Visible-light-mediated cascade cyanoalkylsulfonylation/cyclization of alkynoates leading to coumarinsviaSO2insertion

Article abstract of DOI:10.1039/d1ob00142f

A visible-light-mediated tandem cyanoalkylsulfonylation/cyclization of alkynoates with cycloketone oxime compounds for the preparation of 3-cyanoalkylsulfonylcoumarinsviaSO₂insertion is reported. The difunctionalization of carbon-carbon triple bonds includes a radical mechanism and involves the formation of an iminyl radical, ring-opening of the cycloketone, insertion of SO₂, addition of the sulfonyl radical to carbon-carbon triple bonds,ipso-cyclization and ester migration.

Full text of DOI:10.1039/d1ob00142f

Organic &
Biomolecular Chemistry
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Visible-light-mediated cascade
cyanoalkylsulfonylation/cyclization of alkynoates
Cite this: Org. Biomol. Chem., 2021,
9, 3181
1
leading to coumarins via SO insertion†
2
a
a
a
b
a
Pu Chen, Zan Chen, Bi-Quan Xiong,
Yun Liang,
Ke-Wen Tang,
a
a,b
Jun Xie * and Yu Liu
*
A visible-light-mediated tandem cyanoalkylsulfonylation/cyclization of alkynoates with cycloketone
oxime compounds for the preparation of 3-cyanoalkylsulfonylcoumarins via SO2 insertion is reported.
The difunctionalization of carbon–carbon triple bonds includes a radical mechanism and involves the for-
Received 25th January 2021,
Accepted 15th March 2021
DOI: 10.1039/d1ob00142f
2
mation of an iminyl radical, ring-opening of the cycloketone, insertion of SO , addition of the sulfonyl
rsc.li/obc
radical to carbon–carbon triple bonds, ipso-cyclization and ester migration.
1
0–13
been developed.
The first example was developed by Zard
Introduction
1
0a
10b,c
10d
10e–h
and co-workers. The groups of Selander,
Li,
Guo,
1
0i
11a,b
11c–g
12a,b
12c,d
13
Coumarins are a class of useful heterocycles, which are found Duan, Uemura,
Xiao,
Yu,
Wu’s
and others
in many drugs, active molecules, natural products, dyes, and have developed similar NCR methods for ring-opening of
1
,2
materials. Additionally, coumarin compounds can be used cycloketone oxime derivatives. The cycloketone oxime deriva-
as antibacterial, anti-inflammatory, anticoagulant, anti-psoria- tives, such as cyclobutane oxime esters, underwent SET and
sis, anti-HIV, and anticancer agents, and enzymatic inhibitors decomposition to generate iminyl radical I. The intermediate I
3
14–16
in medicinal chemistry. Therefore, development of simple underwent ring-opening to afford cyanoalkyl radical II.
and convenient ways for the preparation of these useful deriva- The cyanoalkyl radical can be trapped by radical acceptors,
1
4a,f,g,15d–g
14h
tives under mild conditions will be important for pharma- including alkenes,
alkynes,
and so on. For another pathway, the cyanoalkylsulfo-
Recently, the insertion of SO2 has appeared to be a con- nyl radical III, which is generated from radical II via the inser-
heteroaromatic
1
5a–c
ceutical synthesis.
rings
1
4b–e
venient and efficient method for the construction of tion of SO
Several cheap SO sources, such as thiourea method for employing alkynes to trap the cyanoalkylsulfonyl
dioxide, DABCO·(SO ) and sodium sulphites, are employed radicals is lacking (Scheme 1).
2
, can be captured by alkenes.
However, the
4
–7
sulfones.
2
5
6
7
2
2
in the SO
venient method for the construction of sulfones under mild alkynes, we wanted to develop a facile strategy by using
conditions and also avoid the use of toxic SO gas. alkynes to capture the cyanoalkylsulfonyl radicals. Moreover,
2
insertion reactions. These strategies provide a con-
Based on less exploration of cyanoalkylsulfonylation of
2
Nitrogen-centered radical (NCR) strategies, as a class of visible-light-catalysis has a lot of advantages, such as high
powerful and efficient methods in free radical transformation, availability and efficiency, safety, and simple and mild con-
have aroused synthetic chemists’ interest because of their ditions, and is widely used in drug synthesis, environmental
8
,9
17
unique reactivity and high efficiency.
Compared with governance, organic synthesis and other related fields.
carbon-centered radical (CCR) strategies, NCR strategies can
be realized under mild conditions, avoiding high temperatures
and usage of strong oxidants. In recent years, many NCR strat-
egies for ring-opening of cycloketone oxime compounds have
a
Department of Chemistry and Chemical Engineering, Hunan Institute of Science and
Technology, Yueyang 414006, China. E-mail: lyxtmj_613@163.com,
xiejun12018014@163.com
b
Key Laboratory of the Assembly and Application of Organic Functional Molecules of
Hunan Province, Hunan Normal University, Changsha, Hunan 410081, China
†
Electronic supplementary information (ESI) available. See DOI: 10.1039/
Scheme 1 NCR strategies for ring-opening of cycloketone oxime
d1ob00142f
compounds.
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Recently, visible-light-catalysis has become a convenient strat- noalkylsulfonylcoumarin 3aa could be obtained in 81% yield
egy for the formation of iminyl radicals from cycloketone (entry 1). The result of the reaction in the absence of Ir(ppy)3
1
4b,c,e–h
oxime compounds.
Herein, we report a visible-light- revealed that the photocatalyst is indispensable for this cya-
catalyzed tandem cyanoalkylsulfonylation/cyclization of noalkylsulfonylation (entry 2). Other photocatalysts, including
alkynoates with cycloketone oxime compounds for the prepa- commercially available Na –Eosin Y, Eosin Y and Ru(bpy) Cl ,
2
3
2
ration of 3-cyanoalkylsulfonylcoumarins via SO
which a new C–C bond, a C–O bond and two C–S bonds are (ppy)
formed (Scheme 2). increase the yield obviously (entry 6). The reaction conducted
2
insertion, in were examined. All of them showed lower efficiency than Ir
3
(entries 3–5). Employing 2 mol% of Ir(ppy) did not
3
Our initial study focused on the cyanoalkylsulfonylation/ without visible-light irradiation led to no generation of any
cyclization of alkynoate 1a with cycloketone oxime compound target product (entry 7). Other light sources, such as 12 W blue
2
a (Table 1). In our initial attempt, we investigated the cya- LED light, 3 W blue LED light and 36 W compact fluorescent
noalkylsulfonylation/cyclization of alkynoates in the presence light, could mediate the reaction, but all of them gave lower
of phenyl 3-phenylpropiolate (1a, 0.2 mmol), cyclobutanone O- yields (entries 8–10). Then, we tested the solvent effects on the
(
4-(trifluoromethyl)benzoyl) oxime (2a, 0.3 mmol, 1.5 equiv.), NCR reaction (entries 11–16). All of them, including DMF,
n
Ir(ppy)
3
(1 mol%), K
2
S
2
O
5
(2 equiv.) and MeCN (2 mL) at 60 °C DMSO, toluene, DCE and AcO Bu, could not provide higher
CN. Among them, DCE provided the desired
under irradiation of 5 W blue light for 18 h. The target 3-cya- yield than CH
3
product in 68% yield (entry 14). The yields decreased on
varying the temperature to 80 °C or 40 °C (entries 17 and 18).
Moreover, the desired 4-((2-oxo-4-phenyl-2H-chromen-3-yl)sul-
fonyl)butanenitrile 3aa could be isolated in 80% yield as the
reaction was carried out for a prolonged time (entry 19). The
target cyclization product could be furnished in 68% yield
when the reaction was carried out in the presence of 1a
Scheme 2 Cascade cyanoalkylsulfonylation/cyclization of alkynoates (1 mmol), 2a (1.5 mmol, 1.5 equiv.), Ir(ppy)
via SO insertion.
1 mol%), K (2 mmol, 2 equiv.) and MeCN (10 mL) at
0 °C under irradiation of 5 W blue light for 72 h (entry 20).
