Palladium-Catalyzed C?H Functionalization of Phenyl 2-Pyridylsulfonates

Article abstract of DOI:10.1002/asia.201601413

An efficient palladium(II)-catalyzed intermolecular direct ortho-alkenylation and acetoxylation of phenols has been developed. The reaction proceeded via a seven-membered cyclopalladated intermediate and showed complete regio- and diastereoselectivity. The approach also provided an efficient route for the synthesis of coumarins and benzofurans.

Full text of DOI:10.1002/asia.201601413

CHEMISTRY
AN ASIAN JOURNAL
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Accepted Article
Title: Palladium-Catalyzed C-H Functionalization of Phenyl 2-
Pyridylsulfonate
Authors: Bin Li, Dong-Dong Guo, Shi-Huan Guo, Gao-Fei Pan, Ya-Ru
Gao, and Yong-Qiang Wang
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To be cited as: Chem. Asian J. 10.1002/asia.201601413
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Palladium-Catalyzed C-H Functionalization of Phenyl 2-
Pyridylsulfonate
Bin Li, Dong-Dong Guo, Shi-Huan Guo, Gao-Fei Pan, Ya-Ru Gao, Yong-Qiang Wang*[a]
Abstract:
intermolecular direct ortho alkenylation and acetoxylation of phenols
have been developed. The reaction proceeded via seven-
A
general and efficient palladium(II)-catalyzed
amounts of the reduced external oxidant as waste.
Recently, Yu et al. reported the Pd-catalyzed C-H olefinations
a
of
cyclopalladated pathway;[9] and 2-pyridyloxyl group was reported
to be powerful directing group for the selective ortho
3-phenylpropionic
acids
via
a
seven-membered
membered cyclopalladated intermediate and showed complete
regio- and diastereoselectivity. The approach also presented an
efficient route for synthesis of corresponding coumarins and
benzofurans.
a
olefination of a variety of aromatic compounds.[10] Inspired by
these pioneering studies, we envisioned that 2-pyridylsulfonyl
group might serve as a promising removable and highly valuable
directing and protecting group of phenols to achieve the
palladium-catalyzed direct ortho-C-H functionalizations through
Introduction
the formation of
a
seven-membered cyclopalladated
intermediate. If the activity of palladium catalyst was improved,
oxygen could be employed as the ideal oxidant with water as
reduced waste. Herein, we report progress toward achieving
these goals.
In the past decade, the direct functionalization of C-H bonds
has revolutionized the field of organic synthesis due to its atom
and step economy by eliminating the need for preactivation of
the starting materials.[1] In this area, the transition-metal-
catalyzed protocol has been greatly developed.[2] Because the
palladium catalyst possesses remarkable reactivity, compatibility
and selectivity, the palladium-catalyzed C-H activation and
functionalization have been studied largely.[3] To date, direct C-H
activation and functionalization via five or six-membered
cyclopalladated intermediates have been well documented.[4]
However, the more than six-membered, such as seven-
membered cyclopalladated processes are fairly rare, which likely
lie in the more instability of these palladacycles than the five-
and six-membered ones.[5]
Results and Discussion
Because ortho-alkenyl phenols are important building blocks
for synthetic organic chemistry,[10,11] we initially aimed to develop
ortho-C-H olefination of phenol derivatives. First, the reaction
was carried out with phenyl 2-pyridylsulfonate (1a) and methyl
acrylate (2a) as model substrates employing Pd(OAc)2 (10
mol%) as the catalyst and oxygen as the oxidant in DCE (Table
1). It was found that the reaction proceeded much slowly (entry
1). Considering trifluoroacetic acid (TFA) and Pd(OAc)2 can
facilitate the generation of more electropositive [Pd(II)O2CCF3]+
specie, which, compared with [Pd(II)OAc]+, possesses higher
activity for electrophilic substitution of C-H bonds to form σ-
phenyl-Pd complex,[12] 1.0 equiv of TFA was added to the
reaction system. To our delight, the reaction was accelerated
greatly and afforded the alkenylation product in 52% yield with
complete ortho-regioselectivity and E diastereoselectivity (entry
2). Next, the amount of TFA was investigated, and 2.0 equiv of
TFA (with respect to the substrate) gave the best result (entries
3-5). Then the palladium source was examined (Table 1, entries
6, 7); Pd(TFA)2 or PdCl2 did not improve the yield of the desired
product. In the absence of palladium catalyst, the reaction would
not occur (entry 8). After careful solvent screening,
hexafluoroisopropanol (HFIP) proved to be the best solvent to
give excellent yield (Table 1, entries 9–10). Finally we checked
the amount of the catalyst Pd(OAc)2, and we found the
conversion decreased remarkably when Pd(OAc)2 was reduced
to 5 mol% (Table 1, entry 11). Accordingly, the reaction
conditions were optimized as follows: Pd(OAc)2 (10% mol), TFA
(2.0 equiv.) under oxygen atmosphere in the solvent HFIP at
60 ℃. Next, we wondered if the reaction would proceed through
a seven-membered cyclopalladated intermediate. So under the
optimized reaction conditions, the substrates 1b and 1c without
pyridyl group were utilized in the transformation. The reactions
Phenol is ubiquitous structural motif in natural products,
pharmaceuticals and organic materials.[6] Therefore, the
functionalization of phenol and its derivatives have attracted
intensive efforts from the community studying C−H activations
and
functionalizations.
In
this
regard,
ortho-C-H
functionalizations of phenols are interesting subjects.[7] Despite
of tremendous progress,[8] further development of efficient ortho-
C-H functionalizations of phenols is still in demand because
most of the systems reported suffered from following synthetic
restrictions: harsh reaction conditions (e.g. high reaction
temperature and highly acidic medium), the challenge with
respect to the removal/transformation of undesired external
directing group or a limited substrate scope. Moreover, most
reactions required large excess of oxidants such as inorganic
salts (AgOAc, Cu(OAc)2, etc.), BQ, DDQ, IBX, and PhI(OAc)2 to
regenerate the catalyst, which produced at least stoichiometric
[a]
B. Li, D. –D. Guo, S. –H. Guo, G. –F. Pan, Y. –R. Gao, Prof. Dr. Y.
–Q. Wang*
Key Laboratory of Synthetic and Natural Functional Molecule
Chemistry of Ministry of Education, Department of Chemistry &
Materials Science, Northwest University, Xi’an 710069, P. R. China,
E-mail: wangyq@nwu.edu.cn.
Supporting information for this article is given via a link at the end of
the document.
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Table 1. Optimization of Reaction Conditions.a
entry
1
Catalyst
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(TFA)2
PdCl2
solvent]
DCE
TFA(equiv)
-
yield (%)b
15
52
76
75
65
45
<5
0
2
DCE
1.0
3
DCE
2.0
4
DCE
3.0
5
DCE
5.0
6
DCE
2.0
7
DCE
2.0
8
-
DCE
2.0
9
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
solventsc
HFIP
HFIP
DCE
2.0
<20
95
45
0
10
11d
12e
2.0
Scheme 1. Alkenylation of Phenol Derivatives.
2.0
2.0
was found at the position ortho to the CO2Et or COMe in spite of
them also being good directing groups for C-H bond activation
reactions (3ia-3ka).[8c,13,14] Pleasingly, disubstituted substrates
and naphthol derivatives were also amenable to the olefination
reaction, which proceeded with high selectivity at the more
accessible position (3oa-3sa). Interestingly, the substrate with
two 2-pyridylsulfonate directing groups only provided
monoalkenylated product in excellent yield under the standard
reaction conditions (3ta).
