,
eq b). Reduction of 3-sulfonyl naphthalene 3aa by LiAlH4
gives 1-benzyl-3-tosylnaphthalen-2-ol 7 in almost quantitative
yield (Scheme 2, eq c).
In order to gain insight into the reaction mechanism, several
control experiments were performed. It did not work when 3-
methyl-1,5-diphenylpenta-1,4-diyn-3-yl benzoate (1v, an ester
of tertiary alcohol) and sodium p-toluenesulfinate (2a) were
subjected to the standard reaction conditions (Scheme 3, eq
a), which suggests that the formation of product 3 may involve
an allene intermediate Int-I that could not be generated from
1v because of the absence of propargyl hydrogen. Product 3aa
was isolated in 79% yield when (E)-1,5-diphenyl-2-tosylpent-1-
en-4-yn-3-yl benzoate (Int-II) was stirred for 24 h under the
standard reaction reactions, indicating the role of Int-II as a
key intermediate in the formation of 3aa (Scheme 3, eq b). No
3aa was detected when the solution of Int-II in DMSO/DCM
was stirred for 24 h in the absence of DBU (Scheme 3, eq c).
Product 3aa could be obtained in 35% yield in the presence of
1.0 equiv DBU without AlCl3 (Scheme 3, eq d). These results
suggest that DBU is necessary to start the reaction by
generating the active allene intermediate and AlCl3 acts as a
promoter to improve the reaction efficiency of 3aa formation
by enhancing the annulation step. Performing the reaction of
1a and 2a under standard conditions in the presence of 10
equiv D2O afforded the corresponding product 3aa-d in72%
yield with deuterium incorporation at C-4 position (D content
32%) and methylene of the benzyl group (D content 48%)
(Scheme 3, eq e), respectively. The reaction of Int-II in the
presence of 10 equiv D2O afforded product 3aa-d in 80% yield
with deuterium incorporation at methylene of the benzyl group
(D content 34%) (Scheme 3, eq f). The reaction of deuterated
1a with sodium p-toluenesulfinate afforded 3aa-d in74% yield
6249
https://doi.org/10.1021/acs.joc.1c00038
J. Org. Chem. 2021, 86, 6247−6258

The Journal of Organic Chemistry
pubs.acs.org/joc
Article
a
Table 3. Substrate Scope of 1,4-Diyne-3-yl Ester
a
Reaction conditions: 1 (0.2 mmol), 2a (0.3 mmol), AlCl3 (50 mol %), DMSO/DCM (1:1) (2.0 mL), rt. Isolated yield.
with deuterium incorporation at C-4 position (D content 33%)
(Scheme 3, eq g). These results indicate the formation of
allene intermediate Int-I and the final product could be formed
from abstraction of H from the proton pool (either from
methine or H2O in the system) and/or intramolecular [1,7]-H
shift.
DBU-promoted deprotonation of Int-II gives allene Int-III,
which is followed by 6π-electrocyclization to form the
intermediate Int-IV. It is assumed that AlCl3 might act as a
Lewis acid to promote this electrocyclization process.20 Finally,
aromatization of Int-IV via abstraction of H from the proton
pool and/or [1,7]-H migration afforded the product 3aa.
On the basis of the above experiments and related
literatures,19 a plausible mechanism for the formation of
product 3aa was proposed (Scheme 4). First, a rapid
transformation of 1,4-diyn-3-yl ester 1a in the presence of
DBU leads to the allene Int-I. Subsequently, intermediate vinyl
sulfone Int-II is generated by the nucleophilic addition of
sodium sulfinate 2a to the central carbon of Int-I. Sequential
CONCLUSIONS
■
In summary, we have developed a simple and atom-economic
method to synthesize sulfonyl-substituted naphthalene deriv-
atives from 1,4-diyn-3-yl esters and sodium sulfinates. The
reaction is general for 1,5-diaryl substituted 1,4-diyn-3-yl esters
and differently substituted naphthalene derivatives could be
6250
https://doi.org/10.1021/acs.joc.1c00038
J. Org. Chem. 2021, 86, 6247−6258

The Journal of Organic Chemistry
pubs.acs.org/joc
Article
obtained under mild conditions, although depressing results
were delivered for 1,4-diyn-3-yl esters containing an alkyl
attached to the triple bond of 1,4-diyn-3-yl esters. Due to the
versatile reactivity of sulfonyl groups, it is predictable that these
compounds are valuable precursors of variously substituted
naphthalene.
Scheme 2. Gram-Scale Synthesis and Transformation of 3aa
EXPERIMENTAL SECTION
General Information. Unless otherwise noted, all chemicals were
■
purchased from commercial sources and used without further
purification. The melting points are uncorrected. H NMR and 13C
1
NMR spectra were recorded on Bruker AV-400 or Bruker AV-500
spectrometers in CDCl3 with TMS as an internal standard at room
temperature. High-resolution mass spectra were recorded on an
Agilent Q-TOF mass spectrometer. Crystals of compound 3aa
suitable for X-ray analysis were grown from the solvent of ethyl
acetate/hexane by slow evaporation method. The crystal structure
analysis of 3aa was performed on a Bruker SMART Bruker Platon II
area detector diffractometer. Compound Int-II was prepared
according to a previously reported similar procedure.21
Scheme 3. Control Experiments
General Procedure for the Synthesis 1,4-Diyn-3-yl esters.
Method for the Synthesis of Symmetrical 1,4-Diyn-3-yl esters (1a−
1r).22 Under argon atmosphere, EtMgBr (20 mL, 20 mmol, 1.0 M
solution in THF) was added to a stirred solution of arylacetylene (20
mmol) in dry THF (20 mL) at 0 °C. The reaction mixture was stirred
for 3 h at 0 °C. Then, ethyl formate (0.81 mL, 10 mmol) was added
and stirred at room temperature for 2 h. The reaction was quenched
with saturated NH4Cl, and extracted with ether (3 × 25 mL). The
combined organic layers were dried over anhydrous Na2SO4, filtered,
and evaporated under reduced pressure. The residue was purified by
flash column chromatography (silica gel, petroleum ether/ethyl
acetate = 10/1) to give 1,5-diaryl-1,4-diyn-3-ol.
Acyl chloride (20 mmol) was added slowly to a solution of 1,5-
diaryl-1,4-diyn-3-ol (10 mmol) and Et3N (4.2 mL, 30 mmol) in
CH2Cl2 (10 mL) at 0 °C. The reaction mixture was stirred at 0 °C
until the complete consumption of 1,5-diaryl-1,4-diyn-3-ol (moni-
tored by TLC). The mixture was then poured into saturated NH4Cl,
and extracted with ether (3 × 20 mL). The organic solution was dried
over anhydrous Na2SO4, filtered, and evaporated under reduced
pressure. The residue was purified by flash column chromatography
on silica gel (petroleum ether/ethyl acetate = 50/1) to give the
product 1,5-diaryl-1,4-diyne-3-yl esters 1a−1r.
Method for the Synthesis of Unsymmetrical 1,4-Diyn-3-yl esters
(1s−1y).22 Pd(PPh3)2Cl2 (210.6 mg, 0.3 mmol) and CuI (114.3 mg,
0.6 mmol) were sequentially added to a stirred solution of aryl iodide
(20 mmol) in Et3N (20 mL) under argon at room temperature. The
mixture was stirred for 10 min and then prop-2-yn-1-ol (1.24 g, 22
mmol) was added. The mixture was stirred at room temperature
overnight. The reaction was quenched with saturated NH4Cl, and
extracted with ether (3 × 10 mL). The combined organic layers were
washed with saturated brine, dried over anhydrous Na2SO4, filtered,
and concentrated under reduced pressure. The residue was purified by
flash column chromatography on silica gel (petroleum ether/ethyl
acetate = 4/1) to afford 3-arylpropan-2-yn-1-ol.
At room temperature, MnO2 (13 g, 150 mmol) was added to a
solution of 3-arylpropan-2-yn-1-ol (1.32 g, 10 mmol) in CH2Cl2 (20
mL). The mixture was stirred overnight. The solid was filtered and the
solution was concentrated under reduced pressure. The residue was
purified by flash column chromatography on silica gel (petroleum
ether/ethyl acetate = 20/1) to afford 3-arylpropiolaldehyde.
Scheme 4. Plausible Mechanism for the Formation of 3aa
3-Arylpropiolaldehyde (1.30 g, 10 mmol) was added to the solution
of alkynyl magnesium bromide (10 mmol) in THF at 0 °C under
argon atmosphere. The mixture was stirred for 3 h at room
temperature. The mixture was quenched with saturated NH4Cl, and
extracted with ether (3 × 25 mL). The combined organic layers were
washed with a saturated NH4Cl, dried over anhydrous Na2SO4,
filtered, and concentrated under reduced pressure. The residue was
purified by flash column chromatography on silica gel (petroleum
ether/ethyl acetate = 10/1) to give the unsymmetrical 1,4-diyn-3-ol,
6251
https://doi.org/10.1021/acs.joc.1c00038
J. Org. Chem. 2021, 86, 6247−6258

The Journal of Organic Chemistry
pubs.acs.org/joc
Article
which was subjected to acyl chloride to generate unsymmetrical 1,4-
diyne-3-yl esters 1s−1y.
6.78 (s, 1H), 6.55 (dd, J1 = 1.7 Hz, J2 = 3.5 Hz, 1H); 13C{1H} NMR
(100 MHz, CDCl3) δ 157.0, 147.1, 143.8, 132.2, 129.2, 128.3, 121.6,
119.4, 112.1, 85.7, 82.6, 54.7; HRMS (APCI) m/z calcd for C22H15O3
(M + H)+: 327.1016, found 327.1016.
1,5-Diphenylpenta-1,4-diyn-3-yl benzoate (1a). Yellow solid; mp
1
72−73 °C; 2.8 g, 83% yield; PE/EA = 50:1; H NMR (400 MHz,
CDCl3) δ 8.18−8.15: (m, 2H), 7.62−7.58 (m, 1H), 7.54−7.46 (m,
6H), 7.36−7.30 (m, 6H), 6.80 (s, 1H); 13C{1H} NMR (100 MHz,
CDCl3) δ 165.0, 133.5, 132.2, 130.1, 129.4, 129.1, 128.5, 128.3, 121.7,
85.4, 83.0, 54.8; HRMS (APCI) m/z calcd for C24H17O2 (M + H)+:
337.1223, found 337.1226.
1,5-Diphenylpenta-1,4-diyn-3-yl acetate (1j). Yellow oil; 2.3 g,
85% yield; PE/EA = 50:1; 1H NMR (400 MHz, CDCl3) δ 7.52−7.49
(m, 4H), 7.36−7.30 (m, 6H), 6.53 (s, 1H), 2.19 (s, 3H); 13C{1H}
NMR (100 MHz, CDCl3) δ 169.3, 132.1, 129.1, 128.3, 121.6, 85.2,
82.8, 54.2, 20.9; HRMS (APCI) m/z calcd for C19H15O2 (M + H)+:
275.1067, found 275.1069.
1,5-Diphenylpenta-1,4-diyn-3-yl-4-methylbenzoate (1b). Yellow
1
solid; mp 130−131 °C; 3.1 g, 89% yield; PE/EA = 50:1; H NMR
1,5-Diphenylpenta-1,4-diyn-3-yl cyclopropanecarboxylate (1k).
1
(400 MHz, CDCl3) δ 8.07 (d, J = 8.3 Hz, 2H), 7.56−7.53 (m, 4H),
7.37−7.31 (m, 6H), 7.29−7.27 (m, 2H), 6.81 (s, 1H), 2.43 (s, 3H);
13C{1H} NMR (100 MHz, CDCl3) δ 165.1, 144.4, 132.2, 130.2,
129.3, 129.2, 128.4, 126.6, 121.8, 85.4, 83.2, 54.7, 21.8; HRMS
(APCI) m/z calcd for C25H19O2 (M + H)+: 351.1380, found
351.1378.
Yellow oil; 2.5 g, 83% yield; PE/EA = 60:1; H NMR (400 MHz,
CDCl3) δ 7.52−7.50 (m, 4H), 7.36−7.30 (m, 6H), 6.57 (s, 1H),
1.77−1.73 (m, 1H), 1.13−1.12 (m, 2H), 0.97−0.94 (m, 2H);
13C{1H} NMR (100 MHz, CDCl3) δ 173.3, 132.1, 129.0, 128.3,
121.7, 85.1, 83.0, 54.1, 12.9, 9.2; HRMS (APCI) m/z calcd for
C21H17O2 (M + H)+: 301.1223, found 301.1220.
1,5-Diphenylpenta-1,4-diyn-3-yl 4-methoxybenzoate (1c). Yel-
low solid; mp 34−35 °C; 3.0 g, 82% yield; PE/EA = 30:1; H NMR
1,5-Diphenylpenta-1,4-diyn-3-yl methacrylate (1l). Yellow oil;
2.1 g, 70% yield; PE/EA = 80:1; H NMR (400 MHz, CDCl3) δ
1
1
(400 MHz, CDCl3) δ 8.13−8.10 (m, 2H), 7.53−7.51 (m, 4H), 7.36−
7.7.30 (m, 6H), 6.96−6.94 (m, 2H), 6.78 (s, 1H), 3.87 (s, 3H);
13C{1H} NMR (100 MHz, CDCl3) δ 164.7, 163.9, 132.2, 132.1,
129.1, 128.3, 121.8, 121.7, 113.8, 85.2, 83.2, 55.5, 54.5; HRMS
(APCI) m/z calcd for C25H19O3 (M + H)+: 367.1329, found
367.1328.