Based on the results of optimizing conditions, the scope of
3
(0.01 mmol,
2
2 2 5
S O
6
a
Table 1 Screening of optimal reaction conditions
aryl alkanoates 1 bearing different substituents at the Ar group
relative to the ester in the presence of cycloketone oxime esters
3 2 2 5 3
2a, Ir(ppy) , K S O and CH CN at 60 °C under irradiation of 5
W blue light for 18 h was determined (Scheme 3). The reaction
system exhibited high functional group tolerance and a broad
substrate scope. For example, the alkynoates 1b–i bearing a
substituent at the para-position on the aromatic rings of
phenol moieties could undergo cyanoalkylsulfonylation/cycli-
b
Entry
1
Variation from the standard conditions
None
Yield (%)
81
0
35
21
20
82
0
70
66
57
10
13
22
68
27
30
75
70
80
68
c
2
Without Ir(ppy)
Na –Eosin Y instead of Ir(ppy)
Eosin Y instead of Ir(ppy)
Ru(bpy) Cl instead of Ir(ppy)
Ir(ppy) (2 mol%)
3
3
4
5
6
2
3
3
3
2
3
3
c
7
Without visible-light
12 W blue LED light
3 W blue LED light
8
9
10
11
12
13
14
15
16
17
18
19
20
36 W compact fluorescent light
DMF instead of CH CN
DMSO instead of CH CN
Toluene instead of CH
DCE instead of CH CN
THF instead of CH CN
d
d
d
3
3
3
CN
3
3
n
AcO Bu instead of CH
At 80 °C
3
CN
At 40 °C
For 48 h
None
e
a
Reaction conditions: 1a (0.2 mmol), 2a (0.3 mmol, 1.5 equiv.), Ir
ppy) (1 mol%), K (0.4 mmol, 2 equiv.) and MeCN (2 mL) at
(
3
2 2 5
S O
b
6
0 °C under irradiation of 5 W blue light for 18 h. Isolated yield.
c
d
Most of the starting materials were recovered. Most of the starting
e
materials were decomposed. 1a (1 mmol), 2a (1.5 mmol, 1.5 equiv.),
Ir(ppy)
3
(0.01 mmol, 1 mol%), K
2
S
O
2 5
(2 mmol, 2 equiv.) and MeCN Scheme 3 Scope of aryl alkanoates bearing different substituents at
the Ar group relative to the ester.
(10 mL) at 60 °C under irradiation of 5 W blue light for 72 h.
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zation and afford the corresponding target products 3ba–ia in reaction, giving the cyanoalkylsulfonylated coumarin 3am in
7–83% yields. Due to the steric effect, the alkynoates 1j–m 70% yield.
bearing a substituent at the meta-position on the aromatic To gain deeper insight into the mechanism for the tandem
6
rings of phenol moieties gave the single products 3ja–ma. cyanoalkylsulfonylation/cyclization, a series of control experi-
However, the alkynoate 1n bearing a substituent at the ortho- ments were carried out (Scheme 4). The cyanoalkylsulfonyla-
position on the aromatic ring could not undergo this trans- tion/cyclization product could only be detected in very low
formation and most of the starting materials were recovered yields when employing 1,1-diphenylethene, TEMPO or BHT as
(
product 3na).
radical inhibitors under the standard conditions (Scheme 4,
Then, the scope of other alkynoates 1 and cycloketone eqn (1)–(3)). Additionally, the cyanoalkylsulfonyl radical and
oxime esters 2 was tested (Table 2). The alkynoates 1o–x cyanoalkyl radical could be captured by 1,1-diphenylethene,
bearing different substituted aromatic rings at the terminal of generating 4-((2,2-diphenylvinyl)sulfonyl)butanenitrile 4 and
carbon–carbon triple bonds were suitable for this reaction, 6,6-diphenylhex-5-enenitrile 5 in 27% and 11% yields, respect-
generating the corresponding products 3oa–xa in moderate to ively (Scheme 4, eqn (1)). The cyanoalkyl radical trapping
good yields. The substrates bearing a thienyl group (1y) or an product 6 could be detected by GC-MS analysis when utilizing
alkyl group (1z–aa) could furnish the corresponding products TEMPO as a radical inhibitor (Scheme 4, eqn (2)). These
3
ya–3aaa under the standard conditions. However, the term- results suggested that a radical process was involved in the
inal alkyne 1ab was an unsuccessful substrate (product 3aba). reaction.
Then, we paid attention to investigating the scope of cycloke-
The cyanoalkylsulfonylated product 3aa could be trans-
tone oxime esters 2. First, a variety of cycloketone oxime esters formed into ester 7 in 70% yield in the presence of ZnCl
2
(1
n
2
b–j bearing a substituent at the 3-position were examined, equiv.) and BuOH (2 mL) at 120 °C for 16 h (Scheme 5, eqn
1
4e
and all of them were good candidate substrates, affording the (1)). The carbon–carbon double bonds on coumarin motifs
corresponding target products 3ab–aj in 58–80% yields. The could be reduced into carbon–carbon single bonds in the pres-
cycloketone oxime ester 2k bearing a phenyl group and a ence of CH COOH/H SO /H O at a ratio of 3 : 3 : 1 (Scheme 5,
methyl group could undergo the transformation smoothly eqn (2)).
product 3ak). However, oxetan-3-one derived O-acyl oxime 2l According to the reported literature and obtained
could not furnish the target product 3al. The cycloketone results,
3
2
4
2
3
f,22d
(
1
8–23
a possible pathway for the visible-light-mediated
oxime ester 2m bearing a Bn group at the 2-position of cycloke- cascade cyanoalkylsulfonylation/cyclization of alkynoates with
tone oxime underwent the cyanoalkylsulfonylation/cyclization cycloketone oxime compounds was proposed (Scheme 6).
III
III
Initially, Ir was converted into Ir * photoexcited by the
a
Table 2 Scope of alkynoates (1) and cycloketone oxime esters (2)
Scheme 4 Control experiments.
a
Reaction conditions: 1a (0.2 mmol), 2a (0.3 mmol, 1.5 equiv.), Ir
ppy) (1 mol%), K (0.4 mmol, 2 equiv.) and MeCN (2 mL) at
0 °C under irradiation of 5 W blue light for 18 h.
(
6
3
2 2 5
S O
Scheme 5 Synthetic applications.
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NMR) nuclear magnetic resonance spectra were recorded at
400 MHz and 100 MHz, respectively. The chemical shifts are
given in parts per million (ppm) on the delta (δ) scale. The
1
solvent peak was used as a reference value, for H NMR: TMS =
1
3
0
.00 ppm, for C NMR: CDCl3 = 77.00 ppm. The following
abbreviations were used to explain multiplicities: s = singlet, d
doublet, dd = doublet of doublet, t = triplet, td = triplet of
=
doublet, q = quartet, m = multiplet, and br = broad. Analytical
TLC was performed on precoated silica gel plates. High-resolu-
tion mass spectra (HRMS) were obtained on an Agilent mass
spectrometer using ESI-TOF (electrospray ionization-time of
flight).
General procedure for the cyanoalkylsulfonylation/cyclization
of alkynoates
Scheme 6 Proposed mechanism.
To a Schlenk tube were added alkynoates 1 (0.2 mmol, 0.1 M),
cycloketone oxime compounds
2 (1.5 equiv.), Ir(ppy)3
2
1a,e
irradiation of light.
from cycloketone oxime 2a (E2a = −1.64 versus SCE)
Then, the iminyl radical A, generated (1 mol%), K S O (0.4 mmol, 2 equiv.) and MeCN (2 mL) at
2
2 5
11c
under 60 °C under irradiation of 5 W blue light for 18 h. Until com-
plete consumption of the starting material was observed by
underwent ring-opening to give intermediate B. Next, the cya- TLC and/or GC-MS analysis. After the reaction was finished,
III
IV III
11c
the reduction of Ir * (E Ir /Ir *) = −1.73 versus (SCE),
1
/2
2
2f
noalkyl radical B reacted with K
2
S
2
O
5
to give intermediate C.
the solvent was removed from the reaction mixture, and the
The cyanoalkylsulfonyl radical C attacked the carbon–carbon crude product was purified by column chromatography (pet-
triple bond in alkynoate 1a (E1a = −1.88 versus SCE, see roleum ether/ethyl acetate, 3 : 1) to provide the desired pro-
Fig. S1†) to furnish the radical D, which underwent ipso-cycli- ducts 3. A scaled-up experiment conducted in the presence of
zation to give the radical E. Next, the radical E underwent SET 1a (1 mmol), 2a (1.5 mmol, 1.5 equiv.), Ir(ppy) (0.01 mmol,
3
IV
IV
by Ir to provide the carbocation F, and Ir was reverted to 1 mol%), K S O (2 mmol, 2 equiv.) and MeCN (10 mL) at
Ir . Finally, the intermediate F underwent 1,2-ester migration 60 °C under irradiation of 5 W blue light for 72 h gave the
2
2 5
III
2
3
and deprotonation to form the target product 3aa.
target product 3aa in 68% yield.