As shown in Scheme 2, the present reaction protocol was
successfully extended to other acrylates. Ethyl acrylate and n-
butyl acrylate reacted efficiently with 1a to give the
corresponding products 3ab and 3ac in 88% and 86% yields,
[a] Reaction conditions: 1a (1.0 mmol), 2a (2.0 mmol), catalyst, O2 (1 atm) and
TFA in solvent (10 ml) for 16 h. [b] Isolated yield after purification by flash
colum chromatography. [c] Solvents: toluene, AcOH, 1,4-Dioxane, DMSO,
MeOH, CH3CN, THF, DMA, i-PrOH, t-BuOH, 2,2,2-trifluoroethanol, CH3NO2.
[d] 5% Pd(OAc)2. [e] 1b or 1c used as substrate.
did not proceed, which demonstrated that the pyridyl group is
absolutely necessary for the reaction. Based on these
experiments and pioneering reports,3e,10b we considered that a
seven-membered palladacycle including nitrogen atom of pyridyl
group was likely a key intermediate.
Then, we moved on to explore the scope of the transformation.
First, we studied the effect of electronic and structural variations
on the phenol ring (Scheme 1). A broad range of substituent
groups with diverse steric and electronic properties (ether, alkyl,
halide, acetyl and ester groups) at ortho-, meta- or para-position
of aryl rings all were compatible with this procedure, affording
the corresponding olefinated products in 72-96% yields with
complete regio- and diastereoselectivity. Halides (F, Cl, Br and I
groups) survived under the reaction conditions. This is a
synthetically interesting result as such substituents are versatile
handles for further transformations. The high regiocontrol was
observed in meta-substituted substrates, in favor of the C-H
functionalization at the sterically less-hindered ortho-position
(3ha-3ja). It is noteworthy that the regioselectivity of the reaction
was highlighted again, alkenylation occurred only at the C-H
ortho to the 2-pyridylsulfonate substituent, while no alkenylation
respectively.
Acrylamide,
vinyl
phosphonate,
1,1-
diphenylethylene and vinyl sulfone were also good partners for
1aa in the olefination reaction, providing the desired products in
excellent yields (3ad-3ag). The smooth reactions of vinyl sulfone
with various phenyl 2-pyridylsulfonates possessing different
steric and electronic property showed the generality of the
olefination reaction (3ag, 3og, 3ug and 3vg).
1,2-Disubstituted alkenes are particular substrates due to the
few precedents and lower reactivity of this kind of olefin in
oxidative alkenylation (Fujiwara-Moritani) reactions.[15]
Delightedly, under the standard reaction conditions, dimethyl
m a l e at e r e ac t e d s m o o t h l y w i t h v ar i o us p h e n yl
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O
O
PyO2S
PyO2S
R
O
O
CO2Me
O
O
Pd(OAc)2 (10 mol%)
TFA (2 equiv), HFIP
OMe
OMe
+
R
CO2Me
O2 (1 atm), 60
℃
,14-20h
2h
1
3
PyO2S
PyO2S
PyO2S
PyO2S
CO2Me
O
CO2Me
CO2Me
O
EtO
CO2Me
3ah, 89%
CO2Me
3wh, 88%
CO2Me
3xh, 96%
Me
PyO2S
PyO2S
O
CO2Me
O
CO2Me
O
CO2Me
CO2Me
3a'h, 88%
CO2Me
CO2Me
3zh, 91%
MeO
Me2N
PyO2S
3yh, 92%
Me
PyO2S
O
CO2Me
O
CO2Me
SO2Py
Me
O
O
CO2Me
CO2Me
3c'h, 92%
OMe
3b'h, 89%
3ai*, 88%
OMe
O
PyO2S
CO2Me
SO2Py
CO2Me
Scheme 2. Alkenylation of various alkenes.
O
CO2Me
CO2Me
2-pyridylsulfonates regardless of their electronic and structural
nature, affording the corresponding trisubstituted alkene
products in excellent yields (Scheme 3, 3ah, 3vh-3zh, and 3a’h-
3c’h). And dimethyl fumarate possessing reversed configuration
with dimethyl maleate was also suitable partner for the reaction
to produce the desired trisubstituted alkenes in high yields (3aj,
3vj and 3xj). It is noteworthy that the configuration of two
CO2Me gruops were completely reversed in both above
reactions, that is two CO2Me gruops were cis-configuration in
starting material but they were trans-configuration in the
products, and vice versa, which were confirmed by single-crystal
X-ray analyses of 3vh and 3vj. These stereochemical results
indicated that the mechanism of the reaction probably was a
syn-carbopalladation followed by a syn-dehydropalladation. (E)-
methyl crotonate was also an amenable substrate to give the
desired product 3ai in 88% yield.
3vh, 85%
Ph
3aj**, 85%
SO2Py
CO2Me
CO2Me
SO2Py
CO2Me
O
O
CO2Me
Me
3vj**, 85%
3xj**, 85%
Ph
*Reacted with (E)-methyl crotonate. **Reacted with dimethyl fumarate.
Scheme 3. Alkenylation of 1,2-Disubstituted Alkenes
Encouraged by the success of ortho-C-H olefination of
phenols via a seven-membered cyclopalladated intermediates,
we next explored the acetoxylation reaction with the similar
strategy. After optimizing the reaction conditions, we found that
the acetoxylation reaction could proceed successfully in the
presence of Pd(OAc)2 (10 mol %), K2S2O8 (2.0 equiv) in DCE /
AcOH (1:1) at 80 ℃ for 14 - 16 h. The reaction could be applied
to various substituted substrates, providing the desired products
in 75-89% yields (Scheme 4). For meta-substituted substrate,
the reaction also exhibited excellent regioselectivity (4h).
Unfortunately, formic acid and benzoic acid did not work under
the present reaction conditions. When TFA / TFAA took the
place of AcOH, the reaction of 1a afforded valueble catechol
derivative (8a) in 88% yield.
Scheme 4. Acetoxylation of Phenol Derivatives
2-Pyridylsulfonyl group could be readily removed by zinc in
NH4Cl (aq.) / THF (1:1) at room temperature, with the olefin
moiety untouched (Scheme 5). To further demonstrate the
synthetic potential of this methodology, we sought to explore the
possibility of the synthesis of coumarins and benzofurans from
phenyl 2-pyridylsulfonates (Scheme 6). It is well known that
coumarins and benzofurans are two kinds of valuable organic
molecules with broad biological and pharmacological activities,
Scheme 5. Removal of 2-Pyridylsulfonyl Group.
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could be facilely utilized in the synthesis of valuable coumarins
and benzofurans. The method might have many applications in
organic and medical chemistry. Detailed mechanistic
investigations and the extension of a similar reaction in other
organic molecules are currently underway.
Experimental Section
General Comments. All commercial reagents and solvents were used
as received without further purification. Reactions were followed with TLC
(0.254 mm silica gel 60-F plates). Visualization was accomplished with
UV light. Flash chromatographies were carried out on silica gel 200-300
mesh. Melting points (m. p.) were measured on electrothermal digital
melting point apparatus and were uncorrected. 1HNMR and 13CNMR
spectra were recorded at 400 MHz using CDCl3 or (CD3)2SO as solvent.
Spectra were referenced internally to the residual proton resonance in
CDCl3 (δ 7.26 ppm), (CD3)2SO (δ 2.50 ppm) or with tetramethylsilane
(TMS, δ 0.00 ppm) as the internal standard. Chemical shifts (δ) were
reported as part per million (ppm) in δ scale downfield from TMS.
Multiplicities are reported as follows: s = singlet, d = doublet, t = triplet, m
= multiplet, br. s = broad singlet. Infrared (IR) data were recorded as films
on potassium bromide plates on a Bruker Tensor 27 FT-IR spectrometer.
Absorbance frequencies are reported in reciprocal centimeters (cm-1).