7.45−7.42 (m, 4H), 7.29−7.22 (m, 6H), 6.53 (s, 1H), 6.21 (s, 1H),
5.61 (t, J = 1.4 Hz, 1H), 1.94 (s, 3H); 13C{1H} NMR (100 MHz,
CDCl3) δ 164.6, 134.5, 131.1, 128.0, 127.3, 126.1, 120.7, 84.2, 81.9,
53.5, 17.3; HRMS (APCI) m/z calcd for C21H17O2 (M + H)+:
301.1223, found 301.1220.
1,5-Diphenylpenta-1,4-diyn-3-yl pivalate (1m). Yellow oil; 2.9 g,
94% yield; PE/EA = 50/1; 1H NMR (400 MHz, CDCl3) δ 7.52−7.50
(m, 4H), 7.36−7.30 (m, 6H), 6.54 (s, 1H), 1.29 (s, 9H); 13C{1H}
NMR (100 MHz, CDCl3) δ 176.8, 132.1, 129.1, 128.4, 121.9, 85.0,
83.1, 54.2, 38.9, 27.1; HRMS (APCI) m/z calcd for C22H21O2 (M +
H)+: 317.1536, found 317.1533.
1,5-Diphenylpenta-1,4-diyn-3-yl 4-fluorobenzoate (1d). Red
1
solid; mp 83−84 °C; 3.0 g, 86% yield; PE/EA = 50:1; H NMR
(400 MHz, CDCl3) δ 8.20−8.17 (m, 2H), 7.54−7.52 (m, 4H), 7.35−
7.33 (m, 6H), 7.17−7.12 (m, 2H), 6.78 (s, 1H); 13C{1H} NMR (100
MHz, CDCl3) δ 166.1 (C−F, 1JC−F = 253.4 Hz), 164.0, 132.8 (C−F,
4
3JC−F = 9.4 Hz), 132.1, 129.2, 128.4, 125.6 (C−F, JC−F = 2.9 Hz),
1,5-Di-p-tolylpenta-1,4-diyn-3-yl benzoate (1n). Yellow solid; mp
1
121.7, 115.7 (C−F, 2JC−F = 21.8 Hz), 85.6, 82.8, 55.0; 19F NMR (376
MHz, CDCl3) δ −104.4; HRMS (APCI) m/z calcd for C24H16FO2
(M + H)+: 355.1129, found 355.1125.
48−49 °C; 3.2 g, 88% yield; PE/EA = 40:1; H NMR (400 MHz,
CDCl3) δ 8.17−8.15 (m, 2H), 7.61−7.57 (m, 1H), 7.49−7.45 (m,
2H), 7.41 (d, J = 8.1 Hz, 4H), 7.13 (d, J = 7.9 Hz, 4H), 6.78 (s, 1H),
2.35 (s, 6H); 13C{1H} NMR (100 MHz, CDCl3) δ 165.0, 139.3,
133.4, 132.0, 130.1, 129.4, 129.1, 128.4, 118.7, 85.5, 82.4, 54.9, 21.5;
HRMS (APCI) m/z calcd for C26H21O2 (M + H)+: 365.1536, found
365.1533.
1,5-Diphenylpenta-1,4-diyn-3-yl 4-chlorobenzoate (1e). Red
1
solid; mp 66−67 °C; 3.5 g, 93% yield; PE/EA = 50:1; H NMR
(400 MHz, CDCl3) δ 8.11−8.08 (m, 2H), 7.54−7.52 (m, 4H), 7.47−
7.44 (m, 2H), 7.38−7.31 (m, 6H), 6.78 (s, 1H); 13C{1H} NMR (100
MHz, CDCl3) δ 164.1, 139.9, 132.0, 131.4, 129.1, 128.8, 128.2, 127.7,
121.5, 85.5, 82.6, 55.0; HRMS (APCI) m/z calcd for C24H16O2Cl (M
+ H)+: 371.0839, found 371.0835.
1,5-Bis(4-methoxyphenyl)penta-1,4-diyn-3-yl benzoate (1o).
1
Yellow oil; 3.6 g, 90% yield; PE/EA = 25:1; H NMR (400 MHz,
CDCl3) δ 8.17−8.15 (m, 2H), 7.59−7.57 (m, 1H), 7.49−7.45 (m,
6H), 6.86−6.83 (m, 4H), 6.78 (s, 1H), 3.81 (s, 6H); 13C{1H} NMR
(100 MHz, CDCl3) δ 165.1, 160.3, 133.8, 133.5, 130.2, 129.5, 128.5,
114.0, 113.9, 85.5, 82.0, 55.4, 55.2; HRMS (APCI) m/z calcd for
C26H21O4 (M + H)+: 397.1434, found 397.1431.
1,5-Bis(4-fluorophenyl)penta-1,4-diyn-3-yl benzoate (1p). Yellow
oil; 3.6 g, 97% yield; PE/EA = 30:1; 1H NMR (400 MHz, CDCl3) δ
8.16−8.14 (m, 2H), 7.62−7.58 (m, 1H), 7.53−7.46 (m, 6H), 7.05−
7.00 (m, 4H), 6.76 (s, 1H); 13C{1H} NMR (125 MHz, CDCl3) δ
164.9, 163.0 (C−F, 1JC−F = 249.2 Hz), 134.1 (C−F, 3JC−F = 8.4 Hz),
133.6, 130.1, 129.2, 128.5, 117.7 (C−F, 4JC−F = 3.2 Hz), 115.7 (C−F,
2JC−F = 22.0 Hz), 84.4, 82.6, 54.6; 19F NMR (376 MHz, CDCl3) δ
−109.4; HRMS (APCI) m/z calcd for C24H15O2F2 (M + H)+:
373.1035, found 373.1031.
1,5-Diphenylpenta-1,4-diyn-3-yl 4-bromobenzoate (1f). Yellow
solid; mp 83−84 °C; 3.5 g, 84% yield; PE/EA = 50:1; 1H NMR (400
MHz, CDCl3) δ 8.03−8.00 (m, 2H), 7.64−7.60 (m, 2H), 7.54−7.52
(m, 4H), 7.37−7.31 (m, 6H), 6.78 (s, 1H); 13C{1H} NMR (100
MHz, CDCl3) δ 164.3, 132.2, 131.9, 131.6, 129.2, 128.8, 128.4, 128.3,
121.6, 85.7, 82.7, 55.1; HRMS (APCI) m/z calcd for C24H16O2Br (M
+ H)+: 415.0334, found 415.0329.
1,5-Diphenylpenta-1,4-diyn-3-yl 4-(trifluoromethyl)benzoate
1
(1g). Yellow oil; 3.2 g, 80% yield; PE/EA = 50:1; H NMR (500
MHz, CDCl3) δ 8.27 (d, J = 8.2 Hz, 2H), 7.73 (d, J = 8.4 Hz, 2H),
7.54−7.52 (m, 4H), 7.38−7.37 (m, 1H), 7.36−7.34 (m, 3H), 7.33−
7.31 (m, 2H), 6.81 (s, 1H); 13C{1H} NMR (125 MHz, CDCl3) δ
2
162.8, 133.9 (C−F, JC−F = 32.5 Hz), 131.5, 131.1, 129.5, 128.2,
127.3, 124.5 (C−F, 3JC−F = 9.9 Hz), 122.6 (C−F, 1JC−F = 270.7 Hz),
120.5, 84.8, 81.5, 54.4; 19F NMR (376 MHz, CDCl3) δ −63.1; HRMS
(APCI) m/z calcd for C25H16O2F3 (M + H)+: 405.1097, found
405.1099.
1,5-Bis(4-chlorophenyl)penta-1,4-diyn-3-yl benzoate (1q). Yel-
1
low solid; mp 62−63 °C; 3.0 g, 75% yield; PE/EA = 25:1; H NMR
(400 MHz, CDCl3) δ 8.16−8.14 (m, 2H), 7.63−7.59 (m, 1H), 7.50−
7.44 (m, 6H), 7.32−7.29 (m, 4H), 6.76 (s, 1H); 13C{1H} NMR (100
MHz, CDCl3) δ 164.9, 135.3, 133.6, 133.4, 133.2, 130.1, 129.1, 128.7,
128.5, 84.4, 83.6, 54.5; HRMS (APCI) m/z calcd for C24H15O2Cl2
(M + H)+: 405.0449, found 405.0447.
1,5-Diphenylpenta-1,4-diyn-3-yl 1-naphthoate (1h). Yellow oil;
3.1 g, 81% yield; PE/EA = 25:1; 1H NMR (400 MHz, CDCl3) δ 9.01
(d, J = 8.6 Hz, 1H), 8.36 (dd, J1 = 7.3 Hz, J2 = 1.1 Hz, 1H), 8.04 (d, J
= 8.2 Hz, 1H), 7.88 (d, J = 8.1 Hz, 1H), 7.63−7.61 (m, 1H), 7.55−
7.53 (m, 6H), 7.35−7.30 (m, 6H), 6.91 (s, 1H); 13C{1H} NMR (100
MHz, CDCl3) δ 165.6, 134.1, 133.8, 132.1, 131.4, 131.1, 129.1, 128.6,
128.3, 128.1, 126.3, 125.8, 125.7, 124.5, 121.7, 85.5, 83.0, 54.7;
HRMS (APCI) m/z calcd for C28H19O2 (M + H)+: 387.1380, found
387.1379.
1,5-Bis(4-bromophenyl)penta-1,4-diyn-3-yl benzoate (1r). Yel-
1
low solid; mp 120−121 °C; 3.95 g, 80% yield; PE/EA = 25:1; H
NMR (400 MHz, CDCl3) δ 8.16−8.14 (m, 2H), 7.63−7.59 (m, 1H),
7.50−7.45 (m, 6H), 7.39−7.36 (m, 4H) 6.74 (s, 1H); 13C{1H} NMR
(100 MHz, CDCl3) δ 164.9, 133.7, 133.6, 131.7, 130.1, 129.2, 128.6,
123.6, 120.6, 84.5, 83.8, 54.6; HRMS (APCI) m/z calcd for
C24H15O2Br2 (M + H)+: 492.9418, found 492.9422.
1,5-Diphenylpenta-1,4-diyn-3-yl furan-2-carboxylate (1i). Red
1
oil; 3.0 g, 92% yield; PE/EA = 40:1; H NMR (400 MHz, CDCl3) δ
1-(4-Methoxyphenyl)-5-phenylpenta-1,4-diyn-3-yl benzoate
1
7.64 (q, J = 2.1 Hz, 1H), 7.54−7.51 (m, 4H), 7.36−7.31 (m, 7H)
(1s). Yellow oil; 3.5 g, 96% yield; PE/EA = 30:1; H NMR (400
6252
https://doi.org/10.1021/acs.joc.1c00038
J. Org. Chem. 2021, 86, 6247−6258

The Journal of Organic Chemistry
pubs.acs.org/joc
Article
MHz, CDCl3) δ 8.18−8.16 (m, 2H), 7.62−7.58 (m, 1H), 7.54−7.52
(m, 2H), 7.49−7.46 (m, 4H), 7.36−7.31 (m, 3H), 6.87−6.84 (m,
2H), 6.80 (s, 1H), 3.81 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ
164.0, 159.2, 132.7, 132.4, 131.1, 129.1, 128.4, 128.0, 127.4, 127.3,
120.7, 112.9, 112.7, 84.5, 84.2, 82.1, 80.7, 54.3, 53.9; HRMS (APCI)
m/z calcd for C25H19O3 (M + H)+: 367.1329, found 367.1328.
1-(4-Chlorophenyl)-5-phenylpenta-1,4-diyn-3-yl benzoate (1t).
122.7, 87.1, 84.4, 54.0, 0.9; HRMS (APCI) m/z calcd for C20H21OSi
(M + H)+: 305.1356, found 305.1352.
General Procedure for the Synthesis of Compounds 3. 1,5-
Diphenylpenta-1,4-diyn-3-yl benzoate (1a) (67.2 mg, 0.2 mmol),
sodium p-toluenesulfinate (2a) (53.5 mg, 0.3 mmol) and anhydrous
AlCl3 (13.3 mg, 0.1 mmol) were dissolved in DMSO/DCM (2 mL, v/
v = 1:1) and then DBU (29.9 μL) was added dropwise to the
solution. The reaction mixture was stirred at room temperature until
the complete consumption of 1a (monitored by TLC). The reaction
was quenched with saturated NH4Cl and extracted with dichloro-
methane (3 × 10 mL). The combined organic layers were dried over
anhydrous Na2SO4, filtered, and concentrated. The residue was
purified by flash column chromatography on silica gel using
petroleum ether/ethyl acetate (v/v = 10/1) as eluent to give the
product 1-benzyl-3-tolylnaphthalene-2-yl benzoate (3aa).