-((2-Oxo-4-phenyl-2H-chromen-3-yl)sulfonyl)butanenitrile
4
(
3aa). Yield: 57.2 mg, 81%; white solid; mp 123.0–123.5 °C
1
(
uncorrected); H NMR (400 MHz, CDCl ) δ: 7.72–7.68 (m, 1H),
3
Conclusion
7.56–7.54 (m, 3H), 7.46–7.44 (m, 1H), 7.30–7.24 (m, 3H),
In conclusion, we have developed a visible-light-mediated 7.11–7.08 (m, 1H), 3.67 (t, J = 7.2 Hz, 2H), 2.55 (t, J = 7.2 Hz,
1
3
1
tandem cyanoalkylsulfonylation/cyclization of alkynoates with 2H), 2.22–2.14 (m, 2H); C{ H}NMR (100 MHz, CDCl ) δ:
3
cycloketone oxime compounds for the preparation of 3-cya- 161.1, 156.7, 153.7, 135.3, 131.6, 130.0, 129.5, 128.2, 127.4,
noalkylsulfonylcoumarins via SO
offers a convenient pathway for the preparation of cyanoalkyl- (ESI-TOF) m/z: C H NO S (M + H) calcd for 354.0795, found
2
insertion. This method 125.3, 123.8, 119.9, 118.1, 117.0, 53.4, 18.7, 16.2; HRMS
+
1
9
16
4
sulfonylated coumarins. The mechanism study reveals that a 354.0801.
NCR process is definitely involved in the transformation. The
4-((7-Methoxy-2-oxo-4-phenyl-2H-chromen-3-yl)sulfonyl)buta-
difunctionalization of carbon–carbon triple bonds includes a nenitrile (3ba). Yield: 63.6 mg, 83%; yellow solid; mp
1
radical mechanism and involves the formation of an iminyl 116.0–116.5 °C (uncorrected); H NMR (400 MHz, CDCl ) δ:
3
radical, ring-opening of cycloketone, insertion of SO
2
, addition 7.54–7.51 (m, 3H), 7.27–7.25 (m, 2H), 6.97 (d, J = 8.8 Hz, 1H),
of the sulfonyl radical to carbon–carbon triple bonds, ipso- 6.89 (d, J = 2.4 Hz, 1H), 6.81–6.78 (m, 1H), 3.92 (s, 3H), 3.64 (t,
1
3
cyclization and ester migration. Further study on NCR reac- J = 7.6 Hz, 2H), 2.54 (t, J = 7.6 Hz, 2H), 2.20–2.13 (m, 2H);
tions is currently underway in our laboratory.
C
1
3
{ H}NMR (100 MHz, CDCl ) δ: 165.7, 161.3, 157.2, 156.0, 132.1,
1
5
31.3, 129.3, 128.1, 127.4, 119.9, 118.2, 114.0. 113.3, 100.4,
6.2, 53.3, 18.7, 16.2; HRMS (ESI-TOF) m/z: C20 S (M +
H
18NO
5
+
H) calcd for 384.0900, found 384.0906.
-((7-Methyl-2-oxo-4-phenyl-2H-chromen-3-yl)sulfonyl)butane-
nitrile (3ca). Yield: 55.8 mg, 76%; yellow solid; mp
Experimental
General methods
4
1
3
All reactions were carried out with magnetic stirring and in 172.0–172.5 °C (uncorrected); H NMR (400 MHz, CDCl ) δ:
dried glassware. Standard syringe techniques were applied for 7.56–7.51 (m, 3H), 7.28–7.24 (m, 3H), 7.06 (d, J = 8.0 Hz, 1H),
the transfer of dry solvents. All reagents and solvents were 6.95 (d, J = 8.0 Hz, 1H), 3.65 (t, J = 7.2 Hz, 2H), 2.54 (t, J = 7.2
1
3
1
commercially available and used without any further purifi- Hz, 2H), 2.49 (s, 3H), 2.20–2.13 (m, 2H);
C{ H}NMR
1
13
cation unless specified. Proton ( H NMR) and carbon ( C (100 MHz, CDCl ) δ: 161.2, 157.0, 153.8, 147.6, 131.8, 129.7,
3
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1
1
29.4, 128.1, 127.4, 126.6, 122.4, 118.2, 117.5, 117.0, 55.3, 22.0,
8.7, 16.2; HRMS (ESI-TOF) m/z: C H NO S (M + H) calcd fonyl)butanenitrile (3ia). Yield: 56.4 mg, 67%; white solid; mp
20 18 4
4-((2-Oxo-4-phenyl-7-(trifluoromethyl)-2H-chromen-3-yl)sul-
+
1
for 368.0951, found 368.0958.
3
174.0–174.5 °C (uncorrected); H NMR (400 MHz, CDCl ) δ:
4
-((2-Oxo-4,7-diphenyl-2H-chromen-3-yl)sulfonyl)butanenitrile 7.70 (s, 1H), 7.60–7.55 (m, 3H), 7.48 (d, J = 8.4 Hz, 1H),
(
3da). Yield: 66.9 mg, 78%; white solid; mp 155.0–155.5 °C 7.30–7.24 (m, 3H), 3.68 (t, J = 7.2 Hz, 2H), 2.56 (t, J = 7.2 Hz,
1
13
1
(
7
(
uncorrected); H NMR (400 MHz, CDCl
.57–7.56 (m, 3H), 7.51–7.48 (m, 4H), 7.32–7.30 (m, 2H), 7.14 159.8, 155.9, 153.2, 136.3 (d, J = 33.6 Hz, 1C), 131.0, 130.9,
d, J = 8.8 Hz, 1H), 3.68 (t, J = 7.6 Hz, 2H), 2.55 (t, J = 7.6 Hz, 130.0, 128.5, 127.4, 125.9, 122.6 (q, J = 274.6 Hz, 1C), 122.5,
3 3
) δ: 7.65–7.62 (m, 3H), 2H), 2.23–2.17 (m, 2H); C{ H}NMR (100 MHz, CDCl ) δ:
1
3
1
2
1
1
5
H), 2.22–2.15 (m, 2H); C{ H}NMR (100 MHz, CDCl
3
) δ: 121.6 (q, J = 3.8 Hz, 1C), 118.0, 114.5, (q, J = 4.3 Hz, 1C), 53.6,
1
9
60.9, 156.9, 154.1, 148.5, 138.0, 131.7, 130.3, 129.5, 129.4, 18.6, 16.2; F NMR (282 MHz, CDCl
29.3, 128.2, 127.4, 127.3, 124.0, 123.0, 118.7, 118.2, 114.8, (ESI-TOF) m/z: C H
3
) δ: −62.4 (s, 3F); HRMS
F NO S (M + H) calcd for 422.0668,
1
9
+
2
0
15
3 4
+
3.4, 18.7, 16.2; HRMS (ESI-TOF) m/z: C25
H
20NO
4
S (M + H)
found 422.0675.
4-((6-Methoxy-2-oxo-4-phenyl-2H-chromen-3-yl)sulfonyl)buta-
-((7-Fluoro-2-oxo-4-phenyl-2H-chromen-3-yl)sulfonyl)buta- nenitrile (3ja). Yield: 61.3 mg, 80%; yellow solid; mp
calcd for 430.1108, found 430.1115.
4
1
nenitrile (3ea). Yield: 59.4 mg, 80%; yellow solid; mp 138.0–138.5 °C (uncorrected); H NMR (400 MHz, CDCl
3
) δ:
) δ: 7.56–7.53 (m, 3H), 7.38 (d, J = 9.2 Hz, 1H), 7.29–7.25 (m, 3H),
.58–7.52 (m, 3H), 7.28–7.26 (m, 2H), 7.18–7.15 (m, 1H), 6.45 (d, J = 2.8 Hz, 1H), 3.69–3.64 (m, 5H), 2.54 (t, J = 7.2 Hz,
1
1
7
7
2
30.0–130.5 °C (uncorrected); H NMR (400 MHz, CDCl
3
1
3
1
.12–7.09 (m, 1H), 7.01–6.97 (m, 1H), 3.65 (t, J = 6.8 Hz, 2H), 2H), 2.21–2.13 (m, 2H); C{ H}NMR (100 MHz, CDCl
.54 (t, J = 7.6 Hz, 2H), 2.21–2.13 (m, 2H); C{ H}NMR 160.7, 156.9, 156.4, 148.2, 131.7, 129.5, 128.2, 127.3, 124.0,
3
) δ:
1
3
1
(
100 MHz, CDCl ) δ: 166.4 (d, J = 259.1 Hz, 1C), 160.6, 156.4, 122.9, 120.4, 118.2, 118.0, 111.8, 55.7, 53.4, 18.7, 16.2; HRMS
3
+
1
1
1
1
55.0 (d, J = 13.6 Hz, 1C), 132.3 (d, J = 10.8 Hz, 1C), 131.4, (ESI-TOF) m/z: C20
5
H18NO S (M + H) calcd for 384.0900, found
29.7, 128.3, 127.8, 122.7, 118.1, 116.7 (d, J = 26.0 Hz, 1C), 384.0906.