High resolution mass spectra were acquired on a Bruker Daltonics
MicroTof-QII mass spectrometer. X-ray crystal structure analyses were
measured on Bruker Smart APEXIICCD instrument using Mo-Kα
radiation. The structures were solved and refined using the SHELXTL
software package.
Scheme 6. Synthesis of Coumarins and Benzofurans.
including antitumor,[16] anti-HIV,[17] antioxidant,[18] antibacterial,[19]
and anti-inflammatory activities.[20] After the coupling reactions of
phenyl 2-pyridylsulfonates and alkenes were complete, 2-
pyridylsulfonyl directing group was removed with above
conditions, then the resulting phenol products were treated with
Bu3P/MeOH to give coumarins (6aa, 6da and 6ha), alternatively
treated with Cs2CO3/CuCl2/DMF to provide benzofurans (7aa,
7da and 7vf). Both procedures proceeded very well to afford the
desired products in good yields.
A plausible mechanism for the reaction is shown in scheme 7.
Pd(OAc)2 is treated with TFA to get active Pd(O2CCF3)+,[12]
which affords the seven-membered cyclopalladated intermediate
(I) through the electronic attack of palladium(II) into phenyl 2-
pyridylsulfonate. Then coordination of alkene (intermediate II)
and insertion of C=C bond forms the palladium (II) complex III.
The subsequent β–hydride elimination results in the product and
librates Pd(0) which can be re-oxidized to Pd(O2CCF3)+ by O2 in
the presence of TFA to complete the catalytic cycle.
General procedure for pyridine-2-sulfonyl chloride synthesis.
To a 500 mL round bottom flask were added 13.5 mmol (1.50 g) pyridine-
2-thiol and 40 mL concerned H2SO4. Then 150 mL sodium hypochlorite
solution was added dropwise to the solution under ice bath. The reaction
mixture was left at 0 ℃ for 15 min, and finally extracted with 150 mL
DCM for three times. The organic layer was combined, dried with Na2SO4
and evaporated in vacuum to remove the solvents to give the product.
The product was used without further purification.
General procedure for phenyl pyridine-2-sulfonate synthesis.
To a solution of 10.6 mmol (1.00 g) of phenol dissolved in 50 mL DCM
was added 20.0 mmol (2.76 mL) Et3N. The mixture was stirred at room
temperature for 15 min and 20.0 mmol (3.54 g) pyridine-2-sulfonyl
chloride was added. Then the reaction was stirred overnight. The solvent
was removed by distillation and the mixture was purified by column
chromatography to give the product 1.
Phenyl pyridine-2-sulfonate (1a) Prepared according to general
procedure as
a white solid (2.24 g, obtained from 10.6 mmol
Scheme 7. Plausible Mechanism for the Alkenylation.
corresponding phenol, 90%) after purification by flash column
chromatography using a mixture of petroleum ether and ethyl acetate
(4:1 v/v). m. p. = 94 - 95 oC 1H NMR (400 MHz, CDCl3) δ 8.72 (d, J = 3.6
Hz, 1H), 7.86 (d, J = 3.2 Hz, 2H), 7.54 (d, J = 4.0 Hz, 1H), 7.25 – 7.10 (m,
3H), 7.02 (d, J = 7.6 Hz, 2H). 13C NMR (100 MHz, CDCl3) δ 153.1, 150.6,
149.6, 138.4, 129.8, 128.4, 127.3, 124.3, 122.2. HRMS (ESI) m/z calcd
for C11H9NO3SNa 258.0195 [M+Na]+; found 258.0188. IR (KBr): 3099,
1585, 1483, 1201, 1147, 1120, 796 cm-1.
Conclusions
In summary, we have successfully developed a simple and
efficient palladium(II)-catalyzed ortho-C-H alkenylation and
acetoxylation of phenyl 2-pyridylsulfonates via
membered cyclopalladated intermediate. The reaction exhibited
complete regio- and diastereoselectivity. 2-Pyridylsulfonyl group
can be easily removed and the resulting phenol derivatives
a seven-
2-Methoxyphenyl pyridine-2-sulfonate (1d) Prepared according to
general procedure as a colorless oil (488 mg, obtained from 2.0 mmol
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corresponding phenol, 92%) after purification by flash column
chromatography using a mixture of petroleum ether and ethyl acetate
(4:1 v/v). 1H NMR (400 MHz, CDCl3) δ 8.72 (d, J = 3.6 Hz, 1H), 7.95 (d, J
= 3.2 Hz, 2H), 7.63 – 7.49 (m, 1H), 7.20 – 7.11 (m, 2H), 6.92 – 6.79 (m,
2H), 3.49 (s, 3H).13C NMR (100 MHz, CDCl3) δ 154.1, 151.5, 150.2,
138.5, 138.2, 128.4, 128.0, 124.0, 123.9, 120.7, 112.7, 55.6. HRMS (ESI)
m/z calcd for C12H11NO4SNa 288.0301 [M+Na]+; found 288.0288. IR
(KBr): 3091, 1585, 1506, 1486, 1374, 1203, 1160, 1108, 875, 792 cm-1.
2-Ethoxyphenyl pyridine-2-sulfonate (1e) Prepared according to
general procedure as a colorless oil (519 mg, obtained from 2.0 mmol
corresponding phenol, 93%) after purification by flash column
chromatography using a mixture of petroleum ether and ethyl acetate
(4:1 v/v). 1H NMR (400 MHz, CDCl3) δ 8.76 (d, J = 3.1 Hz, 1H), 8.06 –
7.86 (m, 2H), 7.65 – 7.56 (m, 1H), 7.29 – 7.12 (m, 2H), 6.93 – 6.75 (m,
2H), 3.83 (q, J = 8.0 Hz, 2H), 1.14 (t, J = 8.0 Hz, 3H). 13C NMR (100 MHz,
CDCl3) δ 154.5, 151.0, 150.17, 138.8, 138.0, 128.2, 127.8, 124.1, 123.8,
120.6, 113.8, 64.2, 14.4. HRMS (ESI) m/z calcd for C13H13NO4SNa
302.0457 [M+Na]+; found 302.0454. IR (KBr): 3094, 1581, 1487, 1468,
1372, 1202, 1156, 1109, 877, 798 cm-1.
found 314.0823. IR (KBr): 2969, 1587, 1432, 1373, 1268, 1203, 1162,
1120, 993, 931, 842, 786 cm-1.
Ethyl 3-(pyridin-2-ylsulfonyloxy)benzoate (1i) Prepared according to
general procedure as a colorless oil (560 mg, obtained from 2.0 mmol
corresponding phenol, 91%) after purification by flash column
chromatography using a mixture of petroleum ether and ethyl acetate
(4:1 v/v). 1H NMR (400 MHz, CDCl3) δ 8.82 (d, J = 4.0 Hz m, 1H), 8.08 –
7.88 (m, 3H), 7.76 (s, 1H), 7.68 – 7.59 (m, 1H), 7.47 – 7.32 (m, 2H), 4.36
(q, J = 8.0 Hz, 2H), 1.38 (t, J = 8.0 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ
165.2, 153.4, 150.7, 149.6, 138.4, 132.4, 129.8, 128.4, 128.3, 126.8,
124.3, 123.4, 61.5, 14.3. HRMS (ESI) m/z calcd for C14H13NO5SNa
330.0407 [M+Na]+; found 330.0401. IR (KBr): 3081, 1585, 1485, 1385,
1203, 1197, 1141, 1124, 782 cm-1.