1-Benzyl-3-tosylnaphthalen-2-ylezoate (3aa). White solid; mp
217−218 °C; 80 mg, 82% yield; PE/EA = 10:1; 1H NMR (400 MHz,
CDCl3) δ 8.81 (s, 1H), 8.07−8.05 (m, 1H), 8.02−8.00 (m, 2H),
7.94−7.92 (m, 1H), 7.68−7.56 (m, 5H), 7.50−7.47 (m, 2H), 7.16−
7.10 (m, 5H), 7.02−7.01 (m, 2H), 4.35 (d, J = 16.3 Hz, 1H), 4.16 (d,
J = 16.3 Hz, 1H), 2.37 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ
164.1, 144.0, 142.5, 138.8, 137.7, 135.3, 133.8, 132.1, 131.4, 130.9,
130.8, 130.4, 130.2, 129.5, 129.3, 128.7, 128.4, 128.3, 128.1, 127.9,
126.9, 126.1, 125.0, 31.9, 21.5; HRMS (APCI) m/z calcd for
C31H25O4S (M + H)+: 493.1468, found 493.1472.
1
Yellow oil; 2.9 g, 79% yield; PE/EA = 50:1; H NMR (500 MHz,
CDCl3) δ 8.17−8.15 (m, 2H), 7.62−7.59 (m, 1H), 7.54−7.52 (m,
2H), 7.50−7.44 (m, 4H), 7.38−7.30 (m, 5H), 6.78 (s, 1H); 13C{1H}
NMR (125 MHz, CDCl3) δ 165.3, 135.6, 134.0, 133.8, 132.5, 130.5,
129.6, 129.1, 128.9, 128.7, 122.0, 120.6,. 86.0, 84.6, 84.3, 83.1, 55.1;
HRMS (APCI) m/z calcd for C24H16ClO2 (M + H)+: 371.0833,
found 371.0828.
1-(4-Chlorophenyl)-5-(4-methoxyphenyl)penta-1,4-diyn-3-yl
benzoate (1u). Yellow oil; 2.9 g, 74% yield; PE/EA = 25:1; 1H NMR
(500 MHz, CDCl3) δ 8.17−8.15 (m, 2H), 7.62−7.58 (m, 1H), 7.49−
7.44 (m, 6H), 7.32−7.28 (m, 2H), 6.87−6.84 (m, 2H), 6.77 (s, 1H),
3.81 (s, 3H); 13C{1H} NMR (125 MHz, CDCl3) δ 165.4, 160.6,
135.6, 134.1, 133.9, 133.7, 130.5, 129.7, 129.1, 128.9, 120.6, 114.4,
114.0, 86.1, 84.5, 84.5, 81.8, 55.7, 55.2; HRMS (APCI) m/z calcd for
C25H18ClO3 (M + H)+: 401.0939, found 401.0940.
3-Methyl-1,5-diphenylpenta-1,4-diyn-3-yl benzoate (1v). Yellow
solid; mp 96−97 °C; 2.9 g, 84% yield; PE/EA = 50:1; 1H NMR (500
MHz, CDCl3) δ 8.12−8.10 (m, 2H), 7.58−7.55 (m, 1H), 7.52−7.50
(m, 4H), 7.47−7.44 (m, 2H), 7.33−7.28 (m, 6H), 2.23 (s, 3H);
13C{1H} NMR (100 MHz, CDCl3) δ 163.9, 133.1, 132.0, 130.3,
129.8, 128.7, 128.3, 128.2, 122.1, 87.0, 84.4, 65.5, 31.1; HRMS
(APCI) m/z calcd for C25H19O2 (M + H)+: 351.1380, found
351.1383.
1-Benzyl-3-(phenylsulfonyl)naphthalen-2-yl benzoate (3ab).
White solid; mp 178−179 °C; 75 mg, 78% yield; PE/EA = 10:1;
1H NMR (400 MHz, CDCl3) δ 8.84 (s, 1H), 8.09−8.07 (m, 1H),
7.99−7.93 (m, 3H), 7.74−7.72 (m, 2H), 7.66−7.63 (m, 1H), 7.61−
7.59 (m, 2H), 7.55−7.46 (m, 3H), 7.35−7.31 (m, 2H), 7.16−7.10
(m, 3H), 7.02−7.00 (m, 2H), 4.35 (d, J = 16.2 Hz, 1H), 4.15 (d, J =
16.2 Hz, 1H); 13C{1H} NMR (100 MHz, CDCl3) δ 164.2, 142.8,
141.0, 139.0, 135.7, 134.1, 133.4, 132.1, 131.9, 131.3, 131.1, 130.7,
130.6, 129.9, 129.0, 128.9, 128.7, 128.6, 128.4, 128.1, 127.2, 126.4,
125.3, 32.3; HRMS (APCI) m/z calcd for C30H23O4S (M + H)+:
479.1312, found 479.1313.
1-Cyclopropyl-5-phenylpenta-1,4-diyn-3-yl benzoate (1w). Yel-
low oil; 2.5 g, 82% yield; PE/EA = 50:1; 1H NMR (500 MHz,
CDCl3) δ 8.14−8.12 (m, 2H), 7.61−7.57 (m, 1H), 7.51−7.45 (m,
4H), 7.36−7.30 (m, 3H), 6.52 (d, J = 2.1 Hz, 1H), 1.36−1.31 (s,
1H), 0.85−0.78 (m,4H); 13C{1H} NMR (100 MHz, CDCl3) δ 165.4,
133.8, 132.5, 130.5, 129.9, 129.4, 128.8, 128.7, 122.3, 90.3, 85.2, 83.9,
69.9, 55.2, 8.82; HRMS (APCI) m/z calcd for C21H17O2 (M + H)+:
301.1223, found 301.1226.
1-Benzyl-3-((4-methoxyphenyl)sulfonyl)naphthalen-2-yl ben-
zoate (3ac). White solid; mp 163−164 °C; 95 mg, 93% yield; PE/
6,6-Dimethyl-1-phenylhepta-1,4-diyn-3-yl benzoate (1x). Yellow
1
1
EA = 8:1; H NMR (400 MHz, CDCl3) δ 8.80 (s, 1H), 8.07−8.03
oil; 2.7 g, 86% yield; PE/EA = 60:1; H NMR (400 MHz, CDCl3) δ
(m, 3H), 7.95−7.93 (m, 1H), 7.68−7.64 (m, 3H), 7.60−7.56 (m,
2H), 7.50 (t, J = 15.9 Hz, 2H), 7.17−7.11 (m, 3H), 7.03−7.02 (m,
2H), 6.79−6.76 (m, 2H), 4.36 (d, J = 16.3 Hz, 1H), 4.16 (d, J = 16.3
Hz, 1H) 3.81 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ 164.7,
163.9, 143.2, 139.4, 135.9, 134.5, 133.1, 132.8, 131.9, 131.5, 131.1,
131.0, 130.9, 130.2, 129.4, 129.1, 129.0, 128.8, 127.5, 126.7, 125.7,
114.6, 56.1, 32.5; HRMS (APCI) m/z calcd for C31H25O5S (M +
H)+: 509.1417, found 509.1420.
8.15−8.12 (m, 2H), 7.61−7.57 (m, 1H), 7.51−7.45 (m, 4H), 7.34−
7.30 (m, 3H), 6.56 (s, 1H), 1.27 (s, 9H); 13C{1H} NMR (100 MHz,
CDCl3) δ 164.6, 132.9, 131.7, 129.6, 129.1, 128.5, 128.0, 127.9, 121.5,
94.2, 84.1, 83.4, 72.4, 54.2, 30.2, 27.1; HRMS (APCI) m/z calcd for
C22H21O2 (M + H)+: 317.1536, found 317.1538.
1-Phenyldeca-1,4-diyn-3-yl benzoate (1y). Yellow oil; 2.7 g, 83%
1
yield; PE/EA = 50:1; H NMR (500 MHz, CDCl3) δ 8.15−8.13 (m,
2H), 7.61−7.57 (m, 1H), 7.51−7.45 (m, 4H), 7.35−7.30 (m, 3H),
6.55−6.54 (m, 1H), 2.28 (td, J = 7.2, 2.1 Hz, 2H), 1.60−1.54 (m,
2H), 1.42−1.29 (m, 4H), 0.89 (t, J = 7.2 Hz, 3H); 13C{1H} NMR
(125 MHz, CDCl3) δ 165.4, 133.8, 132.5, 130.4, 129.9, 129.3, 128.8,
128.7, 122.2, 87.5, 85.1, 84.0, 74.6, 55.1, 31.4, 28.3, 22.6, 19.2, 14.4;
HRMS (APCI) m/z calcd for C23H23O2 (M + H)+: 331.1693, found
331.1697.
1-Benzyl-3-((4-chlorophenyl)sulfonyl)naphthalen-2-yl benzoate
(3ad). White solid; mp 186−187 °C; 76 mg, 74% yield; PE/EA =
1
10:1; H NMR (400 MHz, CDCl3) δ 8.84 (s, 1H), 8.10−8.08 (m,
1H), 8.01−7.95 (m, 3H), 7.70−7.60 (m, 5H), 7.54−7.50 (m, 2H),
7.31−7.28 (m, 2H), 7.19−7.12 (m, 3H), 7.03−7.01 (m, 2H), 4.37 (d,
J = 16.2 Hz, 1H), 4.17 (d, J = 16.2 Hz, 1H); 13C{1H} NMR (100
MHz, CDCl3) δ 164.1, 142.4, 139.7, 139.1, 138.6, 135.5, 134.0, 131.7,
131.4, 131.1, 130.7, 130.4, 130.3, 129.8, 129.3, 129.0, 128.6, 128.5,
128.4, 128.0, 127.0, 126.2, 125.1, 32.0. HRMS (APCI) m/z calcd for
C30H22O4ClS (M + H)+: 513.0927, found 513.0920.
(3-Methoxypenta-1,4-diyne-1,5-diyl)dibenzene (z1). Yellow oil;
1
1.3 g, 52% yield; PE/EA = 60:1; H NMR (500 MHz, CDCl3) δ
7.52−7.50 (m, 4H), 7.37−7.31 (m, 6H), 5.40 (s, 1H), 3.58 (s, 3H);
13C{1H} NMR (125 MHz, CDCl3) δ 132.4, 129.2, 128.7, 122.4, 85.9,
84.2, 61.3, 55.3; HRMS (APCI) m/z calcd for C18H15O (M + H)+:
247.1117, found 247.1121.
1-Benzyl-3-((4-fluorophenyl)sulfonyl)naphthalen-2-yl benzoate
(3ae). White solid; mp 171−172 °C; 79 mg, 80% yield; PE/EA =
1
10:1; H NMR (400 MHz, CDCl3) δ 8.82 (s, 1H), 8.09−8.07 (m,
(3-Ethoxypenta-1,4-diyne-1,5-diyl)dibenzene (z2). Yellow oil; 1.6
1
1H), 8.01−7.94 (m, 3H), 7.76−7.72 (m, 2H), 7.69−7.64 (m, 1H),
7.62−7.58 (m, 2H),7.52−7.48 (m, 2H), 7.17−7.11 (m, 3H), 7.02−
6.97 (m, 4H), 4.36 (d, J = 16.2 Hz, 1H), 4.16 (d, J = 16.2 Hz, 1H);
13C{1H} NMR (125 MHz, CDCl3) δ 165.8 (C−F, 1JC−F = 252.3 Hz)
164.4, 142.7, 139.0, 137.0 (C−F, 4JC−F = 3.1 Hz), 135.8, 134.3, 132.0,
131.9, 131.5, 131.1, 131.0, 130.7 (C−F, 3JC−F = 7.4 Hz), 130.2, 128.9,
g, 62% yield; PE/EA = 80:1; H NMR (500 MHz, CDCl3) δ 7.52−
7.49 (m, 4H), 7.36−7.30 (m, 6H), 5.44 (s, 1H), 3.84 (q, J = 7.1 Hz,
2H); 1.34 (t, J = 7.1 Hz, 3H); 13C{1H} NMR (125 MHz, CDCl3) δ
132.4, 129.1, 128.7, 122.5, 85.5, 84.8, 63.7, 60.0, 15.5; HRMS m/z
(APCI) calcd for C19H17O (M + H)+ 261.1274, found 261.1279.
((1,5-Diphenylpenta-1,4-diyn-3-yl)oxy)trimethylsilane (z3). Yel-
low oil; 1.8 g, 60% yield; PE/EA = 20:1; 1H NMR (500 MHz,
CDCl3) δ 7.51−7.48 (m, 4H), 7.34−7.30 (m, 6H), 5.66 (s, 1H), 0.31
(s, 3H); 13C{1H} NMR (125 MHz, CDCl3) δ 132.2, 129.1, 128.7,
2
128.8, 128.7, 128.4, 127.4, 126.5, 125.4, 116.4 (C−F, JC−F = 22.6
Hz), 32.4; 19F NMR (376 MHz, CDCl3) δ −103.9; HRMS (APCI)
m/z calcd for C30H22O4FS (M + H)+: 497.1217, found 497.1219.