13.7 (d, J = 25.4 Hz, 1C), 104.5 (d, J = 25.6 Hz, 1C), 53.4, 18.6,
4-((6-Methyl-2-oxo-4-phenyl-2H-chromen-3-yl)sulfonyl)buta-
1
9
6.2; F NMR (282 MHz, CDCl
3
) δ: −98.5 (s, 1F); HRMS nenitrile (3ka). Yield: 55.8 mg, 76%; white solid; mp
1
9
+
1
(ESI-TOF) m/z: C19
H
15 FNO
4
S (M + H) calcd for 372.0700, 65.0–65.5 °C (uncorrected); H NMR (400 MHz, CDCl
3
) δ:
found 372.0708.
7.57–7.54 (m, 3H), 7.52–7.49 (m, 1H), 7.28 (d, J = 8.8 Hz, 1H),
4
-((7-Chloro-2-oxo-4-phenyl-2H-chromen-3-yl)sulfonyl)buta- 7.29–7.27 (m, 2H), 6.82 (d, J = 2.0 Hz, 1H), 3.66 (t, J = 7.2 Hz,
1
3
nenitrile (3fa). Yield: 60.4 mg, 78%; yellow solid; mp 2H), 2.54 (t, J = 7.2 Hz, 2H), 2.29 (s, 3H), 2.21–2.13 (m, 2H);
75.0–175.5 °C (uncorrected); H NMR (400 MHz, CDCl ) δ: { H}NMR (100 MHz, CDCl ) δ: 161.1, 156.9, 151.9, 136.5, 135.2,
3 3
.58–7.54 (m, 3H), 7.46 (d, J = 2.0 Hz, 1H), 7.28–7.25 (m, 2H), 131.7, 129.5, 129.4, 128.1, 127.4, 123.6, 119.5, 118.2, 116.7,
.24–7.21 (m, 1H), 7.02 (d, J = 8.8 Hz, 1H), 3.65 (t, J = 7.2 Hz, 53.4, 20.9, 18.7, 16.2; HRMS (ESI-TOF) m/z: C20 S (M +
C
1
1
1
7
7
2
H
18NO
4
1
3
1
+
H), 2.56 (t, J = 6.8 Hz, 2H), 2.21–2.14 (m, 2H); C{ H}NMR H) calcd for 368.0951, found 368.0958.
) δ: 160.4, 156.2, 153.8, 141.7, 131.2, 130.9, 4-((6-Chloro-2-oxo-4-phenyl-2H-chromen-3-yl)sulfonyl)buta-
29.7, 128.3, 127.4, 126.0, 123.7, 118.5, 118.1, 117.2, 53.4, 18.6, nenitrile (3la). Yield: 58.1 mg, 75%; yellow solid; mp
(
100 MHz, CDCl
3
1
1
3
3
5
+
1
6.2; HRMS (ESI-TOF) m/z: C H
88.0405, found 388.0412.
ClNO S (M + H) calcd for 181.0–181.5 °C (uncorrected); H NMR (400 MHz, CDCl ) δ:
1
9
15
4
3
7.76–7.74 (m, 1H), 7.57–7.55 (m, 3H), 7.28 (t, J = 1.6 Hz, 2H),
4
-((7-Bromo-2-oxo-4-phenyl-2H-chromen-3-yl)sulfonyl)buta- 7.20 (t, J = 8.0 Hz, 1H), 7.02–6.99 (m, 1H), 3.67 (t, J = 7.2 Hz,
1
3
1
nenitrile (3ga). Yield: 63.8 mg, 74%; white solid; mp 2H), 2.55 (t, J = 7.2 Hz, 2H), 2.22–2.15 (m, 2H); C{ H}NMR
83.0–183.5 °C (uncorrected); H NMR (400 MHz, CDCl
.63 (d, J = 2.0 Hz, 1H), 7.57–7.55 (m, 3H), 7.39–7.37 (m, 1H), 128.5, 128.3, 127.5, 125.1, 124.7, 122.3, 121.3, 118.0, 55.6, 18.7,
.27–7.25 (m, 2H), 6.94 (d, J = 8.8 Hz, 1H), 3.66 (t, J = 7.6 Hz, 16.2; HRMS (ESI-TOF) m/z: C H
1
1
7
7
2
3 3
) δ: (100 MHz, CDCl ) δ: 160.6, 155.7, 149.4, 135.3, 131.3, 129.8,
3
5
+
ClNO S (M + H) calcd for
4
1
9
15
1
3
1
H), 2.55 (t, J = 7.2 Hz, 2H), 2.21–2.14 (m, 2H); C{ H}NMR 388.0405, found 388.0410.
) δ: 160.5, 156.1, 153.6, 131.2, 130.9, 130.1, 4-((6-Bromo-2-oxo-4-phenyl-2H-chromen-3-yl)sulfonyl)buta-
29.8, 128.9, 128.3, 127.4, 123.9, 120.2, 118.9, 118.1, 53.5, 18.6, nenitrile (3ma). Yield: 60.4 mg, 70%; white solid; mp
(
100 MHz, CDCl
3
1
1
4
8
0
+
1
6.2; HRMS (ESI-TOF) m/z: C19
31.9900, found 431.9906.
H
15 BrNO
4
S (M + H) calcd for 175.0–175.5 °C (uncorrected); H NMR (400 MHz, CDCl
3
) δ:
7.79–7.77 (m, 1H), 7.59–7.56 (m, 3H), 7.34 (d, J = 8.8 Hz, 1H),
4
-((7-Acetyl-2-oxo-4-phenyl-2H-chromen-3-yl)sulfonyl)buta- 7.28 (t, J = 1.6 Hz, 2H), 7.18 (d, J = 2.0 Hz, 1H), 3.67 (t, J = 7.2
1
3
1
nenitrile (3ha). Yield: 56.1 mg, 71%; white solid; mp Hz, 2H), 2.55 (t, J = 7.2 Hz, 2H), 2.22–2.14 (m, 2H); C{ H}
30.0–130.5 °C (uncorrected); H NMR (400 MHz, CDCl
.95 (d, J = 2.0 Hz, 1H), 7.79–7.77 (m, 1H), 7.60–7.55 (m, 3H), 130.8, 130.0, 128.5, 127.4, 124.9, 121.4, 118.7, 118.2, 118.0,
4
.30–7.27 (m, 2H), 7.21 (d, J = 7.6 Hz, 1H), 3.69 (t, J = 7.2 Hz, 55.6, 18.6, 16.2; HRMS (ESI-TOF) m/z: C19H15 BrNO S (M +
1
1
7
7
2
{
1
1
3 3
) δ: NMR (100 MHz, CDCl ) δ: 159.8, 156.1, 152.5, 138.0, 132.0,
8
0
1
3
+
H), 2.67 (s, 3H), 2.56 (t, J = 7.2 Hz, 2H), 2.23–2.16 (m, 2H);
C
H) calcd for 431.9900, found 431.9906.
4-((4-(4-Methoxyphenyl)-2-oxo-2H-chromen-3-yl)sulfonyl)buta-
31.1, 130.5, 129.9, 128.4, 127.4, 125.7, 124.1, 123.0, 18.1, nenitrile (3oa). Yield: 65.1 mg, 85%; white solid; mp
1
H}NMR (100 MHz, CDCl ) δ: 195.9, 160.0, 156.3, 153.6, 141.6,
3
1
16.7, 53.6, 26.9, 18.6, 16.2; HRMS (ESI-TOF) m/z: C21
M + H) calcd for 396.0900, found 396.0910.
H
18NO
5
S
3
176.0–176.5 °C (uncorrected); H NMR (400 MHz, CDCl )
+
(
δ: 7.72–7.67 (m, 1H), 7.44 (d, J = 8.4 Hz, 1H), 7.28–7.19 (m,
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4
2
H), 7.06 (d, J = 8.8 Hz, 2H), 3.90 (s, 3H), 3.68 (t, J = 7.2 Hz, 127.9 (2C), 125.5, 125.3 (q, J = 3.7 Hz, 1C), 124.2, 123.7 (q, J =
H), 2.55 (t, J = 7.2 Hz, 2H), 2.21–2.14 (m, 2H); C{ H}NMR 270.8 Hz,) 119.3, 118.0, 117.2, 53.5, 18.6, 16.2; F NMR
1
3
1
19
(
1
1
100 MHz, CDCl
3
) δ: 161.3, 160.6, 156.8, 153.6, 135.1, 130.0, (282 MHz, CDCl
3
) δ: −62.7 (s, 3F); HRMS (ESI-TOF) m/
S (M + H) calcd for 422.0668, found
1
9
+
29.2, 127.8, 125.2, 123.4, 120.1, 118.2, 116.9, 113.7, 55.3, 53.5, z: C20
8.7, 16.2; HRMS (ESI-TOF) m/z: C H NO S (M + H) calcd 422.0673.