3-Acetylphenyl pyridine-2-sulfonate (1j) Prepared according to general
procedure as
a colorless oil (492 mg, obtained from 2.0 mmol
corresponding phenol, 93%) after purification by flash column
chromatography using a mixture of petroleum ether and ethyl acetate
1
(4:1 v/v). H NMR (400 MHz, CDCl3) δ 8.82 (s, 1H), 8.01 - 7.97 (m, 2H),
7.86 (d, J = 7.6 Hz, 1H), 7.69 – 7.65 (m, 2H), 7.55 – 7.24 (m, 2H), 2.57 (s,
3H). 13C NMR (100 MHz, CDCl3) δ 196.4, 153.3, 150.7, 149.9, 138.7,
138.4, 130.1, 128.4, 127.1, 126.9, 124.3, 122.0, 26.7. HRMS (ESI) m/z
calcd for C12H11NO4SNa 288.0301 [M+Na]+; found 288.0306. IR (KBr):
3083, 1756, 1585, 1486, 1345, 1199, 1132, 1020, 788 cm-1.
2-Chlorophenyl pyridine-2-sulfonate (1f) Prepared according to
general procedure as a white solid (484 mg, obtained from 2.0 mmol
corresponding phenol, 90%) after purification by flash column
chromatography using a mixture of petroleum ether and ethyl acetate
(4:1 v/v). m. p. = 102 – 104 oC. 1H NMR (400 MHz, CDCl3) δ 8.78 (d, J =
4.0 Hz, 1H), 8.06 (d, J = 6.0 Hz, 1H), 8.00- 7.95 (m, 1H), 7.65 – 7.61 (m,
1H), 7.44 (d, J = 8.0 Hz, 1H), 7.46 – 7.42 (m, 1H), 7.39 – 7.33 (m, 1H),
7.32 – 7.19 (m, 2H). 13C NMR (100 MHz, CDCl3) δ 153.9, 150.5, 146.0,
138.4, 130.7, 128.2, 128.1, 128.0, 127.3, 124.5, 124.1. HRMS (ESI) m/z
calcd for C11H8ClNO3SNa 291.9806 [M+Na]+; found 291.9809. IR (KBr):
3102, 1585, 1486, 1164, 1089, 856, 792 cm-1.
Ethyl 4-(pyridin-2-ylsulfonyloxy)benzoate (1k) Prepared according to
general procedure as a colorless oil (521 mg, obtained from 2.0 mmol
corresponding phenol, 85%) after purification by flash column
chromatography using a mixture of petroleum ether and ethyl acetate
(4:1 v/v). m. p. = 144 – 145 oC. 1H NMR (400 MHz, CDCl3) δ 8.93 – 8.69
(m, 1H), 8.01 – 7.79 (m, 4H), 7.71 – 7.55 (m, 1H), 7.35 – 7.03 (m, 2H),
4.36 (q, J = 8.0 Hz, 2H), 1.37 (t, J = 8.0 Hz,, 3H). 13C NMR (100 MHz,
CDCl3) δ 165.3, 153.2, 152.9, 150.7, 138.4, 131.3, 129.4, 128.3, 124.2,
122.2, 61.3, 14.2. HRMS (ESI) m/z calcd for C14H13NO5SNa 330.0407
[M+Na]+; found 330.0398. IR (KBr): 3088, 1582, 1481, 1383, 1201, 1197,
1140, 1124, 784 cm-1.
2-Bromophenyl pyridine-2-sulfonate (1g) Prepared according to
general procedure as a white solid (556 mg, obtained from 2.0 mmol
corresponding phenol, 89%) after purification by flash column
chromatography using a mixture of petroleum ether and ethyl acetate
(4:1 v/v). m. p. = 104 – 105 oC. 1H NMR (400 MHz, CDCl3) δ 8.76 (d, J =
4.5 Hz, 1H), 8.07 (d, J = 8.0 Hz, 1H), 8.01 – 7.95 (m, 1H), 7.65 – 7.61 (m,
1H), 7.52 (d, J = 8.0 Hz, 1H), 7.41 (d, J = 8.4 Hz, 1H), 7.34 – 7.30 (m,
1H), 7.21 – 7.09 (m, 1H). 13C NMR (100 MHz, CDCl3) δ 153.8 , 150.6 ,
147.3 , 138.5 , 133.8 , 128.8 , 128.5 , 128.4 , 124.2 , 124.2 . HRMS (ESI)
m/z calcd for C11H8BrNO3SNa 335.9300 [M+Na]+; found 335.9301. IR
(KBr): 3099, 1585, 1486, 1203, 1197, 1122, 1045, 997, 867, 707 cm-1.
3-tert-Butylphenyl pyridine-2-sulfonate (1h) Prepared according to
general procedure as a white solid (518 mg, obtained from 2.0 mmol
corresponding phenol, 89%) after purification by flash column
chromatography using a mixture of petroleum ether and ethyl acetate
(5:1 v/v). m. p. = 111 – 112 oC. 1H NMR (400 MHz, CDCl3) δ 8.86 (s, 1H),
7.97 – 7.93 (m , 2H), 7.66 – 7.64 (m, 1H), 7.38 – 7.21 (m, 2H), 7.01 –
6.97 (m, 2H), 1.21 (s, 9H). 13C NMR (100 MHz, CDCl3) δ 153.4 , 150.6 ,
149.6 , 138.1 , 129.3 , 128.0 , 124.5 , 124.2 , 119.5 , 119.3 , 34.7 , 31.1 .
55.5 . HRMS (ESI) m/z calcd for C15H17NO3SNa 314.0821 [M+Na]+;
4-Iodophenyl pyridine-2-sulfonate (1l) Prepared according to general
procedure as
a colorless oil (671 mg, obtained from 2.0 mmol
corresponding phenol, 93%) after purification by flash column
chromatography using a mixture of petroleum ether and ethyl acetate
(4:1 v/v). m. p. = 144 – 145 oC. 1H NMR (400 MHz, CDCl3) δ 8.81 (d, J =
4.4 Hz, 1H), 7.96 (d, J = 5.6 Hz, 2H), 7.63 – 7.58 (m, 3H), 6.89 (d, J = 8.8
Hz, 2H).13C NMR (100 MHz, CDCl3) δ 153.2, 150.7, 149.5, 138.9, 138.5,
128.4, 124.4, 124.3, 92.0. HRMS (ESI) m/z calcd for C11H8INO3SNa
383.9162 [M+Na]+; found 383.9167. IR (KBr): 3089, 1585, 1486, 1207,
1172, 842, 786 cm-1.
4-Chlorophenyl pyridine-2-sulfonate (1m) Prepared according to
general procedure as a white solid (500 mg, obtained from 2.0 mmol
corresponding phenol, 93%) after purification by flash column
chromatography using a mixture of petroleum ether and ethyl acetate
(4:1 v/v). m. p. = 114 – 115 oC. 1H NMR (400 MHz, CDCl3) δ 8.81 (d, J =
4.0 Hz, 1H), 7.98 (d, J = 4.0 Hz, 2H), 7.67 – 7.63 (m, 1H), 7.26 (d, J = 8.8
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Hz, 2H), 7.08 (d, J = 8.8 Hz, 2H). 13C NMR (100 MHz, CDCl3) δ 152.9,
150.7, 148.1, 138.5, 132.8, 129.8, 128.5, 124.3, 123.7. HRMS (ESI) m/z
calcd for C11H8ClNO3SNa 291.9806 [M+Na]+; found 291.9809. IR (KBr):
3099, 1585, 1486, 1203, 1164, 1141, 1089, 993, 871, 856 cm-1.
corresponding phenol, 92%) after purification by flash column
chromatography using a mixture of petroleum ether and ethyl acetate
(4:1 v/v). m. p. = 239 – 240 oC. 1H NMR (400MHz, CDCl3): δ 8.78 (d, J =
4.0 Hz, 1H), 7.92 (d, J = 7.6Hz, 1H), 7.83 – 7.67 (m, 4H), 7.58 (s, 1H),
7.54 – 7.48 (m, 1H), 7.46 – 7.39 (m, 2H), 7.24 – 7.17 (m, 1H). 13C NMR
(100MHz, CDCl3) δ 153.2, 150.7, 147.2, 138.4, 133.4, 131.9, 130.0,
128.3, 127.9, 127.8, 127.1, 126.6, 124.3, 120.9, 119.9. HRMS (ESI) m/z
calcd for C15H11NO3SNa 308.0352 [M+Na]+; found 308.0357. IR (KBr):
2957, 1574, 1433, 1265, 1195, 1121, 1072, 1043, 893, 789, 704 cm-1.