6253
https://doi.org/10.1021/acs.joc.1c00038
J. Org. Chem. 2021, 86, 6247−6258

The Journal of Organic Chemistry
pubs.acs.org/joc
Article
1-Benzyl-3-(naphthalen-2-ylsulfonyl)naphthalen-2-yl benzoate
(3af). White solid; mp 170−171 °C; 76 mg, 72% yield; PE/EA =
8:1; 1H NMR (400 MHz, CDCl3) δ 8.93 (s, 1H), 8.32 (d, J = 1.7 Hz,
1H), 8.12−8.10 (m, 1H), 7.95−7.92 (m, 1H),7.89−7.78 (m, 4H),
7.67−7.52 (m, 7H), 7.44−7.40 (m, 2H), 7.12−7.07 (m, 3H), 7.00−
7.67 (m, 2H), 4.33 (d, J = 16.3 Hz, 1H), 4.13 (d, J = 16.3 Hz, 1H);
13C{1H} NMR (100 MHz, CDCl3) δ 164.1, 142.6, 138.8, 137.4,
135.5, 135.0, 133.9, 131.9, 131.8, 131.7, 131.1, 130.9, 130.5, 130.4,
129.8, 129.7, 129.3, 129.2, 129.1, 128.6, 128.5, 128.4, 128.1, 127.9,
127.4, 127.0, 126.2, 125.1, 122.8, 32.1; HRMS (APCI) m/z calcd for
C34H25O4S (M + H)+: 529.1468, found 529.1467.
1-Benzyl-3-(thiophen-2-ylsulfonyl)naphthalen-2-yl benzoate
(3ag). White solid; mp 172−173 °C; 76 mg, 78% yield; PE/EA =
8:1; 1H NMR (400 MHz, CDCl3) δ 8.76 (s, 1H), 8.13−8.11 (m, 2H),
8.06−8.03 (m, 1H), 7.97−7.94 (m, 1H), 7.65 (t, J = 7.3 Hz, 1H),
7.62−7.55 (m, 4H), 7.50 (t, J = 7.8 Hz, 2H), 7.19−7.12 (m, 3H),
7.06−7.04 (m, 2H), 6.97−6.94 (m, 1H), 4.40 (d, J = 16.2 Hz, 1H),
4.22 (d, J = 16.2 Hz, 1H); 13C{1H} NMR (100 MHz, CDCl3) δ
164.6, 142.6, 142.4, 138.9, 135.5, 134.1, 134.0, 133.9, 132.7, 131.4,
131.2, 131.0, 130.5, 130.4, 129.9, 128.9, 128.6, 128.5, 128.2, 127.3,
127.0, 126.3, 125.1, 32.1; HRMS(APCI) m/z calcd for
C28H21O4S2(M + H)+: 485.0876, found 485.0871.
1-Benzyl-3-(pyridin-3-ylsulfonyl)naphthalen-2-yl benzoate
(3ah). White solid; mp 209−210 °C; 76 mg, 79% yield; PE/EA =
8:1; 1H NMR (400 MHz, CDCl3) δ 8.97 (s, 1H), 8.85 (s, 1H), 8.77
(s, 1H), 8.10−8.07 (m, 1H), 8.02−7.95 (m, 4H), 7.70−7.60 (m, 3H),
7.54−7.50 (m, 2H), 7.32−7.30 (m, 1H), 7.17−7.11 (m, 3H), 7.01−
6.99 (m, 2H), 4.38 (d, J = 16.2 Hz, 1H), 4.16 (d, J = 16.2 Hz, 1H);
13C{1H} NMR (100 MHz, CDCl3) δ 164.4, 153.6, 148.9, 142.5,
139.0, 137.8, 135.4, 132.7, 132.4, 131.4, 131.0, 130.8, 130.3, 129.6,
129.4, 128.4, 128.2, 128.1, 127.0, 126.2, 125.1, 121.1, 113.8, 55.6,
32.1, 21.6; HRMS (APCI) m/z calcd for C32H27O5S (M + H)+:
523.1574, found 523.1572.
1-Benzyl-3-tosylnaphthalen-2-yl 4-fluorobenzoate (3da). White
1
solid; mp 180−181 °C; 68 mg, 67% yield; PE/EA = 10:1; H NMR
(400 MHz, CDCl3) δ 8.80 (s, 1H), 8.08−7.92 (m, 4H), 7.63−7.58
(m, 4H), 7.19−7.12 (m, 7H), 7.01−7.00 (m, 2H), 4.36 (d, J = 16.3
Hz, 1H), 4.15 (d, J = 16.3 Hz, 1H), 2.40 (s, 3H); 13C{1H} NMR (100
MHz, CDCl3) δ 166.4 (C−F, 1JC−F = 254.1 Hz), 163.3, 144.3, 142.5,
138.8, 137.9, 135.4, 133.2 (C−F, 3JC−F = 9.4 Hz), 132.1, 131.6, 131.0,
130.9, 130.4, 129.8, 129.5, 128.5, 128.2, 127.9, 127.1, 126.3, 125.1
4
2
(C−F, JC−F = 2.3 Hz), 115.8 (C−F, JC−F = 22 Hz), 32.1, 21.7; 19F
NMR (376 MHz, CDCl3) δ −103.5; HRMS (APCI) m/z calcd for
C31H24O4SF (M + H)+: 511.1374, found 511.1372.
1-Benzyl-3-tosylnaphthalen-2-yl 4-chlorobenzoate (3ea). Yellow
1
solid; mp 217−218 °C; 67 mg, 64% yield; PE/EA = 10:1; H NMR
(400 MHz, CDCl3) δ 8.79 (s, 1H), 8.07−8.05 (m, 1H), 7.95−7.91
(m, 3H), 7.62−7.58 (m, 4H), 7.47−7.45 (m, 2H), 7.16−7.11 (m,
5H), 7.00−6.98 (m, 2H), 4.36 (d, J = 16.3 Hz, 1H), 4.13 (d, J = 16.3
Hz, 1H), 2.39 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ 163.4,
144.3, 142.4, 140.5, 138.7, 137.9, 135.4, 132.1, 131.8, 131.6, 130.9,
130.4, 129.8, 129.5, 128.9, 128.5, 128.1, 127.9, 127.3, 127.1, 126.3,
125.1, 32.1, 21.6; HRMS (APCI) m/z calcd for C31H24O4ClS (M +
H)+: 527.1078, found 527.1079.
1-Benzyl-3-tosylnaphthalen-2-yl-4-bromobenzoate (3fa). Yellow
1
solid; mp 222−223 °C; 71 mg, 62% yield; PE/EA = 10:1; H NMR
(400 MHz, CDCl3) δ 8.79 (s, 1H), 8.08−8.05 (m, 1H), 7.95−7.93
(m, 1H), 7.86−7.83 (m, 2H), 7.64−7.58 (m, 6H), 7.16−7.10 (m,
5H), 7.00−6.98 (m, 2H), 4.35 (d, J = 16.3 Hz, 1H), 4.13 (d, J = 16.3
Hz, 1H), 2.39 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ 163.5,
144.3, 142.4, 138.7, 137.9, 135.4, 132.0, 131.9, 131.8, 131.6, 130.9,
130.4, 129.8, 129.5, 129.2, 128.5, 128.1, 127.9, 127.7, 127.1, 126.3,
125.1, 32.1, 21.6; HRMS (APCI) m/z calcd for C31H24O4BrS (M +
H)+: 571.0573, found 571.0576.
138.6, 137.6, 135.8, 135.6, 134.2, 132.1, 131.4, 131.2, 130.9, 130.5,
130.4, 130.2, 128.8, 128.6, 128.5, 128.1, 127.3, 126.3, 125.2, 123.4,
32.1; HRMS (APCI) m/z calcd for C29H22O4NS (M + H)+:
480.1264, found 480.1268.
1-Benzyl-3-(methylsulfonyl)naphthalen-2-yl benzoate (3ai). Yel-
1
low solid; mp 138−139 °C; 37 mg, 45% yield; PE/EA = 10:1; H
NMR (400 MHz, CDCl3) δ 8.64 (s, 1H), 8.19−8.16 (m, 2H), 8.06−
8.02 (m, 2H), 7.60−7.58 (m, 3H), 7.53−7.50 (m, 2H), 7.22−7.12
(m, 5H), 4.50 (d, J = 16.1 Hz, 1H), 4.30 (d, J = 16.1 Hz, 1H), 3.21 (s,
3H); 13C{1H} NMR (100 MHz, CDCl3) δ 164.9, 142.7, 138.9, 135.5,
134.0, 131.7, 131.5, 131.2, 130.9, 130.4, 130.3, 129.9, 128.9, 128.8,
128.6, 128.2, 127.1, 126.4, 125.1, 44.0, 32.2; HRMS (APCI) m/z
calcd for C25H21O4S (M + H)+: 417.1155, found 417.1159.
1-Benzyl-3-tosylnaphthalen-2-yl 4-(trifluoromethyl)benzoate
(3ga). White solid; mp 132−133 °C; 78 mg, 70% yield; PE/EA =
1
10:1; H NMR (400 MHz, CDCl3) δ 8.78 (s, 1H), 8.13−8.05 (m,
3H), 7.96−7.93 (m, 1H), 7.77−7.75 (m, 2H), 7.63−7.59 (m, 4H),
7.17−7.12 (m, 5H), 7.01−6.99 (m, 2H), 4.38 (d, J = 16.3 Hz, 1H),
4.15 (d, J = 16.3 Hz, 1H), 2.40 (s, 3H); 13C{1H} NMR (100 MHz,
CDCl3) δ 163.1, 144.3, 142.3, 138.6, 137.9, 135.5, 135.4, 135.1, 132.1,
1-Benzyl-3-(ethylsulfonyl)naphthalen-2-yl benzoate (3aj). Yel-
2
3
131.8 (C−F, JC−F = 24.4 Hz), 131.0, 130.9 (C−F, JC−F = 9.6 Hz),
1
low solid; mp 166−167 °C; 51 mg, 59% yield; PE/EA = 10:1; H
130.8, 130.4, 129.8, 129.5, 128.5, 128.1, 127.8, 126.3, 126.1 (C−F,
NMR (400 MHz, CDCl3):δ 8.60 (s, 1H), 8.17−8.15 (m, 2H), 8.06−
8.01 (m, 2H), 7.68−7.58 (m, 3H), 7.53−7.49 (m, 2H), 7.23−7.16
(m, 3H), 7.12−7.10 (m, 2H), 4.48 (d, J = 16.1 Hz, 1H), 4.29 (d, J =
16.1 Hz, 1H), 3.32 (q, J = 7.5 Hz, 2H), 1.27 (t, J = 7.5 Hz, 3H);
13C{1H} NMR (100 MHz, CDCl3) δ 164.8, 142.9, 139.0, 135.5,
133.9, 132.9, 131.2, 130.9, 130.4, 130.3, 129.9, 129.3, 128.9, 128.8,
128.6, 128.2, 127.1, 126.3, 125.1, 50.0, 32.2, 7.4; HRMS (APCI) m/z
calcd for C26H23O4S (M + H)+: 431.1312, found 431.1311.
1JC−F = 257.2 Hz), 125.5 (C−F, 4JC−F = 3.7 Hz), 122.2, 32.1, 21.6; 19
F
NMR (376 MHz, CDCl3) δ −63.1; HRMS (ESI) m/z calcd for
C32H24F3O4S (M + H)+: 561.1342, found 561.1346.
1-Benzyl-3-tosylnaphthalen-2-yl 1-naphthoate (3ha). Yellow
1
solid; mp 173−174 °C; 96 mg, 89% yield; PE/EA = 8:1; H NMR
(400 MHz, CDCl3) δ 8.86 (s, 1H), 8.77−8.74 (m, 1H), 8.35 (dd, J1 =
1.2 Hz, J2 = 7.3 Hz, 1H), 8.15−8.08 (m, 2H), 7.98−7.92 (m, 2H),
7.61−7.54 (m, 7H), 7.17−7.13 (m, 3H), 7.06−7.05 (m, 2H), 6.93 (d,
J = 6.6 Hz, 2H), 4.45 (d, J = 16.4 Hz, 1H), 4.28 (d, J = 16.4 Hz, 1H),
2.23 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ 164.4, 144.1,
142.7, 138.9, 137.7, 135.5, 134.9, 133.9, 132.6, 131.9, 131.8, 131.5,
131.0, 130.9, 130.4, 129.7, 129.4, 128.6, 128.5, 128.3, 128.2, 128.0,
127.0, 126.5, 126.3, 126.1, 125.1, 124.8, 124.4, 32.2, 21.5; HRMS
(ESI) m/z calcd for C35H26O4SNa (M + Na)+: 565.1444, found
565.1447.
1-Benzyl-3-tosylnaphthalen-2-yl-4-methylbenzoate (3ba). White
1
solid; mp 187−188 °C; 76 mg, 75% yield; PE/EA = 10:1; H NMR
(400 MHz, CDCl3) δ 8.81(s, 1H), 8.06−8.04 (m, 1H), 7.94−7.89
(m, 3H), 7.64−7.62 (m, 2H), 7.59−7.56 (m, 2H), 7.30−7.27 (m,
2H), 7.16−7.09 (m, 5H), 7.02−7.00 (m, 2H), 4.34 (d, J = 16.2 Hz,
1H), 4.14 (d, J = 16.2 Hz, 1H), 2.47 (s, 3H), 2.38 (s, 3H); 13C{1H}
NMR (100 MHz, CDCl3) δ 164.3, 144.9, 144.1, 142.8, 139.0, 137.9,
135.5, 132.4, 131.5, 131.1, 130.9, 130.7, 130.4, 129.7, 129.5, 129.3,
128.5, 128.3, 128.1, 126.9, 126.2, 126.1, 125.2, 32.2, 21.9, 21.7;
HRMS (APCI) m/z calcd for C32H27O4S (M + H)+: 507.1625, found
507.1621.