H
15
F
3
NO
4
+
2
0
18
5
for 384.0900, found 384.0906.
4-((2-Oxo-4-(m-tolyl)-2H-chromen-3-yl)sulfonyl)butanenitrile
4
-((2-Oxo-4-(p-tolyl)-2H-chromen-3-yl)sulfonyl)butanenitrile (3ua). Yield: 58.7 mg, 80%; white solid; mp 153.0–153.5 °C
1
(
(
3pa). Yield: 60.2 mg, 82%; white solid; mp 188.0–188.5 °C (uncorrected); H NMR (400 MHz, CDCl ) δ: 7.72–7.67 (m, 1H),
uncorrected); H NMR (400 MHz, CDCl
3
1
3
) δ: 7.69–7.67 (m, 1H), 7.43 (t, J = 7.6 Hz, 2H), 7.35 (d, J = 7.6 Hz, 1H), 7.28–7.24 (m,
7
.44 (d, J = 8.0 Hz, 1H), 7.35 (d, J = 8.0 Hz, 2H), 7.27–7.23 (m, 1H), 7.12–7.07 (m, 3H), 3.66 (t, J = 7.2 Hz, 2H), 2.55 (t, J = 7.2
1
3
1
1
H), 7.18–7.13 (m, 3H), 3.67 (t, J = 7.2 Hz, 2H), 2.55 (t, J = 7.2 Hz, 2H), 2.45 (s, 3H), 2.21–2.14 (m, 2H);
C{ H}NMR
1
3
1
Hz, 2H), 2.47 (s, 3H), 2.22–2.15 (m, 2H);
C{ H}NMR (100 MHz, CDCl ) δ: 161.5, 156.8, 153.7, 138.0, 135.2, 131.6,
3
(
100 MHz, CDCl
3
) δ: 161.5, 156.8, 153.7, 139.7, 135.2, 130.1, 130.3, 130.1, 128.1, 128.0, 125.3, 1246, 123.6, 120.0, 118.3,
1
1
28.9, 128.6, 127.5, 125.2, 123.9, 120.1, 118.1, 117.0, 53.6, 21.5, 117.0, 53.4, 21.6, 18.8, 16.2; HRMS (ESI-TOF) m/z: C H NO S
20 18 4
+
+
8.8, 16.3; HRMS (ESI-TOF) m/z: C20
H
18NO
4
S (M + H) calcd (M + H) calcd for 368.0951, found 368.0957.
4-((4-(2-Methoxyphenyl)-2-oxo-2H-chromen-3-yl)sulfonyl)buta-
-((4-(4-Fluorophenyl)-2-oxo-2H-chromen-3-yl)sulfonyl)buta- nenitrile (3va). Yield: 58.2 mg, 76%; yellow solid; mp
for 368.0951, found 368.0957.
4
1
nenitrile (3qa). Yield: 59.4 mg, 80%; white solid; mp 142.0–142.5 °C (uncorrected); H NMR (400 MHz, CDCl
3
) δ:
1
1
7
7
2
1
1
1
92.0–192.5 °C (uncorrected); H NMR (400 MHz, CDCl ) δ: 7.70–7.66 (m, 1H), 7.52–7.50 (m, 1H), 7.43 (d, J = 7.2 Hz, 1H),
3
.74–7.70 (m, 1H), 7.46 (d, J = 7.2 Hz, 1H), 7.31–7.23 (m, 5H), 7.24–7.23 (m, 1H), 7.13–7.05 (m, 4H), 3.79 (s, 3H), 3.74–3.67
.11–7.09 (m, 1H), 3.69 (t, J = 7.2 Hz, 2H), 2.56 (t, J = 7.2 Hz, (m, 1H), 3.60–3.53 (m, 1H), 2.57–2.46 (m, 2H), 2.20–2.13 (m,
H), 2.22–2.15 (m, 2H); C{ H}NMR (100 MHz, CDCl ) δ: 2H); C{ H}NMR (100 MHz, CDCl ) δ: 159.0, 156.8, 155.4,
3 3
1
3
1
13
1
63.3 (d, J = 248.9 Hz, 1C), 160.1, 156.6, 153.7, 135.4, 129.7, 153.7, 135.0, 131.0, 129.3, 128.7, 125.1, 123.8, 120.6, 120.3,
29.6 (d, J = 8.4 Hz, 1C), 127.4 (d, J = 3.7 Hz, 1C), 125.4, 124.3, 119.6, 118.3, 116.8, 110.7, 55.7, 52.6, 18.6, 16.1; HRMS
+
19.8, 118.1, 117.1, 115.7 (d, J = 22.2 Hz, 1C), 53.5, 18.6, 16.2; (ESI-TOF) m/z: C20
H
18NO
5
S (M + H) calcd for 384.0900, found
1
9
F NMR (282 MHz, CDCl ) δ: −110.4 (s, 1F); HRMS (ESI-TOF) 384.0906.
3
1
9
+
m/z: C19
H
15 FNO
4
S (M + H) calcd for 372.0700, found
4-((2-Oxo-4-(o-tolyl)-2H-chromen-3-yl)sulfonyl)butanenitrile
3
72.0710.
(3wa). Yield: 54.3 mg, 74%; yellow solid; mp 115.0–115.5 °C
1
4
-((4-(4-Chlorophenyl)-2-oxo-2H-chromen-3-yl)sulfonyl)buta- (uncorrected); H NMR (400 MHz, CDCl ) δ: 7.72–7.68 (m, 1H),
3
nenitrile (3ra). Yield: 59.6 mg, 77%; white solid; mp 7.47–7.43 (m, 2H), 7.36 (d, J = 7.2 Hz, 2H), 7.27–7.23 (m, 1H),
1
1
7
7
2
42.0–142.5 °C (uncorrected); H NMR (400 MHz, CDCl
.72–7.70 (m, 1H), 7.54–7.50 (m, 2H), 7.46 (d, J = 8.0 Hz, 1H), 2.58–2.54 (m, 2H), 2.22–2.15 (m, 5H); C{ H}NMR (100 MHz,
.31–7.22 (m, 3H), 7.09–7.07 (m, 1H), 3.68 (t, J = 7.2 Hz, 2H), CDCl ) δ: 161.3, 156.7, 153.8, 135.4, 134.7, 131.6, 130.1, 129.5,
.56 (t, J = 7.6 Hz, 2H), 2.22–2.15 (m, 2H); C{ H}NMR 129.3, 126.6, 125.7, 125.5, 123.8, 119.2, 118.1, 117.1, 53.2, 19.8,
3
) δ: 7.08 (t, J = 7.6 Hz, 1H), 6.98–6.96 (m, 1H), 3.75–3.59 (m, 2H),
1
3
1
3
1
3
1
+
(
100 MHz, CDCl ) δ: 159.8, 156.5, 153.7, 135.9, 135.5, 129.9, 18.6, 16.2; HRMS (ESI-TOF) m/z: C H NO S (M + H) calcd
3
20 18
4
1
1
3
29.7, 128.9, 128.6, 125.4, 124.1, 119.6, 118.1, 117.1, 53.5, 18.6, for 368.0951, found 368.0957.