1-Acetylnaphthalen-2-yl pyridine-2-sulfonate (1s) Prepared according
to general procedure as a colorless solid (556 mg, obtained from 2.0
mmol corresponding phenol 85%) after purification by flash column
chromatography using a mixture of petroleum ether and ethyl acetate
(4:1 v/v). m. p. = 103 – 104 oC. 1H NMR (400MHz, CDCl3): δ 8.77 (d, J =
4.4 Hz, 1H), 7.97 – 7.79 (m, 4H), 7.79 – 7.64 (m, 1H), 7.64 – 7.34 (m,
4H), 2.64 (s, 3H). 13C NMR (100MHz, CDCl3) δ 201.7, 152.9, 150.8,
143.5, 138.5, 132.1, 131.6, 131.3, 129.6, 128.5, 128.4, 128.1, 126.8,
124.8, 124.3, 120.9, 32.9. HRMS (ESI) m/z calcd for C17H13NO4SNa
350.0457 [M+Na]+; found 350.0451. IR (KBr): 3085, 2955, 1774, 1574,
1433, 1265, 1174, 1072, 1043, 890, 789, 744 cm-1.
4-Fluorophenyl pyridine-2-sulfonate (1n) Prepared according to
general procedure as a coloelrss solid (471 mg, obtained from 2.0 mmol
corresponding phenol, 93%) after purification by flash column
chromatography using a mixture of petroleum ether and ethyl acetate
(4:1 v/v). m. p. = 144 – 145 oC. 1H NMR (400 MHz, CDCl3) δ 8.82 (d, J =
4.5 Hz, 1H), 7.97 (d, J = 4.0 Hz, 2H), 7.70 – 7.57 (m, 1H), 7.12 – 7.08 (m,
2H), 7.00 – 6.96 (m, 2H). 13C NMR (100 MHz, CDCl3) δ 161.0 (JC-F
=
245.2 Hz), 153.1, 150.7, 145.4 (JC-F = 2.8 Hz), 138.4, 128.4, 124.4, 124.0
(JC-F = 8.8 Hz), 116.5 (JC-F = 23.8 Hz). HRMS (ESI) m/z calcd for
C11H8FNO3SNa 276.0101 [M+Na]+; found 276.0103. IR (KBr): 3099,
1585, 1486, 1203, 1147, 1120, 865, 796, 705 cm-1.
2-Methoxy-4-methylphenyl pyridine-2-sulfonate (1o) Prepared
according to general procedure as a colorless oil (531 mg, obtained from
2.0 mmol corresponding phenol, 95%) after purification by flash column
chromatography using a mixture of petroleum ether and ethyl acetate
(4:1 v/v). 1H NMR (400MHz, CDCl3): δ 8.86 – 8.71 (m, 1H), 8.11 – 7.88
(m, 2H), 7.73 – 7.56 (m, 1H), 7.06 (d, J = 8.0 Hz, 1H), 6.70 – 6.66 (m,
2H), 3.51 (s, 3H), 2.30 (s, 3H). 13C NMR (100MHz, CDCl3) δ 154.4, 151.1,
150.2, 138.5, 138.0, 136.4, 127.8, 123.9, 123.6, 121.2, 113.5, 55.6, 21.5.
HRMS (ESI) m/z calcd for C13H13NO4SNa 302.0457 [M+Na]+; found
302.0452. IR (KBr): 3097,3083, 1581, 1371, 1190, 1111, 874, 792 cm-1.
2-tert-Butyl-4-methoxyphenyl pyridine-2-sulfonate (1p) Prepared
according to general procedure as a colorless oil (545 mg, obtained from
2.0 mmol corresponding phenol, 85%) after purification by flash column
chromatography using a mixture of petroleum ether and ethyl acetate
(4:1 v/v). 1H NMR (400MHz, CDCl3): δ 8.81 (d, J = 4.0 Hz, 1H), 8.13 (d, J
= 8.0 Hz, 2H), 8.10 - 7.97 (m, 1H), 7.63 – 7.59 (m, 1H), 7.39 (d, J = 8.8
Hz, 1H), 6.92 (d, J = 3.2 Hz, 1H), 6.69 – 6.65 (m, 1H), 3.75 (s, 3H), 1.38
(s, 9H). 13C NMR (100MHz, CDCl3) δ 157.3, 154.9, 150.6, 143.2, 142.9,
138.6, 128.1, 123.8, 122.3, 114.5, 110.6, 55.5, 34.8, 30.3. HRMS (ESI)
m/z calcd for C16H19NO4SNa 344.0927 [M+Na]+; found 344.0933. IR
(KBr): 3091, 2969, 1587, 1429, 1373, 1203, 1162, 1120, 993, 931, 842,
774 cm-1.
1,2-Phenylene dipyridine-2-sulfonate (1t) Prepared according to
general procedure as a colorless oil (666 mg, obtained from 2.0 mmol
corresponding phenol, 85%) after purification by flash column
chromatography using a mixture of petroleum ether and ethyl acetate
(4:1 v/v). m. p. = 136 – 138 oC. 1H NMR (400MHz, CDCl3): δ 8.71 (d, J =
4.4 Hz, 2H), 7.98 (d, J = 4.0 Hz, 4H), 7.67 – 7.54 (m, 1H), 7.37 - 7.24 (m,
4H). 13C NMR (100MHz, CDCl3) δ 153.2, 150.4, 141.4, 138.5, 128.4,
128.3, 124.6, 124.2. HRMS (ESI) m/z calcd for C16H12N2O6S2Na
415.0029 [M+Na]+; found 415.0022. IR (KBr): 3085, 1585, 1485, 1203,
1148, 1123, 788 cm-1.
4-Ethoxyphenyl pyridine-2-sulfonate (1u) Prepared according to
general procedure as a colorless oil (519 mg, obtained from 2.0 mmol
corresponding phenol, 93%) after purification by flash column
chromatography using a mixture of petroleum ether and ethyl acetate
1
(4:1 v/v). H NMR (400 MHz, CDCl3) δ 8.83 – 8.79 (m, 1H), 7.94 – 7.90
(m, 2H), 7.62 – 7.58 (m, 1H), 7.08 – 6.93 (m, 2H), 6.79 – 6.71 (m, 2H),
3.95 (q, J = 8.0 Hz, 2H), 1.37 (t, J = 8.0 Hz,, 3H). 13C NMR (100 MHz,
CDCl3) δ 157.7, 153.4, 150.6, 142.9, 138.2, 128.1, 124.4, 123.2, 115.1,
63.8, 14.7.HRMS (ESI) m/z calcd for C13H13NO4SNa 302.0457 [M+Na]+;
found 302.0451. IR (KBr): 3097, 3085, 1581, 1489, 1474, 1374, 1203,
1156, 1108, 877, 792 cm-1.