1-Benzyl-3-tosylnaphthalen-2-yl furan-2-carboxylate (3ia).
White solid; mp 241−242 °C; 70 mg, 73% yield; PE/EA = 12:1;
1H NMR (400 MHz, CDCl3) δ 8.79 (s, 1H), 8.06−8.04 (m, 1H),
7.92−7.90 (m, 1H), 7.76 (d, J = 8.3 Hz, 2H), 7.69−7.68 (m, 1H),
7.60−7.55 (m, 2H), 7.29−7.27 (m, 1H), 7.21 (d, J = 8.0 Hz, 2H),
7.17−7.07 (m, 3H), 7.04−7.02 (m, 2H), 6.62−6.61 (m, 1H), 4.36 (d,
J = 16.2 Hz, 1H), 4.13 (d, J = 16.2 Hz, 1H), 2.40 (s, 3H); 13C{1H}
NMR (100 MHz, CDCl3) δ 155.9, 147.3, 144.3, 143.5, 141.7, 138.8,
137.9, 135.3, 132.3, 131.6, 131.2, 131.0, 130.3, 129.7, 129.4, 128.5,
128.2, 128.1, 127.0, 126.2, 125.2, 120.2, 112.3, 32.1, 21.7; HRMS
1-Benzyl-3-tosylnaphthalen-2-yl 4-methoxybenzoate (3ca).
1
White solid; mp 185−186 °C; 84 mg, 80% yield; PE/EA = 7:1; H
NMR (500 MHz, CDCl3) δ 8.81 (s, 1H), 8.07−8.05 (m, 1H), 7.96−
7.92(m, 3H),7.63 (d, J = 7.6 Hz, 2H), 7.58−7.56 (m, 2H), 7.15−7.09
(m, 5H), 7.01 (d, J = 7.6 Hz, 2H), 6.95−6.94 (m, 2H), 4.34 (d, J =
16.3 Hz, 1H), 4.15 (d, J = 16.3 Hz, 1H), 2.92 (s, 3H), 2.28 (s, 3H);
13C{1H} NMR (125 MHz, CDCl3) δ 164.1, 163.8, 144.1, 142.8,
6254
https://doi.org/10.1021/acs.joc.1c00038
J. Org. Chem. 2021, 86, 6247−6258

The Journal of Organic Chemistry
pubs.acs.org/joc
Article
(APCI) m/z calcd for C29H23O5S (M + H)+: 483.1261, found
483.1266.
7.39−7.34 (m, 1H), 7.12 (d, J = 8.0 Hz, 2H), 6.98−6.95 (m, 2H),
6.83 (t, J = 8.6 Hz, 2H) 4.23 (d, J = 16.4 Hz, 1H), 4.07 (d, J = 16.4
Hz, 1H), 2.38 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ 164.1,
1-Benzyl-3-tosylnaphthalen-2-yl acetate (3ja). White solid; mp
258−259 °C; 54 mg, 63% yield; PE/EA = 10:1; 1H NMR (400 MHz,
CDCl3) δ 8.70 (s, 1H), 8.02−7.99 (m, 1H), 7.88−7.86 (m, 1H),
7.84−7.81 (m, 2H), 7.56−7.52 (m, 2H), 7.31−7.29 (m, 2H), 7.19−
7.13 (m, 3H), 7.02−7.00 (m, 2H), 4.25 (br, 2H), 2.41 (s, 3H), 2.35
(s, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ 168.9, 144.4, 142.5,
138.8, 138.6, 135.3, 131.8, 131.6, 130.9, 130.3, 129.7, 129.6, 128.5,
128.2, 127.6, 126.9, 126.3, 125.1, 32.0, 21.7, 21.1; HRMS (APCI) m/
z calcd for C26H23O4S (M + H)+: 431.1312, found 431.1311.
1-Benzyl-3-tosylnaphthalen-2-yl cyclopropanecarboxylate
(3ka). Yellow solid; mp 73−74 °C; 68 mg, 75% yield; PE/EA =
1
1
163.0 (C−F, JC−F = 250.1 Hz), 161.5 (C−F, JC−F = 243.4 Hz),
144.4, 143.7, 137.6, 137.0 (C−F, 3JC−F = 9.8 Hz), 134.1, 133.9 (C−F,
3
4
4JC−F = 3.1 Hz), 133.1 (C−F, JC−F = 9.7 Hz), 131.9 (C−F, JC−F
=
2.8 Hz), 131,5, 130.5, 130.4 (C−F, 3JC−F = 5.7 Hz), 129.6, 129.5 (C−
F, JC−F = 2.0 Hz), 128.6, 128.5, 128.1, 127.9, 117.6 (C−F, JC−F
25.3 Hz), 115.5 (C−F, JC−F = 21.1 Hz), 109.3 (C−F, JC−F = 22.7
Hz), 31.5, 21.7; 19F NMR (376 MHz, CDCl3) δ −106.3, −116.3;
HRMS (APCI) m/z calcd for C31H23O4F2S (M + H)+: 529.1280,
found 529.1283.
4
2
=
2
2
7-Chloro-1-(4-chlorobenzyl)-3-tosylnaphthalen-2-yl benzoate
1
10:1; H NMR (400 MHz, CDCl3) δ 8.72 (s, 1H), 8.02−8.00 (m,
(3qa). White solid; mp 176−177 °C; 73 mg, 65% yield; PE/EA =
1
1H), 7.89−7.85 (m, 3H), 7.56−7.52 (m, 2H), 7.29 (d, J = 8.1 Hz,
2H), 7.19−7.11 (m, 3H), 7.02 (d, J = 6.8 Hz, 2H), 4.23 (br, 2H),
2.42 (s, 3H) 1.86−1.82 (m, 1H), 1.10−1.02 (m, 4H); 13C{1H} NMR
(100 MHz, CDCl3) δ 172.6, 144.2, 142.5, 138.9, 138.3, 135.4, 132.1,
131.4, 130.8, 130.7, 130.3, 129.6, 129.5, 128.5, 128.2, 127.9, 126.8,
126.2, 125.0, 31.9, 21.6, 13.0, 9.7; HRMS (APCI) m/z calcd for
C28H25O4S (M + H)+: 457.1468, found 457.1474.
10:1; H NMR (400 MHz, CDCl3) δ 8.78 (s, 1H), 8.02−7.97 (m,
3H), 7.84 (s, 1H), 7.68 (t, J = 7.4 Hz, 1H), 7.60 (d, J = 8.2 Hz,
2H),7.56−7.48 (m, 3H), 7.12 (d, J = 8.2 Hz, 4H), 6.93 (d, J = 8.3 Hz,
2H), 4.26 (d, J = 16.5 Hz, 1H), 4.07 (d, J = 16.5 Hz, 1H), 2.38 (s,
3H); 13C{1H} NMR (100 MHz, CDCl3) δ 164.0, 144.4, 143.8, 137.5,
136.7, 136.3, 136.1, 134.1, 132.8, 132.3, 131.9, 131.4, 130.5, 129.9,
129.5, 129.4, 129.2, 128.7, 128.6, 128.5, 128.2, 128.1, 124.0, 31.4,
21.6; HRMS (APCI) m/z calcd for C31H23Cl2O4S (M + H)+:
561.0694, found 561.0692.
1-Benzyl-3-tosylnaphthalen-2-yl methacrylate (3la). Yellow
1
solid; mp 108−109 °C; 64 mg, 70% yield; PE/EA = 8:1; H NMR
(400 MHz, CDCl3) δ 8.75 (s, 1H), 8.04−8.02 (m, 1H), 7.93−7.90
(m, 1H), 7.76 (d, J = 8.3 Hz, 2H), 7.57−7.55 (m, 2H), 7.24 (s, 1H),
7.18−7.11 (m, 3H), 7.02 (d, J = 6.8 Hz, 2H), 6.19 (s, 1H), 5.77 (t, J =
1.4 Hz, 1H), 4.31 (d, J = 16.2 Hz, 1H), 4.11 (d, J = 16.2 Hz, 1H),
2.40 (s, 3H), 1.96 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ
164.9, 144.2, 142.7, 138.9, 138.2, 135.5, 135.4, 132.1, 131.5, 130.9,
130.8, 130.3, 129.6, 129.5, 128.5, 128.2, 127.9, 127.8, 126.9, 126.2,
125.0, 32.0, 21.6, 18.4; HRMS (APCI) m/z calcd for C28H25O4S (M
+ H)+: 457.1468, found 457.1472.
1-Benzyl-3-tosylnaphthalen-2-yl pivalate (3ma). White solid; mp
193−194 °C; 67 mg, 71% yield; PE/EA = 10:1; 1H NMR (400 MHz,
CDCl3) δ 8.56 (s, 1H), 7.97−7.95 (m, 1H), 7.90−7.87 (m, 1H), 7.80
(d, J = 8.4 Hz, 2H), 7.55−7.52 (m, 2H), 7.28 (d, J = 8.0 Hz, 2H),
7.20−7.13 (m, 3H), 7.03 (d, J = 7.0 Hz, 2H), 4.37 (d, J = 16.4 Hz,
1H), 4.15 (d, J = 16.4 Hz, 1H), 2.41 (s, 3H), 1.32 (s, 9H); 13C{1H}
NMR (100 MHz, CDCl3) δ 176.6, 144.1, 143.0, 138.8, 138.5, 135.4,
132.1, 131.9, 130.7, 130.5, 130.2, 129.6, 128.5, 128.1, 127.3, 126.8,
126.2, 124.8, 39.3, 31.6, 27.4, 21.6; HRMS (APCI) m/z calcd for
C29H29O4S (M + H)+: 473.1781, found 473.1778.
7-Methyl-1-(4-methylbenzyl)-3-tosylnaphthalen-2-yl benzoate
(3na). White solid; mp 138−139 °C; 81 mg, 78% yield; PE/EA =
9:1; 1H NMR (500 MHz, CDCl3) δ 8.75 (s, 1H), 8.01−8.00 (m, 2H),
7.95 (d, J = 6.7 Hz, 1H), 7.72 (s, 1H), 7.65−7.61 (m, 3H), 7.49 (t, J =
6.3 Hz, 2H), 7.42−7.40 (m, 1H), 7.11 (d, J = 6.5 Hz, 2H), 6.93 (dd,
J1 = 6.5 Hz, J2 = 17.0 Hz, 4H), 4.29 (d, J = 16.0 Hz, 1H), 4.13 (d, J =
16.0 Hz, 1H), 2.47 (s, 3H), 2.38 (s, 3H), 2.24 (s, 3H); 13C{1H} NMR
(125 MHz, CDCl3) δ 164.6, 144.4, 143.0, 140.4, 138.4, 136.2, 136.1,
136.0, 134.2, 131.5, 130.9, 130.8, 130.5, 129.8, 129.6, 129.5, 129.4,
129.3, 128.9, 128.4, 128.3, 124.6, 32.0, 22.8, 22.0, 21.3; HRMS
(APCI) m/z calcd for C33H29O4S (M + H)+: 521.1781, found
521.1783.
7-Bromo-1-(4-bromobenzyl)-3-tosylnaphthalen-2-yl benzoate
(3ra). Yellow solid; mp 184−185 °C; 91 mg, 70% yield; PE/EA =
8:1; 1H NMR (400 MHz, CDCl3) δ 8.77 (s, 1H), 8.03−7.92 (m, 4H),
7.69−7.65 (m, 2H), 7.60 (d, J = 8.3 Hz, 2H), 7.50 (t, J = 8.0 Hz, 2H),
7.28−7.26 (m, 2H), 7.12 (d, J = 8.0 Hz, 2H), 6.86 (d, J = 8.4 Hz,
2H), 4.24 (d, J = 16.5 Hz, 1H), 4.04 (d, J = 16.5 Hz, 1H), 2.38 (s,
3H); 13C{1H} NMR (100 MHz, CDCl3) δ 164.0, 144.4, 143.7, 137.5,
137.2, 136.3, 134.1, 133.0, 131.8, 131.7, 131.5, 130.7, 130.5, 129.8,
129.7, 129.5, 129.4, 128.6, 128.5, 128.1, 127.3, 124.9, 120.3, 31.5,
21.6; HRMS (APCI) m/z calcd for C31H23O4Br2S (M + H)+:
648.9678, found 648.9675.
1-(4-Methoxybenzyl)-3-tosylnaphthalen-2-yl benzoate (3sa)
and 1-Benzyl-7-methoxy-3-tosylnaphthalen-2-yl benzoate (3sa′).