3
5
+
6.2; HRMS (ESI-TOF) m/z: C19
H
15 ClNO
4
S (M + H) calcd for
4-((4-(3,5-Dimethylphenyl)-2-oxo-2H-chromen-3-yl)sulfonyl)
88.0405, found 388.0411.
butanenitrile (3xa). Yield: 54.1 mg, 71%; white solid; mp
1
4
-(3-((3-Cyanopropyl)sulfonyl)-2-oxo-2H-chromen-4-yl)benzo- 209.0–209.5 °C (uncorrected); H NMR (400 MHz, CDCl
3
) δ:
nitrile (3sa). Yield: 52.9 mg, 70%; yellow solid; mp 7.71–7.67 (m, 1H), 7.43 (d, J = 8.4 Hz, 1H), 7.26 (t, J = 7.2 Hz,
1
1
7
3
58.0–158.5 °C (uncorrected); H NMR (400 MHz, CDCl ) δ: 1H), 7.14 (t, J = 9.2 Hz, 2H), 6.88 (s, 2H), 3.66 (t, J = 7.2 Hz,
3
1
3
.81 (d, J = 8.0 Hz, 2H), 7.74 (t, J = 8.8 Hz, 1H), 7.49–7.42 (m, 2H), 2.56 (t, J = 7.2 Hz, 2H), 2.40 (s, 6H), 2.22–2.15 (m, 2H);
H), 7.29 (d, J = 7.6 Hz, 1H), 7.00–6.96 (m, 1H), 3.69 (t, J = 7.6 { H}NMR (100 MHz, CDCl ) δ: 161.7, 156.8, 153.5, 137.7, 135.1,
3
Hz, 2H), 2.56 (t, J = 7.2 Hz, 2H), 2.22–2.15 (m, 2H); C{ H} 131.4, 131.1, 130.2, 125.1 (2C), 123.3, 120.0, 118.2, 116.8, 53.3,
C
1
1
3
1
+
NMR (100 MHz, CDCl
3
) δ: 159.3, 156.4, 153.8, 135.7, 131.8, 21.3, 18.7, 16.1; HRMS (ESI-TOF) m/z: C21
4
H20NO S (M + H)
1
1
31.5, 129.5, 128.0, 125.5, 125.3, 125.3, 124.3, 119.3, 118.0, calcd for 382.1108, found 382.1116.
17.2, 53.5, 18.6, 16.2; HRMS (ESI-TOF) m/z: C H N O S (M +
4-((2-Oxo-4-(thiophen-2-yl)-2H-chromen-3-yl)sulfonyl)buta-
2
0
15 2 4
+
H) calcd for 379.0747, found 379.0752.
nenitrile (3ya). Yield: 33.7 mg, 47%; white solid; mp
1
4
-((2-Oxo-4-(4-(trifluoromethyl)phenyl)-2H-chromen-3-yl)sul- 123.0–123.5 °C (uncorrected); H NMR (400 MHz, CDCl
3
) δ:
fonyl)butanenitrile (3ta). Yield: 59.8 mg, 71%; yellow solid; 7.72–7.66 (m, 2H), 7.45–7.38 (m, 2H), 7.34–7.30 (m, 1H),
1
mp 136.0–136.5 °C (uncorrected); H NMR (400 MHz, CDCl
3
)
7.25–7.23 (m, 1H), 7.20–7.19 (m, 1H), 3.70 (t, J = 7.2 Hz, 2H),
1
3
1
δ: 7.81 (d, J = 8.0 Hz, 2H), 7.76–7.13 (m, 1H), 7.48 (d, J = 2.58 (t, J = 7.6 Hz, 2H), 2.25–2.18 (m, 2H); C{ H}NMR
8
6
2
.4 Hz, 1H), 7.43 (d, J = 8.0 Hz, 2H), 7.31–7.27 (m, 1H), (100 MHz, CDCl ) δ: 156.4, 154.8, 153.3, 135.4, 130.0, 129.8,
3
.99–6.96 (m, 1H), 3.69 (t, J = 7.2 Hz, 2H), 2.56 (t, J = 7.2 Hz, 129.5, 128.6, 127.4, 125.8, 125.4, 120.2, 118.1, 117.0, 53.7, 18.7,
1
3
1
+
H), 2.22–2.15 (m, 2H);
C{ H}NMR (100 MHz, CDCl
3
)
4 2
16.3; HRMS (ESI-TOF) m/z: C17H14NO S (M + H) calcd for
δ: 159.3, 156.4, 153.7, 135.7, 131.6 (q, J = 32.8 Hz, 1C), 129.5, 360.0359, found 360.0365.
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1
4
-((2-Oxo-4-pentyl-2H-chromen-3-yl)sulfonyl)butanenitrile mp 194.0–194.5 °C (uncorrected); H NMR (400 MHz, CDCl
3
)
(
3za). Yield: 50.7 mg, 73%; white solid; mp 88.0–88.5 °C δ: 7.62 (t, J = 7.2 Hz, 1H), 7.56–7.47 (m, 3H), 7.34 (d, J = 8.4 Hz,
1
(uncorrected); H NMR (400 MHz, CDCl
3
) δ: 7.87 (d, J = 8.4 Hz, 1H), 7.25 (d, J = 8.4 Hz, 3H), 7.19–7.15 (m, 3H), 7.07–7.05 (m,
1
H), 7.71 (t, J = 7.2 Hz, 1H), 7.45–7.39 (m, 2H), 3.77 (t, J = 7.6 1H), 6.95 (d, J = 8.0 Hz, 1H), 4.58–4.51 (m, 1H), 3.61–3.56 (m,
13
1
Hz, 2H), 3.49 (t, J = 8.0 Hz, 2H), 3.65 (t, J = 7.2 Hz, 2H), 2H), 2.80–2.67 (m, 2H), 1.05 (s, 9H); C{ H}NMR (100 MHz,
2
1
.31–2.24 (m, 2H), 1.77–1.69 (m, 2H), 1.59–1.51 (m, 2H), CDCl
.44–1.39 (m, 2H), 0.94 (t, J = 7.2 Hz, 3H); C{ H}NMR 128.1, 127.7, 127.3, 126.9, 125.8, 125.0, 124.0, 119.6, 117.1,
3
) δ: 159.6, 156.8, 153.4, 151.4, 134.8, 131.4, 129.6, 128.6,
1
3
1
(
1
1
100 MHz, CDCl ) δ: 164.4, 156.7, 153.6, 135.0, 126.5, 125.4, 116.8, 58.0, 37.1, 34.3, 30.9, 24.7; HRMS (ESI-TOF) m/z:
3
+
23.3, 118.5, 118.1, 117.6, 54.0, 32.3, 31.3, 27.7, 22.3, 18.9,
6.4, 13.9; HRMS (ESI-TOF) m/z: C18H22NO S (M + H) calcd
4
C
29
H
28NO
4
S (M + H) calcd for 486.1734, found 486.1739.
4-((2-Oxo-4-phenyl-2H-chromen-3-yl)sulfonyl)-3-phenylbuta-
nenitrile (3af). Yield: 60.1 mg, 70%; white solid; mp
+
for 348.1264, found 348.1269.
3
-((4-Methyl-2-oxo-2H-chromen-3-yl)sulfonyl)butanenitrile 105.0–105.5 °C (uncorrected); H NMR (400 MHz, CDCl ) δ:
1
4
(
3aaa). Yield: 36.1 mg, 62%; yellow solid; mp 102.0–102.5 °C 7.68–7.64 (m, 1H), 7.57–7.52 (m, 3H), 7.35 (d, J = 8.4 Hz, 1H),
1
(uncorrected); H NMR (400 MHz, CDCl ) δ: 7.93–7.90 (m, 1H), 7.29–7.20 (m, 6H), 7.18–7.16 (m, 1H), 7.12–7.09 (m, 1H),
3
7
3
.74–7.70 (m, 1H), 7.46–7.39 (m, 2H), 3.76 (t, J = 7.2 Hz, 2H), 7.06–7.04 (m, 1H), 4.36–4.30 (m, 1H), 3.71–3.60 (m, 2H),
.03 (s, 3H), 2.65 (t, J = 7.2 Hz, 2H), 2.32–2.25 (m, 2H); C{ H} 2.89–2.74 (m, 2H); C{ H}NMR (100 MHz, CDCl ) δ: 160.1,
3
1
3
1
13
1
NMR (100 MHz, CDCl ) δ: 160.0, 156.5, 153.1, 135.1, 127.8, 156.8, 153.5, 138.1, 135.0, 131.5, 129.7, 129.1, 128.3, 128.3,
3
1
26.6, 125.4, 119.4, 118.1, 117.4, 54.0, 18.9, 16.4, 15.0; HRMS 127.9, 127.5, 127.0, 125.1, 124.0, 119.6, 117.1, 116.8, 58.3, 37.2,
+
+
(ESI-TOF) m/z: C14
H
14NO
4
S (M + H) calcd for 292.0638, found 24.5; HRMS (ESI-TOF) m/z: C25
H
20NO
4
S (M + H) calcd for
2
92.0645.
-(Benzyloxy)-4-((2-oxo-4-phenyl-2H-chromen-3-yl)sulfonyl)
butanenitrile (3ab). Yield: 73.5 mg, 80%; yellow solid; mp nyl)butanenitrile (3ag). Yield: 59.9 mg, 67%; white solid; mp
430.1108, found 430.1118.