2-Acetyl-4-chlorophenyl pyridine-2-sulfonate (1q) Prepared according
to general procedure as
a white solid (528 mg from 2.0 mmol
corresponding phenol, 85%) after purification by flash column
chromatography using a mixture of petroleum ether and ethyl acetate
(4:1 v/v). m. p. = 132 – 133 oC. 1H NMR (400MHz, CDCl3): δ 8.89 – 8.68
(m, 1H), 8.12 – 7.97 (m, 2H), 7.79 – 7.55 (m, 2H), 7.36 – 7.30 (m, 1H),
7.49 – 7.23 (m, 1H), 2.60 (s, 3H). 13C NMR (100MHz, CDCl3) δ 196.6,
152.8, 150.8, 145.8, 138.6, 134.5, 133.2, 132.8, 130.0, 128.6, 124.8,
124.4, 30.6. HRMS (ESI) m/z calcd for C13H10ClNO4SNa 333.9911
[M+Na]+; found 333.9909. IR (KBr): 3103, 3083, 1582, 1476, 1223, 1164,
1124, 1088, 993, 872, 848 cm-1.
Biphenyl-4-yl pyridine-2-sulfonate (1v) Prepared according to general
procedure as
a white solid (578 mg, obtained from 2.0 mmol
corresponding phenol, 93%) after purification by flash column
chromatography using a mixture of petroleum ether and ethyl acetate
(4:1 v/v). m. p. = 137 – 138 oC. 1H NMR (400 MHz, CDCl3) δ 8.85 (d, J =
3.6 Hz, 1H), 8.08 – 7.92 (m, 1H), 7.70 – 7.60 (m, 1H), 7.58 – 7.51 (m,
4H), 7.49 – 7.34 (m, 3H), 7.21 (d, J = 8.4 Hz, 2H). 13C NMR (100 MHz,
CDCl3) δ 153.4, 150.7, 149.1, 140.4, 139.6, 138.4, 128.9, 128.4, 128.3,
127.8, 127.1, 124.4, 122.6. HRMS (ESI) m/z calcd for C17H13NO3SNa
Naphthalen-2-yl pyridine-2-sulfonate (1r) Prepared according to
general procedure as a white solid (525 mg, obtained from 2.0 mmol
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334.0508 [M+Na]+; found 334.0515. IR (KBr): 3099, 1585, 1486, 1203,
1147, 1120, 1022, 873,796, 775 cm-1.
(4:1 v/v). 1H NMR (400 MHz, CDCl3) δ 8.82 (d, J = 4.4 Hz, 1H), 8.08 –
7.90 (m, 2H), 7.55 – 7.42 (m, 1H), 7.08 (d, J = 8.4 Hz, 2H), 6.97 – 6.93
(m, 2H), 2.29 (s, 3H).13C NMR (100 MHz, CDCl3) δ 153.5 , 150.6 , 147.5 ,
138.2 , 137.2 , 130.2 , 128.0 , 124.3 , 122.0 , 20.9. HRMS (ESI) m/z
calcd for C12H11NO3SNa 272.0352 [M+Na]+; found 272.0354. IR (KBr):
3089, 1581, 1371, 1190, 1111, 879, 782 cm-1.
Ethyl 2-(pyridin-2-ylsulfonyloxy)benzoate (1w) Prepared according to
general procedure as a colorless oil (540 mg, obtained from 2.0 mmol
corresponding phenol, 88%) after purification by flash column
chromatography using a mixture of petroleum ether and ethyl acetate
(4:1 v/v). 1H NMR δ 8.69(d, J = 4.0 Hz, 1H), 7.97 – 7.88 (m, 2H), 7.83 (d,
J = 7.6 Hz, 1H), 7.63 – 7.53 (m, 1H), 7.46 – 7.36 (m, 1H), 7.31 – 7.23 (m,
1H), 7.07 (d, J = 8.0 Hz, 1H), 4.22 (q, J = 8.0 Hz,, 2H), 1.29 (t, J = 8.0 Hz,,
3H). 13C NMR (100 MHz, CDCl3) δ 164.5, 153.7 , 150.4 , 148.2, 138.5,
133.4, 131.9, 128.2, 127.2, 125.6, 124.0, 123.7, 61.5, 14.0. HRMS (ESI)
m/z calcd for C14H13NO5SNa 330.0407 [M+Na]+; found 330.0391. IR
(KBr): 3085, 1627, 1585, 1486, 1378, 1203, 1197, 1147, 1120, 782 cm-1.
3-Methylphenyl pyridine-2-sulfonate (1x) Prepared according to
general procedure as a colorless oil (448 mg, obtained from 2.0 mmol
corresponding phenol, 90%) after purification by flash column
chromatography using a mixture of petroleum ether and ethyl acetate
(4:1 v/v). 1H NMR (400 MHz, CDCl3) δ 8.83 (d, J = 4.0 Hz, 1H), 7.92 (d, J
= 4.0 Hz, 2H), 7.62 (d, J = 8.0 Hz, 1H), 7.21 – 7.11 (m, 1H), 7.07 – 6.97
(m, 1H), 6.97 (s, 1H), 6.85 (d, J = 8.0 Hz, 1H), 2.3 (s, 3H). 13C NMR (100
MHz, CDCl3) δ 153.4, 150.6, 149.5, 140.2, 138.3, 129.4, 128.2, 128.1,
124.3, 122.8, 119.0, 21.3. HRMS (ESI) m/z calcd for C12H11NO3SNa
272.0352 [M+Na]+; found 272.0342. IR (KBr): 3085, 1585, 1378, 1197,
1120, 782 cm-1.
4-Methoxyphenyl pyridine-2-sulfonate (1b’) Prepared according to
general procedure as a colorless oil (445 mg, obtained from 2.0 mmol
corresponding phenol, 84%) after purification by flash column
chromatography using a mixture of petroleum ether and ethyl acetate
(4:1 v/v). 1H NMR (400 MHz, CDCl3) δ 8.83 (d, J = 4.0 Hz, 1H), 7.94 (d, J
= 3.2 Hz, 2H), 7.64 – 7.53 (m, 1H), 7.00 (d, J = 2.8 Hz, 2H), 6.81 (d, J =
8.8 Hz, 3H), 3.74 (s, 3H).13C NMR (100 MHz, CDCl3) δ 158.3, 153.2,
150.6, 143.0, 138.3, 128.2, 124.4, 123.2, 116.1, 114.7, 114.6, 55.6.
HRMS (ESI) m/z calcd for C12H11NO4SNa 288.0301 [M+Na]+; found
288.0299. IR (KBr): 3097, 1581, 1489, 1474, 1374, 1203, 1156, 1108,
877, 792 cm-1.
Naphthalen-1-yl pyridine-2-sulfonate (1c’) Prepared according to
general procedure as a colorless oil (524 mg, obtained from 2.0 mmol
corresponding phenol 92%) after purification by flash column
chromatography using a mixture of petroleum ether and ethyl acetate
(4:1 v/v). 1H NMR (400 MHz, CDCl3) δ 8.77 (d, J = 4.0 Hz, 1H), 8.08 –
8.02 (m, 1H), 7.98 (d, J = 7.6 Hz, 1H), 7.90 – 7.80 (m, 2H), 7.79 – 7.69
(m, 1H), 7.58 – 7.35 (m, 5H). 13C NMR (100 MHz, CDCl3) δ153.5, 150.7,
145.7, 138.3, 134.7, 128.2, 127.8, 127.4, 127.1, 126.9, 126.8, 125.3,
124.2, 121.6, 118.6. HRMS (ESI) m/z calcd for C15H11NO3SNa 308.0352
[M+Na]+; found 308.0355. IR (KBr): 2956, 1585, 1436, 1265, 1195, 1120,
1072, 1043, 894, 798, 713 cm-1.