1
Yellow solid; mp 191−192 °C; 75 mg, 72% yield; PE/EA = 8:1; H
NMR (400 MHz, CDCl3) δ 8.80 (s, 1.2H), 8.72 (s, 0.7H), 8.07−8.01
(m, 5H), 7.95−7.92 (m, 2H), 7.66−7.56 (m, 8H),7.51−7.45 (m,
4H), 7.21−7.06 (m, 9H), 6.94−6.92 (m, 2.4H), 6.70−6.67 (m,
2.4H), 4.31−4.24 (m, 2H), 4.14−4.07 (m, 2H), 3.70 (s, 3H), 3.70 (s,
1.7H), 2.37 (s, 5H); 13C{1H} NMR (100 MHz, CDCl3) δ 164.2,
160.4, 157.9, 144.1, 143.9, 143.3, 142.5, 139.0, 138.2, 137.8, 137.3,
135.4, 133.9, 133.9, 132.2, 131.8, 131.4, 131.3, 131.1, 130.9, 130.5,
130.3, 129.5, 129.4, 129.4, 129.1, 128.8, 128.5, 128.5, 128.3, 128.0,
127.9, 126.9, 126.2, 126.1, 125.2, 119.5, 113.9, 104.2, 55.3, 55.2, 32.5,
31.2, 21.6; HRMS (APCI) m/z calcd for C32H27O5S (M + H)+:
523.1574, found 523.1578.
1-Benzyl-7-chloro-3-tosylnaphthalen-2-yl benzoate (3ta). White
1
solid; mp 136−137 °C, 53 mg, 50% yield; PE/EA = 10:1; H NMR
(500 MHz, CDCl3) δ 8.78 (s, 1H), 8.00−7.99 (m, 3H), 7.93 (d, J =
1.4 Hz, 1H), 7.68−7.65 (m, 1H), 7.62−7.58 (m, 2H), 7.54−7.48 (m,
3 H), 7.18−7.13 (m, 5H), 7.03−7.00 (m, 2H), 4.28 (d, J = 16.4 Hz,
1H), 4.12 (d, J = 16.4 Hz, 1H), 2.38 (s, 3H); 13C{1H} NMR (125
MHz, CDCl3) δ 164.0, 144.3, 143.6, 138.3, 137.5, 136.2, 136.1, 134.0,
131.8, 131.2, 130.5, 130.5, 129.5, 129.2, 128.6, 128.5, 128.1, 128.0,
126.4, 124.3, 32.1, 21.6; HRMS (APCI) m/z calcd for C31H24ClO4S
(M + H)+: 527.1078, found 527.1073.
7-Methoxy-1-(4-methoxybenzyl)-3-tosylnaphthalen-2-yl ben-
zoate (3oa). White solid; mp 211−212 °C; 94 mg, 85% yield; PE/
1
EA = 6:1; H NMR (400 MHz, CDCl3) δ 8.71 (s, 1H), 8.04−8.02
(m, 2H), 7.93 (d, J = 9.0 Hz, 1H), 7.71−7.60 (m, 3H), 7.49 (t, J = 7.9
Hz, 2H), 7.21−7.19 (m, 1H), 7.14−7.10 (m, 3H), 6.98 (d, J = 8.6 Hz,
2H), 6.72−6.68 (m, 2H), 4.20 (d, J = 16.2 Hz, 1H), 4.05 (d, J = 16.2
Hz, 1H), 3.73 (s, 3H), 3.71 (s, 3H), 2.38 (s, 3H); 13C{1H} NMR
(100 MHz, CDCl3) δ 164.2, 160.4, 158.0, 143.9, 143.2, 138.2, 137.3,
133.8, 131.8, 131.1, 131.0, 130.5, 129.8, 129.5, 129.4, 129.2, 128.9,
128.5, 127.9, 126.1, 119.4, 113.9, 104.3, 55.3, 55.2, 31.6, 21.6; HRMS
(APCI) m/z calcd for C33H29O6S (M + H)+: 553.1679, found
553.1677.
1-(4-Chlorobenzyl)-3-tosylnaphthalen-2-yl benzoate (3ta′).
White solid; mp 140−141 °C; 28 mg, 27% yield; PE/EA = 10:1;
1H NMR (500 MHz, CDCl3) δ 8.82 (s, 1H), 8.09−8.07 (m, 1H),
8.01−7.99 (m, 2H), 7.87−7.85 (m, 1H), 7.69−7.66 (m, 1H), 7.61−
7.59 (m, 4H), 7.52−7.49 (m, 2H), 7.13−7.10 (m, 4H), 6.95−6.93
(m, 2H), 4.32 (d, J = 16.4 Hz, 1H), 4.11 (d, J = 16.4 Hz, 1H), 2.38 (s,
3H); 13C{1H} NMR (125 MHz, CDCl3) δ 164.6, 144.6, 143.1, 138.1,
137.7, 135.6, 134.4, 132.7, 132.4, 132.1, 131.3, 130.9, 130.8, 130.2,
129.9, 129.9, 129.0, 129.0, 128.4, 127.5, 125.3, 31.8, 22.0; HRMS
(APCI) m/z calcd for C31H23ClO4S (M + H)+: 527.1078, found
527.1080.
7-Fluoro-1-(4-fluorobenzyl)-3-tosylnaphthalen-2-yl benzoate
(3pa). Yellow solid; mp 188−189 °C; 76 mg, 72% yield; PE/EA =
1
10:1; H NMR (400 MHz, CDCl3) δ 8.81 (s, 1H), 8.08−8.05 (m,
1H), 8.01−7.98 (m, 2H), 7.70−7.60 (m, 3H), 7.52−7.46 (m, 3H),
6255
https://doi.org/10.1021/acs.joc.1c00038
J. Org. Chem. 2021, 86, 6247−6258

The Journal of Organic Chemistry
pubs.acs.org/joc
Article
7-Chloro-1-(4-methoxybenzyl)-3-tosylnaphthalen-2-yl benzoate
(3ua) and 1-(4-Chlorobenzyl)-7-methoxy-3-tosylnaphthalen-2-yl
benzoate (3ua′). Yellow solid; mp 164−165 °C; 76 mg, 68% yield;
AUTHOR INFORMATION
■
Corresponding Authors
1
PE/EA = 8:1; H NMR (500 MHz, CDCl3) δ 8.77 (s, 1H), 8.73 (s,
Meihua Xie − Key Laboratory of Functional Molecular Solids
(Ministry of Education), Anhui Key Laboratory of Molecular
Based Materials, College of Chemistry and Materials Science,
Anhui Normal University, Wuhu 241002, China;
orcid.org/0000-0002-1921-790X; Email: xiemh@
mail.ahnu.edu.cn
Jitan Zhang − Key Laboratory of Functional Molecular Solids
(Ministry of Education), Anhui Key Laboratory of Molecular
Based Materials, College of Chemistry and Materials Science,
Anhui Normal University, Wuhu 241002, China;
orcid.org/0000-0002-8249-8329; Email: zhangjt@
ahnu.edu.cn
0.4H), 8.01−7.92 (m, 5.6H), 7.69−7.65 (m, 1.6H), 7.62−7.60 (m,
2.8H), 7.54−7.48 (m, 4H), 7.23−7.21 (m, 0.5H), 7.13−7.11 (m,
3.7H), 7.04−7.03 (m, 0.4H), 7.00−6.98 (m, 0.9H), 6.93−6.91 (m,
2H), 6.71−6.69 (m, 2H), 4.23−4.20 (m, 1.6H), 4.08−4.03 (m,
1.5H), 3.73 (s, 1.3H), 3.72 (s, 3H), 2.38 (s, 4.2H); 13C{1H} NMR
(125 MHz, CDCl3) δ 164.1, 164.0, 160.5, 158.0, 144.2, 144.0, 143.4,
138.0, 137.5, 137.2, 137.0, 136.1, 136.0, 133.9, 133.8, 132.6, 131.7,
131.3, 131.0, 130.7, 130.5, 130.4, 130.2, 129.5, 129.4, 129.3, 129.0,
128.7, 128.6, 128.5, 128.4, 128.0, 127.9, 127.8, 126.0, 124.2, 119.4,
113.9, 103.9, 55.2, 55.1, 31.7, 31.1, 21.5; HRMS (APCI) m/z calcd
for C32H25ClO5S (M + H)+: 557.1184, found 557.1187.
General Procedure for the Synthesis of Compound 6. Under
argon atmosphere, 3aa (98.4 mg, 0.2 mmol), Pd(PPh3)2Cl2 (14.1 mg,
0.02 mol) and THF (1.0 mL) were added to a flask and cooled to 0
°C. Phenylmagnesium bromide (1 M in THF, 0.4 mL) was added
dropwise and stirred for 0.5 h at 40 °C. The reaction was quenched
with water, and extracted with ether (3 × 10 mL). The combined
organic layers were washed with saturated brine, dried over anhydrous
Na2SO4, filtered, and concentrated under reduced pressure. The
residue was purified by flash column chromatography on silica gel
(petroleum ether/ethyl acetate = 40/1) to afford 6.
Authors
Ziyi Guo − Key Laboratory of Functional Molecular Solids
(Ministry of Education), Anhui Key Laboratory of Molecular
Based Materials, College of Chemistry and Materials Science,
Anhui Normal University, Wuhu 241002, China
Yiming Zhao − Key Laboratory of Functional Molecular
Solids (Ministry of Education), Anhui Key Laboratory of
Molecular Based Materials, College of Chemistry and
Materials Science, Anhui Normal University, Wuhu 241002,
China
Yu Wang − Key Laboratory of Functional Molecular Solids
(Ministry of Education), Anhui Key Laboratory of Molecular
Based Materials, College of Chemistry and Materials Science,
Anhui Normal University, Wuhu 241002, China
1-Benzyl-3-phenylnaphthalen-2-yl benzoate (6). Yellow solid;
1
mp 49−50 °C; 68 mg, 82% yield; PE/EA = 40:1; H NMR (400
MHz, CDCl3) δ 8.03−8.00 (m, 1H), 7.97−7.95 (m, 2H), 7.93−7.92
(m, 1H), 7.88 (s, 1H), 7.59−7.53 (m, 3H), 7.51−7.47 (m, 2H),
7.41−7.37 (m, 2H), 7.32−7.29 (m, 2H), 7.25−7.21 (m, 5H), 7.18−
7.13 (m, 1H), 4.46 (m, 2H); 13C{1H} NMR (100 MHz, CDCl3) δ
164.7, 145.3, 140.0, 138.1, 134.8, 133.3, 132.4, 132.3, 130.0, 129.2,
129.1, 128.7, 128.4, 128.3, 128.2, 128.0, 127.4, 126.6, 126.0, 125.7,
124.7, 32.4; HRMS (APCI) m/z calcd for C30H23O2 (M + H)+:
415.1693, found 415.1695.
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.joc.1c00038
General Procedure for the Synthesis of Compound 7. Under
argon atmosphere, 3aa (98.4 mg, 0.2 mmol), LiAlH4 (15.2 mg, 0.4
mmol) and THF (2.0 mL) were added to a flask and the mixture was
stirred at room temperature until the complete consumption of 3aa
(monitored by TLC). The mixture was poured into saturated NH4Cl
and extracted with ether (3 × 10 mL). The combined organic layers
were washed with saturated NH4Cl, dried over anhydrous Na2SO4,
filtered, and concentrated under reduced pressure. The residue was
purified by flash column chromatography (silica gel, petroleum ether/
ethyl acetate = 10/1) to give 7.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We gratefully acknowledge the National Natural Science
Foundation of China (Nos. 21272004 and 21702237) for
financial support of this work.
1-Benzyl-3-tosylnaphthalen-2-ol (7). Yellow solid; mp 124−125
°C; 76 mg, 98% yield; PE/EA = 8:1; 1H NMR (400 MHz, CDCl3) δ
9.04 (s, 1H), 8.34 (m, 1H), 7.90−7.82 (m, 4H), 7.51−7.47 (m, 1H),
7.37−7.30 (m, 3H), 7.23−7.11 (m, 5H), 4.47 (s, 2H), 2.39 (s, 3H);
13C{1H} NMR (100 MHz, CDCl3) δ 148.3, 145.0, 140.0, 138.6,
136.6, 130.3, 130.2, 130.0, 129.7, 128.4, 128.2, 127.7, 127.0, 126.2,
126.0, 124.6, 123.8, 122.9, 30.6, 21.6; HRMS (APCI) m/z calcd for
C24H21O3S (M + H)+: 389.1206, found 389.1208.
REFERENCES
■
(1) For selected examples, see: (a) Tshitenge, D. T.; Feineis, D.;
Mudogo, V.; Kaiser, M.; Brun, R.; Seo, E.-J; Efferth, T.; Bringmann,
G. Mbandakamine-Type Naphthylisoquinoline Dimers and Related
Alkaloids from the Central African Liana Ancistrocladus ealaensis with
Antiparasitic and Antileukemic Activities. J. Nat. Prod. 2018, 81, 918−
933. (b) Abdissa, N.; Pan, F. F.; Gruhonjic, A.; Gräfenstein, J.;
Fitzpatrick, P. A.; Landberg, G.; Rissanen, K.; Yenesew, A.; Erdélyi,
M. Naphthalene Derivatives from the Roots of Pentas parvifolia and
Pentas bussei. J. Nat. Prod. 2016, 79, 2181−2187. (c) Ge, Y.; Kazi, A.;
Marsilio, F.; Luo, Y.; Jain, S.; Brooks, W.; Daniel, K. G.; Guida, W. C.;
Sebti, S. M.; Lawrence, H. R. Discovery and Synthesis of
Hydronaphthoquinones as Novel Proteasome Inhibitors. J. Med.