3-(4-Fluorophenyl)-4-((2-oxo-4-phenyl-2H-chromen-3-yl)sulfo-
3
1
1
1
7
7
6
1
1
1
1
2
4
32.0–132.5 °C (uncorrected); H NMR (400 MHz, CDCl ) δ: 185.0–185.5 °C (uncorrected); H NMR (400 MHz, CDCl ) δ:
3
3
.66–7.62 (m, 1H), 7.54–7.51 (m, 3H), 7.34 (d, J = 8.4 Hz, 1H), 7.70–7.66 (m, 1H), 7.58–7.54 (m, 3H), 7.40 (d, J = 8.0 Hz, 1H),
.26–7.24 (m, 1H), 7.19 (t, J = 8.4 Hz, 3H), 7.08–7.01 (m, 4H), 7.31–7.18 (m, 5H), 7.09–7.07 (m, 1H), 6.97 (t, J = 8.4 Hz, 2H),
.94 (d, J = 8.0 Hz, 1H), 4.64 (d, J = 11.2 Hz, 1H), 4.51 (d, J = 4.26–4.21 (m, 1H), 3.72–3.63 (m, 2H), 2.89–2.73 (m, 2H);
1.2 Hz, 1H), 4.28–4.21 (m, 2H), 3.63–3.58 (m, 1H), 2.72 (t, J = { H}NMR (100 MHz, CDCl
.6 Hz, 2H); C{ H}NMR (100 MHz, CDCl
1
3
C
1
3
) δ: 162.4 (d, J = 246.7 Hz, 1C),
1
3
1
3
) δ: 159.4, 156.9, 160.3, 156.8, 153.5, 135.2, 134.0 (d, J = 3.5 Hz, 1C), 131.4, 129.7
53.4, 136.0, 134.8, 131.6, 129.7, 129.5, 128.3, 128.2, 128.0, (d, J = 2.1 Hz, 1C), 129.2 (d, J = 8.2 Hz, 1C), 128.4 (d, J = 4.8 Hz,
27.4, 127.1, 125.0, 124.9, 119.7, 116.9, 116.4, 72.2, 69.9, 57.7, 1C), 128.0, 126.1 (d, J = 176.4 Hz, 1C), 124.1, 119.5, 117.0,
+
19
5
3.0; HRMS (ESI-TOF) m/z: C26H22NO S (M + H) calcd for 116.9, 116.2, 115.9, 58.5, 36.3, 24.6; F NMR (282 MHz,
1
9
60.1213, found 460.1220.
CDCl ) δ: −113.0 (s, 1F); HRMS (ESI-TOF) m/z: C H
FNO4S
3
25 19
+
3
-Benzyl-4-((2-oxo-4-phenyl-2H-chromen-3-yl)sulfonyl)buta- (M + H) calcd for 448.1013, found 448.1021.
nenitrile (3ac). Yield: 65.6 mg, 74%; yellow solid; mp 3-(4-Chlorophenyl)-4-((2-oxo-4-phenyl-2H-chromen-3-yl)sulfo-
32.0–132.5 °C (uncorrected); H NMR (400 MHz, CDCl ) δ: nyl)butanenitrile (3ah). Yield: 59.3 mg, 64%; yellow solid; mp
1
1
7
7
3
2
3
1
3
.72–7.67 (m, 1H), 7.55–7.53 (m, 3H), 7.45–7.42 (m, 1H), 162.0–162.5 °C (uncorrected); H NMR (400 MHz, CDCl ) δ:
.32–7.22 (m, 6H), 7.19 (t, J = 2.0 Hz, 2H), 7.09–7.07 (m, 1H), 7.67 (t, J = 8.8 Hz, 1H), 7.58–7.50 (m, 3H), 7.40 (d, J = 8.4 Hz,
.76 (d, J = 4.0 Hz, 1H), 3.54–3.48 (m, 1H), 2.95–2.81 (m, 2H), 1H), 7.28–7.16 (m, 7H), 7.08 (d, J = 8.8 Hz, 1H), 4.30–4.25 (m,
13
13
1
.72 (t, J = 6.4 Hz, 1H), 2.64–2.58 (m, 1H), 2.50–2.44 (m, 1H);
C
1H), 3.68–3.60 (m, 2H), 2.85–2.71 (m, 2H);
C{ H}NMR
1
{
H}NMR (100 MHz, CDCl
3
) δ: 160.7, 156.6, 153.7, 136.7, 135.2, (100 MHz, CDCl ) δ: 160.2, 156.7, 153.4, 136.5, 135.2, 134.4,
3
1
1
C
31.6, 130.0, 129.5, 129.1, 128.9, 128.2, 127.6, 127.2, 125.2, 124.2, 131.4, 129.6, 129.1, 128.9, 128.4, 128.3, 127.9, 127.0, 125.2,
19.8, 117.4, 117.0, 57.3, 39.3, 32.2, 21.1; HRMS (ESI-TOF) m/z: 123.9, 119.4, 116.9, 58.1, 36.6, 24.3; HRMS (ESI-TOF) m/z:
+
35
+
26
H
22NO
4
S (M + H) calcd for 444.1264, found 444.1271.
C
25
H
19 ClNO
4
S (M + H) calcd for 464.0718, found 464.0725.
4
-((2-Oxo-4-phenyl-2H-chromen-3-yl)sulfonyl)-3-(p-tolyl)buta-
3-(4-Bromophenyl)-4-((2-oxo-4-phenyl-2H-chromen-3-yl)sulfo-
nenitrile (3ad). Yield: 67.4 mg, 76%; yellow solid; mp nyl)butanenitrile (3ai). Yield: 58.8 mg, 58%; white solid; mp
1
1
1
7
7
7
2
3 3
16.0–116.5 °C (uncorrected); H NMR (400 MHz, CDCl ) δ: 174.0–174.5 °C (uncorrected); H NMR (400 MHz, CDCl ) δ:
.67–7.62 (m, 1H), 7.58–7.51 (m, 3H), 7.37 (d, J = 8.4 Hz, 1H), 7.70–7.66 (m, 1H), 7.58–7.52 (m, 3H), 7.41 (t, J = 7.6 Hz, 3H),
.27–7.24 (m, 1H), 7.22–7.19 (m, 2H), 7.11 (d, J = 8.0 Hz, 2H), 7.29–7.25 (m, 2H), 7.23–7.18 (m, 1H), 7.13–7.08 (m, 3H),
1
3
.07–7.02 (m, 3H), 4.40–4.35 (m, 1H), 3.62–3.53 (m, 2H), 4.29–4.24 (m, 1H), 3.69–3.58 (m, 2H), 2.87–2.72 (m, 2H);
C
1
3
1
1
.83–2.73 (m, 2H), 2.04 (s, 3H); C{ H}NMR (100 MHz, CDCl ) { H}NMR (100 MHz, CDCl ) δ: 160.3, 156.8, 153.6, 137.1, 135.3,
3
3
δ: 159.7, 156.8, 153.5, 138.5, 134.8, 134.8, 131.5, 129.6, 128.7, 132.2, 131.4, 129.7, 129.2, 128.5, 128.0, 127.0, 125.3, 124.1,
1
5
28.4, 127.9, 127.5, 127.1, 125.0, 124.1, 119.6, 117.1, 116.7, 122.6, 119.5, 117.0, 116.8, 58.2, 36.7, 24.3; HRMS (ESI-TOF) m/
8
0
+
8.3, 37.1, 24.5, 20.7; HRMS (ESI-TOF) m/z: C H NO S (M + z: C H
BrNO S (M + H) calcd for 508.0213, found
4
2
6
22
4
25 19
+
H) calcd for 444.1264, found 444.1270.
-(4-(tert-Butyl)phenyl)-4-((2-oxo-4-phenyl-2H-chromen-3-yl)
sulfonyl)butanenitrile (3ae). Yield: 69.9 mg, 72%; white solid; fonyl)methyl)butanenitrile (3aj). Yield: 75.9 mg, 77%; white
508.0221.
3
4-(Naphthalen-1-yl)-3-(((2-oxo-4-phenyl-2H-chromen-3-yl)sul-
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1
solid; mp 180.0–180.5 °C (uncorrected); H NMR (400 MHz,
Conflicts of interest
CDCl ) δ: 7.95 (d, J = 8.4 Hz, 1H), 7.77–7.71 (m, 2H), 7.68 (d, J =
3
7
7
7
3
2
1
1
1
.2 Hz, 1H), 7.52–7.49 (m, 3H), 7.44 (t, J = 8.4 Hz, 1H), There are no conflicts to declare.