3-Methoxyphenyl pyridine-2-sulfonate (1y) Prepared according to
general procedure as a colorless oil (493 mg, obtained from 2.0 mmol
corresponding phenol, 93%) after purification by flash column
chromatography using a mixture of petroleum ether and ethyl acetate
(4:1 v/v). 1H NMR (400 MHz, CDCl3) δ 8.87 (d, J = 3.6 Hz, 1H), 8.07 –
7.77 (m, 2H), 7.75 – 7.53 (m, 1H), 7.26 – 7.09 (m, 1H), 6.90 – 6.76 (m,
1H), 6.74 – 6.57 (m, 2H), 3.75 (s, 3H). 13C NMR (100 MHz, CDCl3) δ
160.5 , 153.4, 150.6 , 150.4 , 138.2, 130.0, 128.1, 124.4, 114.2, 113.2,
108.2, 55.5. HRMS (ESI) m/z calcd for C12H11NO4SNa 288.0301
[M+Na]+; found 288.0299. IR (KBr): 3095, 1581, 1498, 1486, 1372, 1203,
1160, 1107, 872, 792 cm-1.
4-Acetylphenyl pyridine-2-sulfonate (1d’) Prepared according to
general procedure as a colorless oil (514 mg, obtained from 2.0 mmol
corresponding phenol, 93%) after purification by flash column
chromatography using a mixture of petroleum ether and ethyl acetate
(4:1 v/v). 1H NMR (400 MHz, CDCl3) δ 8.85 - 8.80 (m, 1H), 8.02 - 7.90 (m,
4H), 7.28 - 7.22 (m, 2H), 2.58 (s, 3H). 13C NMR (100 MHz, CDCl3) δ
196.7, 153.3, 153.1, 150.7, 138.4, 135.8, 130.2, 128.3, 124.2, 122.4,
26.7. HRMS (ESI) m/z calcd for C13H11NO4SNa 300.0301 [M+Na]+; found
300.0304. IR (KBr): 3359, 3104, 2921, 1683, 1365, 1222, 1140, 796, 623
cm-1.
3-(Dimethylamino)phenyl
pyridine-2-sulfonate
(1z)
Prepared
according to general procedure as a white solid (517 mg, obtained from
2.0 mmol corresponding phenol, 93%) after purification by flash column
chromatography using a mixture of petroleum ether and ethyl acetate
(4:1 v/v). m. p. = 124 – 125 oC. 1H NMR (400 MHz, CDCl3) δ 8.75 (d, J =
4.0 Hz, 1H), 8.11 – 7.85 (m, 2H), 7.67 – 7.50 (m, 1H), 7.11 – 6.99 (m,
1H), 6.66 – 6.44 (m, 1H), 6.41 – 6.11 (m, 2H), 2.79 (s, 6H). 13C NMR
(100 MHz, CDCl3) δ 153.4, 151.5, 150.7, 150.5, 138.3, 129.8, 128.2,
124.4, 110.9, 109.0, 105.6, 40.1. HRMS (ESI) m/z calcd for
C13H14N2O3SNa 301.0617 [M+Na]+; found 301.0619. IR (KBr): 3085,
2915,1585, 1486, 1203, 1147, 1120, 1087, 799 cm-1.
General procedure for alkenylation of phenyl pyridine-2-sulfonate
synthesis.
A
round bottom flask containing the phenyl pyridine-2-sulfonate
derivative 1 (2.0 mmol), Pd(OAc)2 (120 mg, 10 mol%) was evacuated
and filled with dioxygen gas using an oxygen containing balloon. Then,
Hexafluoroisopropanol (10 mL), alkene 2 (4.0 mmol) and trifluoroacetic
acid (TFA, 4 mmol) were sequentially added to the system under an
oxygen atmosphere. (If alkene 2 is a solid, it can be charged with phenyl
pyridine-2-sulfonate derivative 1 in the full oxygen round bottom flask.)
The mixture was heated to 60 ºC for 12-16 h. It was allowed to reach
room temperature and concentrated under reduced pressure. Purification
4-Methylphenyl pyridine-2-sulfonate (1a’) Prepared according to
general procedure as a colorless oil (464 mg, obtained from 2.0 mmol
corresponding phenol, 93%) after purification by flash column
chromatography using a mixture of petroleum ether and ethyl acetate
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by flash chromatography afforded the alkenylated phenyl pyridine-2-
sulfonate derivative 3.
(KBr): 3099, 2940, 1725, 1656, 1617, 1496, 1384, 1270, 1201, 1176,
1085, 860, 715 cm-1.
Methyl 3-(2-(pyridin-2-ylsulfonyloxy)phenyl)acrylate (3aa) Prepared
according to general procedure as a colorless oil (30.3 mg, obtained from
0.1 mmol corresponding phenyl 2-pyridinesulfonate, 95%) after
purification by flash column chromatography using a mixture of petroleum
2-(2-(Diethoxyphosphoryl)vinyl)phenyl pyridine-2-sulfonate (3ae)
Prepared according to general procedure as a yellow oil (38.1 mg,
obtained from 0.1 mmol corresponding phenyl 2-pyridinesulfonate, 96%)
after purification by flash column chromatography using a mixture of
petroleum ether and ethyl acetate (3:1 v/v). 1H NMR (400MHz, CDCl3): δ
8.94 – 8.73 (m, 1H), 8.03 – 7.99 (m, 2H), 7.69 – 7.48 (m, 3H), 7.42 –
7.25 (m, 3H), 6.28 – 6.24 (m, 1H), 4.14 (q, J = 8.0 Hz, 4H), 1.37 (t, J =
8.0 Hz, 6H). 13C NMR (100MHz, CDCl3) δ 153.1, 150.7, 147.7, 140.8,
140.7, 138.5, 131.2, 128.7, 128.5, 128.4, 127.6, 127.4, 124.1, 123.3,
118.1 ,116.2 ,62.1 ,62.0 ,16.4 ,16.3 . HRMS (ESI) m/z calcd for
C17H20NO6PSNa 420.0641 [M+Na]+; found 420.0642. IR (KBr): 2991,
1623, 1354, 1255, 1203, 1164, 1049, 973, 881, 781 cm-1.
1
ether and ethyl acetate (3:1 v/v). H NMR (400MHz, CDCl3): δ 8.74 (d, J
= 4.4 Hz, 1H), 8.03 – 7.87 (m, 2H), 7.64 – 7.57 (m, 3H), 7.54 – 7.50 (m,
2H), 7.43 – 7.25 (m, 1H), 6.24 (d, J = 16.4 Hz, 1H), 3.75 (s, 3H). 13C
NMR (100MHz, CDCl3) δ 166.5, 153.0, 150.7, 148.0, 138.5, 137.3, 131.5,
128.3, 128.0, 127.7, 127.6, 124.2, 123.7, 120.1, 51.8. HRMS (ESI) m/z
calcd for C15H13NO5SNa 342.0407 [M+Na]+; found 342.0404. IR (KBr):
3083, 2960, 1722, 1643, 1488, 1326, 1205, 1087, 781 cm-1.
Ethyl 3-(2-(pyridin-2-ylsulfonyloxy)phenyl)acrylate (3ab) Prepared
according to general procedure as a colorless oil (29.3 mg, obtained from
0.1 mmol corresponding phenyl 2-pyridinesulfonate, 88%) after
purification by flash column chromatography using a mixture of petroleum
ether and ethyl acetate (3:1 v/v). 1H NMR (400MHz, CDCl3): δ 8.77 –
8.71 (m, 1H), 8.10 – 7.89 (m, 2H), 7.65 - 7.51 (m, 3H), 7.43 - 7.39 (m,
2H), 7.33 - 7.27 (m, 1H), 6.22 (d, J = 16.0 Hz, 2H), 4.23 (q, J = 8.0 Hz,
2H), 1.33 (t, J = 8.0 Hz, 3H). 13C NMR (100MHz, CDCl3) δ 166.1, 153.1,
150.7, 148.0, 138.5, 137.0, 131.4, 128.2, 128.1 , 127.7, 127.6, 124.2,
123.8, 120.6, 60.6, 14.4. HRMS (ESI) m/z calcd for C16H15NO5SNa
356.0563 [M+Na]+; found 356.0559. IR (KBr): 3072, 2989, 1714, 1641,
1585, 1484, 1376, 1201, 1087, 781, 698 cm-1.