Chem. 2012, 55, 1978−1998. (d) Kozlowski, M. C.; Morgan, B. J.;
Linton, E. C. Rapid Formation of Molecular Complexity in Organic
Synthesis issue. Chem. Soc. Rev. 2009, 38, 3193−3207. (e) Krohn, K.;
Kouam, S. F.; Cludius-Brandt, S.; Draeger, S.; Schulz, B. Bioactive
Nitronaphthalenes from an Endophytic Fungus, Coniothyrium sp., and
Their Chemical Synthesis. Eur. J. Org. Chem. 2008, 2008, 3615−3618.
(f) Sommer, M. Conjugated polymers based on naphthalene diimide
for organic electronics. J. Mater. Chem. C 2014, 2, 3088−3098.
(2) For selected examples, see: (a) Jin, T.; Zhao, J.; Asao, N.;
Yamamoto, Y. Metal-Catalyzed Annulation Reactions for π-Con-
jugated Polycycles. Chem. - Eur. J. 2014, 20, 3554−3576.
ASSOCIATED CONTENT
■
sı
* Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.joc.1c00038.
X-ray crystallographic structure for compound 3aa, and
1
copies of H NMR and 13C NMR spectra (PDF)
Accession Codes
CCDC 1993167 contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge
via www.ccdc.cam.ac.uk/data_request/cif, or by emailing
data_request@ccdc.cam.ac.uk, or by contacting The Cam-
bridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
6256
https://doi.org/10.1021/acs.joc.1c00038
J. Org. Chem. 2021, 86, 6247−6258

The Journal of Organic Chemistry
pubs.acs.org/joc
Article
(b) Yamamoto, K.; Oyamada, N.; Xia, S.; Kobayashi, Y.; Yamaguchi,
M.; Maeda, H.; Nishihara, H.; Uchimaru, T.; Kwon, E. Equatorenes:
Synthesis and Properties of Chiral Naphthalene, Phenanthrene,
Chrysene, and Pyrene Possessing Bis(1-adamantyl) Groups at the
Peri-position. J. Am. Chem. Soc. 2013, 135, 16526−16532. (c) Sun,
C.; Hunt, D. K.; Clark, R. B.; Lofland, D.; O’Brien, W. J.; Plamondon,
L.; Xiao, X.-Y. Synthesis and Antibacterial Activity of Pentacyclines: A
Novel Class of Tetracycline Analogs. J. Med. Chem. 2011, 54, 3704−
3731. (d) Liu, J.; Li, B.-W.; Tan, Y.-Z.; Giannakopoulos, A.; Sanchez-
(Alkynyl)styrenes. J. Org. Chem. 2019, 84, 12848−12855. (b) Li,
H.; Zhou, P.; Xie, F.; Hu, J.-Q.; Yang, S.-Z.; Wang, Y.-J.; Hao, W.-J.;
Tu, S.-J.; Jiang, B. I2-Mediated Iodobenzannulation of Yne-Allenones
toward 1-Naphthols and Their Synthetic Application. J. Org. Chem.
2018, 83, 13335−13343. (c) Sha, H.-K.; Liu, F.; Lu, J.; Liu, Z.-Q.;
Hao, W.-J.; Tang, J.-L.; Tu, S.-J.; Jiang, B. Metal-free benzannulation
of yne-allenone esters for atom economical synthesis of functionalized
1-naphthols. Green Chem. 2018, 20, 3476−3485. (d) Liu, Y.; Guo, J.;
Liu, Y.; Wang, X.; Wang, Y.; Jia, X.; Wei, G.; Chen, L.; Xiao, J.;
Cheng, M. Au(I)-catalyzed Triple Bond Alkoxylation/Dienolether
Aromaticity-Driven Cascade Cyclization to Naphthalenes. Chem.
Commun. 2014, 50, 6243−6245. (e) Feng, C.; Loh, T.-P. Palladium-
Catalyzed Bisolefination of C-C Triple Bonds: A Facile Method for
the Synthesis of Naphthalene Derivatives. J. Am. Chem. Soc. 2010,
132, 17710−17712. (f) Shen, H.-C.; Pal, S.; Lian, J.-J.; Liu, R.-S.
Ruthenium-Catalyzed Aromatization of Aromatic Enynes via the 1,2-
Migration of Halo and Aryl Groups: A New Process Involving
Electrocyclization and Skeletal Rearrangement. J. Am. Chem. Soc.
2003, 125, 15762−15763.
(7) (a) Kong, L.; Han, X.; Li, X. Access to 2-Naphthols via Ru(II)-
Catalyzed C-H Annulation of Nitrones with α-Diazo Sulfonyl
Ketones. Chem. Commun. 2019, 55, 7339−7342. (b) Wang, H.; Xu,
H.; Li, B.; Wang, B. Annulation of β-Enaminonitriles with Alkynes via
RhIII-Catalyzed C-H Activation: Direct Access to Highly Substituted
1-Naphthylamines and Naphtho[1,8-bc]pyridines. Org. Lett. 2018, 20,
5640−5643. (c) Liang, G.; Rong, J.; Sun, W.; Chen, G.; Jiang, Y.; Loh,
T.-P. Synthesis of Polyaromatic Rings: Rh(III)-Catalyzed [5 + 1]
Annulation of Enaminones with Vinyl Esters through C-H Bond
Functionalization. Org. Lett. 2018, 20, 7326−7331. (d) Zhou, S.;
Wang, J.; Wang, L.; Song, C.; Chen, K.; Zhu, J. Enaminones as
Synthons for a Directed C-H Functionalization: RhIII-Catalyzed
Synthesis of Naphthalenes. Angew. Chem., Int. Ed. 2016, 55, 9384−
9388. (e) Wang, D.; Ling, F.; Liu, X.; Li, Z.; Ma, C. Aerobic
Dimerization of Enediyne Compounds: Construction of Naphthalene
Frameworks. Chem. - Eur. J. 2016, 22, 124−128.
Sanchez, C.; Beljonne, D.; Ruffieux, P.; Fasel, R.; Feng, X.; Mullen, K.
̈
Toward Cove-Edged Low Band Gap Graphene Nanoribbons. J. Am.
Chem. Soc. 2015, 137, 6097−6103. (e) Brunel, J. M. BINOL: A
Versatile Chiral Reagent. Chem. Rev. 2005, 105, 857−897.
(3) For selected examples, see: (a) Mandal, M.; Sakthivel, S.;
Balamurugan, R. Brønsted/Lewis Acid-Promoted Site-Selective Intra-
molecular Cycloisomerizations of Aryl-Fused 1,6-Diyn-3-ones for
Diversity-Oriented Synthesis of Benzo-Fused Fluorenes and Fluo-
renones and Naphthyl Ketones. J. Org. Chem. 2021, 86, 333−351.
(b) Su, L.; Ren, T.; Dong, J.; Liu, L.; Xie, S.; Yuan, L.; Zhou, Y.; Yin,
S.-F. Cu(I)-Catalyzed 6-endo-dig Cyclization of Terminal Alkynes, 2-
Bromoaryl Ketones, and Amides toward 1-Naphthylamines: Applica-
tions and Photophysical Properties. J. Am. Chem. Soc. 2019, 141,
2535−2544. (c) Singh, S.; Samineni, R.; Pabbaraja, S.; Mehta, G.
Nitromethane as a Carbanion Source for Domino Benzoannulation
with Ynones: One-Pot Synthesis of Polyfunctional Naphthalenes and
a Total Synthesis of Macarpine. Angew. Chem., Int. Ed. 2018, 57,
16847−16851. (d) Sha, H.-K.; Liu, F.; Lu, J.; Liu, Z.-Q.; Hao, W.-J.;
Tang, J.-L.; Tu, S.-J.; Jiang, B. Metal-free benzannulation of yne-
allenone esters for atom economical synthesis of functionalized 1-
naphthols. Green Chem. 2018, 20, 3476−3485. (e) Hein, S. J.;
Lehnherr, D.; Arslan, H.; Uribe-Romo, F. J.; Dichtel, W. R. Alkyne
Benzannulation Reactions for the Synthesis of Novel Aromatic
Architectures. Acc. Chem. Res. 2017, 50, 2776−2788. (f) García-
López, J. A.; Greaney, M. F. Synthesis of biaryls using aryne
intermediates. Chem. Soc. Rev. 2016, 45, 6766−6798. (g) Saito, S.;
Yamamoto, Y. Recent Advances in the Transition-Metal-Catalyzed
Regioselective Approaches to Polysubstituted Benzene Derivatives.
Chem. Rev. 2000, 100, 2901−2915.
(8) For selected examples, see: (a) Kumar, N.; Kumar, A. Amino
Acid-Catalyzed Direct Synthesis of β-Keto Sulfones via Aerobic
Difunctionalization of Terminal Alkynes in an Aqueous Medium. ACS
Sustainable Chem. Eng. 2019, 7, 9182−9188 and references cited
therein. (b) Das, J.; Dey, S.; Pathak, T. Metal-Free Route to
Carboxylated 1,4-Disubstituted 1,2,3-Triazoles from Methoxycarbon-
yl-Modified Vinyl Sulfone. J. Org. Chem. 2019, 84, 15437−15447.
(c) Trost, B. M.; Kalnmals, C. A. Sulfones as chemical chameleons:
versatile synthetic equivalents of small-molecule synthons. Chem. -
Eur. J. 2019, 25, 11193−11213. (d) Scott, K. A.; Njardarson, J. T.
Analysis of US FDA-Approved Drugs Containing Sulfur Atoms. Top
Curr. Chem. (Z) 2018, 376, 5. (e) Konduru, N. K.; Dey, S.; Sajid, M.;
Owais, M.; Ahmed, N. Synthesis and Antibacterial and Antifungal
Evaluation of Some Chalcone Based Sulfones and Bisulfones. Eur. J.
Med. Chem. 2013, 59, 23−30. (f) Nielsen, M.; Jacobsen, C. B.; Holub,
(4) For selected examples, see: (a) Ma, Y.; Lv, J.; Liu, C.; Yao, X.;
Yan, G.; Yu, W.; Ye, J. Electrochemical [4 + 2] Annulation-
Rearrangement-Aromatization of Styrenes: Synthesis of Naphthalene
Derivatives. Angew. Chem., Int. Ed. 2019, 58, 6756−6760. (b) Manna,
S.; Antonchick, A. P. A Metal-Free Oxidative Dehydrogenative Diels-
Alder Reaction for Selective Functionalization of Alkylbenzenes.
Chem. - Eur. J. 2017, 23, 7825−7829. (c) Chang, M.-Y.; Cheng, Y.-C.
Synthesis of 1-Aryltetralins and 1-Arylnaphthalenes via (4 + 2)
Annulation of β-Ketosulfones with Styryl Bromides. Org. Lett. 2016,
18, 1682−1685.
(5) (a) Zhang, C.; Chen, L.; Chen, K.; Jiang, H.; Zhu, S. Iron/zinc-
catalyzed benzannulation reactions of 2-(2-oxo-alkyl)benzketones
leading to naphthalene and isoquinoline derivatives. Org. Chem.
Front. 2018, 5, 1028−1033 and references cited therein. (b) Man-
ojveer, S.; Balamurugan, R. Synthesis of Naphthalene Derivatives from
ortho-Alkynylacetophenone Derivatives via Tandem in Situ Incorpo-
ration of Acetal and Intramolecular Heteroalkyne Metathesis/
Annulation. Org. Lett. 2014, 16, 1712−1715. (c) Malhotra, D.; Liu,
L.-P.; Mashuta, M. S.; Hammond, G. B. Gold-Catalyzed Annulations
of 2-Alkynyl Benzaldehydes with Vinyl Ethers: Synthesis of
Dihydronaphthalene, Isochromene, and Bicyclo[2.2.2]octane Deriva-
tives. Chem. - Eur. J. 2013, 19, 4043−4050. (d) Hu, Z.-L.; Qian, W.-J.;
Wang, S.; Wang, S.; Yao, Z.-J. Transformation of Reactive
Isochromenylium Intermediates to Stable Salts and Their Cascade
Reactions with Olefins. Org. Lett. 2009, 11, 4676−4679. (e) Asao, N.;
Nogami, T.; Lee, S.; Yamamoto, Y. Lewis Acid-Catalyzed
Benzannulation via Unprecedented [4 + 2] Cycloaddition of o-
Alkynyl(oxo)benzenes and Enynals with Alkynes. J. Am. Chem. Soc.
2003, 125, 10921−10925.
N.; Paixao, M. W.; Jørgensen, K. A. Asymmetric Organocatalysis with
̃
Sulfones. Angew. Chem., Int. Ed. 2010, 49, 2668−2679. (g) Back, T.
G.; Clary, K. N.; Gao, D. Cycloadditions and Cyclizations of
Acetylenic, Allenic, and Conjugated Dienyl Sulfones. Chem. Rev.
2010, 110, 4498−4553. (h) El-Awa, A.; Noshi, M. N.; du Jourdin, X.
M.; Fuchs, P. L. Evolving Organic Synthesis Fostered by the
Pluripotent Phenylsulfone Moiety. Chem. Rev. 2009, 109, 2315−
2349. (i) Meadows, D. C.; Gervay-Hague, J. Vinyl Sulfones: Synthetic
Preparations and Medicinal Chemistry Applications. Med. Res. Rev.
2006, 26, 793−814.
(9) For selected examples, see: (a) Yavari, I.; Shaabanzadeh, S.