.38–7.33 (m, 3H), 7.30–7.22 (m, 1H), 7.20 (t, J = 7.2 Hz, 2H),
.09 (d, J = 8.0 Hz, 1H), 6.96–6.94(m, 1H), 3.91–3.86 (m, 1H),
.44–3.34 (m, 2H), 3.29–3.23 (m, 1H), 2.85–2.80 (m, 1H),
Acknowledgements
1
3
1
3
.60–2.49 (m, 2H); C{ H}NMR (100 MHz, CDCl ) δ: 161.0,
56.1, 153.4, 135.0, 133.9, 132.7, 131.5, 131.2, 129.9, 129.4, We thank the National Natural Science Foundation of China
29.0, 128.2, 128.2, 128.1, 128.1, 127.9, 126.7, 126.4, 125.6, (No. 22078084 and 51874132), Scientific Research Fund of
25.6, 125.0, 123.3, 123.1, 117.0, 57.0, 37.1, 31.8, 21.9; HRMS Hunan Provincial Education Department (No. 20A224 and
+
(ESI-TOF) m/z: C H NO S (M + H) calcd for 494.1421, found 18B355), Science and Technology Planning Project of Hunan
3
0
24
4
4
94.1428.
-Methyl-4-((2-oxo-4-phenyl-2H-chromen-3-yl)sulfonyl)-3-phenyl- Science Foundation of Hunan Province (No. 2020JJ5212) for
butanenitrile (3ak). Yield: 54.9 mg, 62%; white solid; mp financial support.
Province (No. 2020RC3056 and 2018TP1017) and Natural
3
1
8
7
7
4
3
3.0–83.5 °C (uncorrected); H NMR (400 MHz, CDCl ) δ:
.67–7.62 (m, 1H), 7.55–7.51 (m, 3H), 7.48 (t, J = 3.2 Hz, 3H),
.26–7.19 (m, 3H), 7.15 (d, J = 8.0 Hz, 2H), 6.99–6.92 (m, 2H),
.31 (d, J = 15.2 Hz, 1H), 3.81 (d, J = 15.2 Hz, 1H), 3.14–3.05
Notes and references
1
3
1
(m, 2H), 1.70 (s, 3H); C{ H}NMR (100 MHz, CDCl
3
) δ: 159.4,
56.8, 153.4, 136.0, 134.8, 131.6, 129.7, 129.5, 128.3, 128.2,
28.0, 127.4, 127.1, 125.0, 124.9, 119.7, 116.9, 116.4, 72.2, 69.9,
1 (a) F. Borges, F. Roleira, N. Milhazes, E. Uriarte and
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2 (a) A. Goth, Science, 1945, 101, 383; (b) T. Eckardt,
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J. Bendig, J. Org. Chem., 2002, 67, 703; (c) R.-M. Christie
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1
1
5
+
4
7.7, 23.0; HRMS (ESI-TOF) m/z: C26H22NO S (M + H) calcd
for 444.1264, found 444.1271.
-((2-Oxo-4-phenyl-2H-chromen-3-yl)sulfonyl)-5-phenylpenta-
nenitrile (3am). Yield: 62.0 mg, 70%; yellow solid; mp
4
1
1
7
7
3
1
2
22.0–122.5 °C (uncorrected); H NMR (400 MHz, CDCl ) δ:
3
.71–7.66 (m, 1H), 7.59–7.55 (m, 3H), 7.41 (d, J = 8.0 Hz, 1H),
.33 (d, J = 6.4 Hz, 1H), 7.29–7.22 (m, 4H), 7.16 (t, J = 8.4 Hz,
H), 7.06 (d, J = 8.4 Hz, 1H), 4.52–4.48 (m, 1H), 3.21–3.16 (m,
H), 2.73–2.67 (m, 1H), 2.56–2.49 (m, 1H), 2.48–2.43 (m, 1H),
1
3
1
.28–2.22 (m, 1H), 2.02–1.95 (m, 1H); C{ H}NMR (100 MHz,
CDCl ) δ: 160.8, 156.8, 153.6, 135.3, 135.1, 131.6, 129.8, 129.6,
1
1
3
29.1, 129.0, 128.2, 128.0, 127.4, 126.7, 125.2, 119.9, 118.6,
4
16.9, 62.2, 35.1, 23.2, 15.3; HRMS (ESI-TOF) m/z: C26 22NO S
H
+
(M + H) calcd for 444.1264, found 444.1270.
Butyl 4-((2-oxo-4-phenyl-2H-chromen-3-yl)sulfonyl)butanoate
(7). Yield: 59.9 mg, 70%; white solid; mp 94.0–94.5 °C (uncor-
1
rected); H NMR (400 MHz, CDCl ) δ: 7.69 (t, J = 1.6 Hz, 1H),
3
7
7
2
2
.66–7.50 (m, 3H), 7.43 (d, J = 8.4 Hz, 1H), 7.29–7.22 (m, 3H),
.07–7.05 (m, 1H), 4.06 (t, J = 6.8 Hz, 2H), 3.59 (t, J = 7.6 Hz,
H), 2.44 (t, J = 7.6 Hz, 2H), 2.10–2.04 (m, 2H), 1.62–1.55 (m,
H), 1.38–1.32 (m, 2H), 0.92 (t, J = 7.6 Hz, 3H); C{ H}NMR
) δ: 172.1, 160.7, 156.7, 153.7, 134.9, 131.9,
29.9, 129.3, 128.1, 127.5, 125.1, 123.8, 120.1, 116.9, 64.6, 5.1,
3 (a) P. Sokkalingam and C.-H. Lee, J. Org. Chem., 2011, 76,
3820; (b) Q. Xu, J. Ouyang, Y. Yang, T. Ito and J. Kido, Appl.
Phys. Lett., 2003, 83, 4695; (c) M.-T. Lee, C.-K. Yen and
W.-P. Yang, Org. Lett., 2004, 6, 1241; (d) X. Peng, G. Damu
and C. Zhou, Curr. Pharm. Des., 2013, 19, 3884;
(e) R.-V. Rajeshwar, K. Srimanth and P. Vijaya Kumar,
Indian J. Heterocycl. Chem., 2004, 14, 141; (f) H. Kima and
J. Yun, Adv. Synth. Catal., 2010, 352, 1881.
1
3
1
(100 MHz, CDCl
3
1
3
+
2.4, 30.6, 19.1, 18.1, 13.7; HRMS (ESI-TOF) m/z: C23
H
25
O
6
S (M
+
H) calcd for 429.1366, found 429.1375.
4
-((2-Oxo-4-phenylchroman-3-yl)sulfonyl)butanenitrile (8).
Yield: 46.9 mg, 66%; yellow solid; mp 108.0–108.5 °C (uncor-
4 For selected examples for SO2 insertion reactions, see:
(a) G.-Y.-S. Qiu, K.-D. Zhou and J. Wu, Chem. Commun.,
2018, 54, 12561; (b) G.-Y.-S. Qiu, L.-F. Lai, J. Cheng and
J. Wu, Chem. Commun., 2018, 54, 10405; (c) H.-G. Xia,
Y.-Y. An, X.-C. Zeng and J. Wu, Chem. Commun., 2017, 53,
12548; (d) S.-Q. Ye, X.-F. Li, W.-L. Xie and J. Wu, Eur. J. Org.
Chem., 2020, 1274; (e) J.-Y. Yu, R.-Y. Mao, Q.-Y. Wang and
J. Wu, Org. Chem. Front., 2017, 4, 617; (f) Y. Liu,
Q.-L. Wang, Z. Chen, P. Chen, K.-W. Tang, Q. Zhou and
J. Xie, Org. Biomol. Chem., 2019, 17, 10020; (g) F.-S. He,
1
rected); H NMR (400 MHz, CDCl
.53–7.51 (m, 3H), 7.43 (d, J = 8.4 Hz, 1H), 7.29–7.22 (m, 3H),
.08–7.05 (m, 1H), 3.61 (t, J = 8.0 Hz, 2H), 3.03 (t, J = 7.6 Hz,
H), 2.51 (t, J = 7.2 Hz, 2H), 2.23 (t, J = 4.4 Hz, 1H), 2.22–2.02
m, 2H); C{ H}NMR (100 MHz, CDCl ) δ: 160.9, 156.8, 153.7,
3
35.0, 131.8, 129.9, 129.3, 128.1, 127.5, 125.1, 120.1, 116.9,
3.8, 51.1, 31.9, 22.8, 17.7; HRMS (ESI-TOF) m/z: C19 18NO S
4
M + H) calcd for 356.0951, found 356.0958.
3
) δ: 7.69–7.65 (m, 1H),
7
7
1
1
3
1
(
1
5
(
H
+
3188 | Org. Biomol. Chem., 2021, 19, 3181–3190
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Paper
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