Electrochemical Synthesis of β-Ketosulfones from Switchable Starting
̀
Materials. Org. Lett. 2020, 22, 464−467. (b) Gómez, J. E.; Cristofol,
̀
A.; Kleij, A. W. Copper-Catalyzed Enantioselective Construction of
Tertiary Propargylic Sulfones. Angew. Chem., Int. Ed. 2019, 58, 3903−
3907. (c) Chen, L.; Liang, J.; Chen, Z.-Y.; Chen, J.; Yan, M.; Zhang,
X.-J. A Convenient Synthesis of Sulfones via Light Promoted
Coupling of Sodium Sulfinates and Aryl Halides. Adv. Synth. Catal.
2018, 361, 956−960. (d) He, F.-S.; Wu, Y.; Li, X.; Xia, H.; Wu, J.
(6) (a) Li, S.-S.; Zhao, M.; Liu, X.-W.; Xu, J.-L.; Xu, Y.-H.; Loh, T.-
P. Palladium-Catalyzed Cycloaromatization/Alkylation of o-
6257
https://doi.org/10.1021/acs.joc.1c00038
J. Org. Chem. 2021, 86, 6247−6258

The Journal of Organic Chemistry
pubs.acs.org/joc
Article
Photoredox-catalyzed sulfonylation of alkenylcyclobutanols with the
insertion of sulfur dioxide through semipinacol rearrangement. Org.
Chem. Front. 2019, 6, 1873−1878 and references cited therein. (e) Jia,
S.; Chen, Z.; Zhang, N.; Tan, Y.; Liu, Y.; Deng, J.; Yan, H.
Organocatalytic Enantioselective Construction of Axially Chiral
Sulfone-Containing Styrenes. J. Am. Chem. Soc. 2018, 140, 7056−
7060. (f) Ning, Y.; Ji, Q.; Liao, P.; Anderson, E. A.; Bi, X. Silver-
Catalyzed Stereoselective Aminosulfonylation of Alkynes. Angew.
Chem., Int. Ed. 2017, 56, 13805−13808. (g) Liu, N.-W.; Liang, S.;
Manolikakes, G. Recent Advances in the Synthesis of Sulfones.
Synthesis 2016, 48, 1939−1973. (h) Fang, Y.; Luo, Z.; Xu, X. Recent
Advances in the Synthesis of Vinyl Sulfones. RSC Adv. 2016, 6,
59661−59676.
(10) For selected examples, see: (a) Zhang, Z.; Wang, S.; Zhang, Y.;
Zhang, G. Regiospecific Cleavage of S-N Bonds in Sulfonyl Azides:
Sulfonyl Donors. J. Org. Chem. 2019, 84, 3919−3926. (b) Zhu, H.;
Shen, Y.; Wen, D. H.; Le, Z.-G.; Tu, T. Selective Synthesis of ortho-
Substituted Diarylsulfones by Using NHC-Au Catalysts under Mild
Conditions. Org. Lett. 2019, 21, 974−979. (c) Laha, J. K.; Sharma, S.
Palladium-Catalyzed Intramolecular Oxidative Arylations for the
Synthesis of Fused Biaryl Sulfones. ACS Omega 2018, 3, 4860−
4870. (d) Liu, N.-W.; Liang, S.; Margraf, N.; Shaaban, S.; Luciano, V.;
Drost, M.; Manolikakes, G. Nickel-Catalyzed Synthesis of Diaryl
Sulfones from Aryl Halides and Sodium Sulfinates. Eur. J. Org. Chem.
2018, 2018, 1208−1210. (e) Cabrera-Afonso, M. J.; Lu, Z.-P.; Kelly,
C. B.; Lang, S.; Dykstra, R.; Gutierrez, O.; Molander, G. A. Engaging
Xie, M. Metal-Free Cascade Rearrangement/Radical Addition/
Oxidative C-H Annulation of Propargyl Alcohols with Sodium
Sulfinates: Access to 2-Sulfenylindenones. Org. Chem. Front. 2019,
6, 2796−2800. (c) Zhang, J.; Liang, Z.; Wang, J.; Guo, Z.; Liu, C.;
Xie, M. Metal-Free Synthesis of Functionalized Tetrasubstituted
Alkenes by Three-Component Reaction of Alkynes, Iodine and
Sodium Sulfinates. ACS Omega 2018, 3, 18002−18015.
(18) For selected examples, see: (a) Huang, L.; Zhu, C.; Yi, L.; Yue,
H.; Kancherla, R.; Rueping, M. Cascade Cross-Coupling of Dienes:
Photoredox and Nickel Dual Catalysis. Angew. Chem., Int. Ed. 2020,
59, 457−464. (b) Wang, B.-W.; Jiang, K.; Li, J.-X.; Luo, S.-H.; Wang,
Z.-Y.; Jiang, H.-F. 1,1-Diphenylvinylsulfide as A Functional AIEgen
Derived from the Aggregation-Caused-Quenching Molecule 1,1-
Diphenylethene through Simple Thioetherification. Angew. Chem.,
Int. Ed. 2020, 59, 2338−2343. (c) Liu, B.; Ning, Y.; Virelli, M.;
Zanoni, G.; Anderson, E. A.; Bi, X. Direct Transformation of Terminal
Alkynes into Amidines by a Silver-Catalyzed Four-Component
Reaction. J. Am. Chem. Soc. 2019, 141, 1593−1598. (d) Ansari, M.
Y.; Kumar, N.; Kumar, A. Regioselective Intermolecular Sulfur-
Oxygen Difunctionalization (Phenoxysulfonylation) of Alkynes: One-
Pot Construction of (Z)-β- Phenoxy Vinylsulfones. Org. Lett. 2019,
21, 3931−3936. (e) Liu, Y.; Wang, Q.-L.; Chen, Z.; Zhou, Q.; Zhou,
C.-S.; Xiong, B.-Q.; Zhang, P.-L.; Yang, C.-A.; Tang, K.-W. Silver-
Mediated Oxidative C-C Bond Sulfonylation/Arylation of Methyl-
enecyclopropanes with Sodium Sulfinates: Facile Access to 3-
Sulfonyl-1,2-Dihydronaphthalenes. Org. Biomol. Chem. 2019, 17,
1365−1369. (f) Chawla, R.; Yadav, L. D. S. Organic Photoredox
Catalysis Enabled Cross-Coupling of Arenediazonium and Sulfinate
Salts: Synthesis of (Un)symmetrical Diaryl/Alkyl Aryl Sulfones. Org.
Biomol. Chem. 2019, 17, 4761−4766. (g) Zhao, J.; Niu, S.; Jiang, X.;
Jiang, Y.; Zhang, X.; Sun, T.; Ma, D. A Class of Amide Ligands Enable
Cu-Catalyzed Coupling of (Hetero)aryl Halides with Sulfinic Acid
Salts under Mild Conditions. J. Org. Chem. 2018, 83, 6589−6598.
(19) (a) Zhou, H.; Xing, Y.; Yao, J.; Chen, J. Sulfur-Assisted
Propargyl-Allenyl Isomerizations and Electrocyclizations for the
Convenient and Efficient Synthesis of Polyfunctionalized Benzenes
and Naphthalenes. Org. Lett. 2010, 12, 3674−3677. (b) Xu, J.; Wang,
Y.; Burton, D. J. Site-Specific Preparation of 3-Fluoro-1-substituted-
naphthalenes via a Novel Base-Catalyzed Cyclization Reaction from
(E)-Monofluoroenynes. Org. Lett. 2006, 8, 2555−2558.
(20) For a related study on 6π-electrocyclization promoted by Lewis
acid: Resende, D. I. S. P.; Guieu, S.; Oliva, C. G.; Silva, A. M.
Synthesis of 2,6-Diaryl-1,2-dihydropyridines through a 6π-Electro-
cyclization of N-Sulfonylazatrienes. Tetrahedron Lett. 2014, 55, 6585−
6588.
(21) (a) Noble, A.; MacMillan, D. W. C. Photoredox α-Vinylation of
α-Amino Acids and N-Aryl Amines. J. Am. Chem. Soc. 2014, 136,
11602−11605. (b) Satoh, T.; Hanaki, N.; Kuramochi, Y.; Oinoue, Y.;
Hosoya, K.; Sakai, K. A New Method for Synthesis of Allenes,
Including an Optically Active Form, From Aldehydes and Alkenyl
Aryl Sulfoxides by Sulfoxide-Metal Exchange as the Key Reaction and
An Application to A Total Synthesis of Male Bean Weevil Sex
Attractant. Tetrahedron 2002, 58, 2533−2549.
(22) (a) Qiu, Y.-F.; Yang, F.; Qiu, Z.-H.; Zhong, M.-J.; Wang, L.-J.;
Ye, Y.-Y.; Song, B.; Liang, Y.-M. Brønsted Acid Catalyzed and NIS-
Promoted Cyclization of Diynones: Selective Synthesis of 4-Pyrone,
4-Pyridone, and 3-Pyrrolone Derivatives. J. Org. Chem. 2013, 78,
12018−12028. (b) Huang, B.; Liffert, R.; Linden, A.; Gademann, K.
Metal-Free Regioselective Chloroazidation of Internal Alkynes. Chem.
- Eur. J. 2018, 25, 981−984.
Sulfinate Salts via Ni/Photoredox Dual Catalysis Enables Facile Csp2
-
SO2R Coupling. Chem. Sci. 2018, 9, 3186−3191. (f) Liu, N.-W.;
Hofman, K.; Herbert, A.; Manolikakes, G. Visible-Light Photoredox/
Nickel Dual Catalysis for the Cross-Coupling of Sulfinic Acid Salts
with Aryl Iodides. Org. Lett. 2018, 20, 760−763.
(11) (a) Grombein, C. M.; Hu, Q.; Heim, R.; Rau, S.; Zimmer, C.;
Hartmann, R. W. 1-Phenylsulfinyl-3-(pyridin-3-yl)naphthalen-2-ols: A
New Class of Potent and Selective Aldosterone Synthase Inhibitors.
Eur. J. Med. Chem. 2015, 89, 597−605. (b) Alhamadsheh, M. M.;
Waters, N. C.; Sachdeva, S.; Lee, P.; Reynolds, K. A. Synthesis and
Biological Evaluation of Novel Sulfonyl-naphthalene-1,4-diols as
FabH Inhibitors. Bioorg. Med. Chem. Lett. 2008, 18, 6402−6405.
(12) Xiao, F.; Chen, S.; Tian, J.; Huang, H.; Liu, Y.; Deng, G.-J.
Chemoselective Cross-Coupling reaction of Sodium Sulfinates with
Phenols Under Aqueous Conditions. Green Chem. 2016, 18, 1538−
1546.
(13) Fu, R.; Hao, W.-J.; Wu, Y.-N.; Wang, N.-N.; Tu, S.-J.; Li, G.;
Jiang, B. Sulfonyl Radical-Enabled 6-Endo-trig Cyclization for
Regiospecific Synthesis of Unsymmetrical Diaryl Sulfones. Org.
Chem. Front. 2016, 3, 1452−1456.
(14) (a) Meng, F.; Zhang, H.; Li, J.; Chun, J.; Shi, Y.; He, H.; Chen,
B.; Gao, Z.; Zhu, Y. Highly Selective and Switchable Access to
Tetrasubstituted Alkenyl Sulfones and Naphthyl Sulfones: 1,4-Aryl
Migration versus Cyclization. Org. Lett. 2019, 21, 8537−8542.
(b) Yang, X.; Zhao, L.; Yuan, B.; Qi, Z.; Yan, R. TBAI/K2S2O8
Initiated Radical Cyclization to Synthesize β-Arylsulfonyl Naphtha-
lenes from Homopropargylic Alcohols and Sulfonyl Hydrazides. Adv.
Synth. Catal. 2017, 359, 3248−3253.
(15) Kong, L.; Han, X.; Li, X. Access to 2-Naphthols via Ru(II)-
Catalyzed C-H Annulation of Nitrones with α-Diazo Sulfonyl
Ketones. Chem. Commun. 2019, 55, 7339−7342.
(16) (a) Shen, R.; Yang, J.; Luo, B.; Zhang, L.; Han, L.-B. Copper-
Catalyzed Allenylation-Isomerization Sequence of Penta-1,4-diyn-3-yl
Acetates with P(O)H Compounds: Facile Synthesis of 1-Phosphonyl
2,4-Diynes. Adv. Synth. Catal. 2016, 358, 3897−3906. (b) Barluenga,
J.; Riesgo, L.; López, L. A.; Rubio, E.; Tomás, M. Discrimination of
Diazo Compounds Toward Carbenoids: Copper(I)-Catalyzed Syn-
thesis of Substituted Cyclobutenes. Angew. Chem., Int. Ed. 2009, 48,
7569−7572.
(17) (a) Fan, J.; Zhao, Y.; Zhang, J.; Xie, M.; Zhang, Y. Acid-
Controlled Access to β-Sulfenyl Ketones and α,β-Disulfonyl Ketones
by Pummerer Reaction of β-Keto Sulfones and Sulfoxides. J. Org.
Chem. 2020, 85, 691−701. (b) Liu, C.; Wang, B.; Guo, Z.; Zhang, J.;
6258
https://doi.org/10.1021/acs.joc.1c00038
J. Org. Chem. 2021, 86, 6247−6258