2-(2,2-Diphenylvinyl)phenyl pyridine-2-sulfonate (3af) Prepared
according to general procedure as a colorless oil (34.3 mg, obtained from
0.1 mmol corresponding phenyl 2-pyridinesulfonate, 83%) after
purification by flash column chromatography using a mixture of petroleum
ether and ethyl acetate (3:1 v/v). 1H NMR (400 MHz, CDCl3) δ 8.50 (d, J
= 4.0 Hz, 1H), 8.00 (d, J = 4.0 Hz, 1H), 7.76 – 7.68 (m, 1H), 7.38 – 7.26
(m, 9H), 7.24 – 7.14 (m, 3H), 7.08 – 7.00 (m, 2H), 6.91 (d, J = 6.8 Hz,
1H), 6.82 (s, 1H), 6.75 (d, J = 3.6Hz, 1H).13C NMR (100 MHz, CDCl3) δ
154.1, 150.5, 148.4, 144.4, 142.6, 139.4, 137.9, 130.9, 130.7, 130.4,
127.9, 126.5, 123.8, 123.4, 121.3. HRMS (ESI) m/z calcd for
C25H19NO3SNa 436.0978 [M+Na]+; found 436.0983. IR (KBr): 3093, 3054,
1581, 1489, 1313, 1203, 1147, 1120, 1021, 840, 796, 775, 578 cm-1.
n-Butyl 3-(2-(pyridin-2-ylsulfonyloxy)phenyl)acrylate (3ac) Prepared
according to general procedure as a colorless oil (31.0 mg, obtained from
0.1 mmol corresponding phenyl 2-pyridinesulfonate, 86%) after
purification by flash column chromatography using a mixture of petroleum
2-(2-(Phenylsulfonyl)vinyl)phenyl
pyridine-2-sulfonate
(3ag)
Prepared according to general procedure as a colorless oil (28.8 mg,
obtained from 0.1 mmol corresponding phenyl 2-pyridinesulfonate, 72%)
after purification by flash column chromatography using a mixture of
petroleum ether and ethyl acetate (3:1 v/v). 1H NMR (400MHz, CDCl3): δ
8.78 (d, J = 4.0 Hz, 1H), 8.06 (d, J = 8.0 Hz, 1H), 8.02 – 7.95 (m, 1H),
7.91 (d, J = 7.2 Hz, 2H), 7.75 (d, J = 16.0 Hz, 1H), 7.68 – 7.59 (m, 2H),
7.56 – 7.52 (m, 2H), 7.47 – 7.44 (m, 3H), 7.34 – 7.25 (m, 1H), 6.86 (d, J
1
ether and ethyl acetate (3:1 v/v). H NMR (400MHz, CDCl3): δ 8.76 (d, J
= 4.0 Hz, 1H), 8.11 – 7.90 (m, 2H), 7.70 – 7.54 (m, 3H), 7.49 – 7.41 (m,
2H), 7.38 - 7.32 (m, 1H), 6.26 (d, J = 16.0 Hz, 1H), 4.20 (t, J = 8.0 Hz,,
2H), 1.76 – 1.63 (m, 2H), 1.58 – 1.43 (m, 2H), 1.00 (t, J = 8.0 Hz,, 3H).
13C NMR (100MHz, CDCl3) δ 166.2, 153.2, 150.6, 148.1, 138.3, 138.2,
137.1, 131.4, 129.7, 128.1, 127.6, 124.2, 123.8, 120.6, 64.5, 30.7, 19.2,
13.8. HRMS (ESI) m/z calcd for C18H19NO5SNa 384.0876 [M+Na]+; found
384.0878. IR (KBr): 3069, 2992, 2987, 1718, 1641, 1585, 1488, 1376,
1201, 1087, 781, 698 cm-1.
=
16.0
Hz,
1H).
13C
NMR
(100MHz,
CDCl3)
δ153.0 ,151.0 ,148.3 ,140.2 ,138.8, 135.6, 133.6, 132.4, 129.8, 129.4,
128.7, 128.5, 127.8, 127.7, 126.1, 124.2, 123.9. HRMS (ESI) m/z calcd
for C19H15NO5S2Na 424.0284 [M+Na]+; found 424.0286. IR (KBr): 3056,
1623, 1452, 1311, 1207, 1085, 877, 815, 808 cm-1.
2-(3-(Dimethylamino)-3-oxoprop-1-enyl)phenyl pyridine-2-sulfonate
(3ad) Prepared according to general procedure as a colorless oil (31.9
mg, obtained from 0.1 mmol corresponding phenyl 2-pyridinesulfonate,
96%) after purification by flash column chromatography using a mixture
of petroleum ether and ethyl acetate (3:1 v/v). 1H NMR (400MHz, CDCl3):
δ 8.79 (d, J = 4.0 Hz, 1H), 8.06 (d, J = 8.0 Hz, 1H), 8.00 – 7.87 (m, 1H),
7.70 – 7.56 (m, 1H), 7.54 – 7.45 (m, 2H), 7.43 – 7.21 (m, 3H), 6.89 (d, J
= 16.0 Hz, 1H), 3.24 – 3.15 (s, 3H), 3.11 – 3.00 (s, 3H). 13C NMR
(100MHz, CDCl3 ) δ 166.1, 153.4, 150.5, 147.9, 138.4, 135.0, 130.4,
129.0, 128.8, 128.2, 127.4, 124.2, 123.4, 121.2, 37.5, 35.9. HRMS (ESI)
m/z calcd for C16H16N2O4Sna 355.0723 [M+Na]+; found 355.0714. IR
Dimethyl
2-(2-(pyridin-2-ylsulfonyloxy)phenyl)maleate
(3ah)
Prepared according to general procedure as a colorless oil (33.5 mg,
obtained from 0.1 mmol corresponding phenyl 2-pyridinesulfonate, 89%)
after purification by flash column chromatography using a mixture of
petroleum ether and ethyl acetate (3:1 v/v). 1H NMR (400MHz, CDCl3): δ
8.77 (d, J = 4.4 Hz, 1H), 7.95 – 7.90 (m, 2H), 7.61 – 7.55 (m, 1H), 7.40 –
7.15 (m, 4H), 7.02 (d, J = 3.6 Hz, 1H), 3.78 (s, 3H), 3.60 (s, 3H). 13C
NMR (100MHz, CDCl3) δ 165.6, 164.7, 153.8, 150.5, 146.9, 139.9, 138.2,
131.1, 130.5, 130.1, 128.0, 127.9, 126.5, 124.1, 122.1, 53.1, 52.0. HRMS
(ESI) m/z calcd for C17H15NO7SNa 400.0461 [M+Na]+; found 400.0465.
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IR (KBr): 3083, 3016, 2960, 1722, 1643, 1488, 1444, 1394, 1326, 1232,
1205, 1174, 831 cm-1.
137.9, 137.8, 129.6, 128.0, 127.8, 123.6, 120.4, 118.5, 115.1, 64.7, 51.7,
14.3. HRMS (ESI) m/z calcd for C17H17NO6SNa 386.0669 [M+Na]+; found
386.0668. IR (KBr): 3079, 1718, 1638, 1472, 1382, 1321, 1208, 1081,
1022, 791, 698 cm-1.
Methyl-3-(2-(pyridin-2-ylsulfonyloxy)phenyl)but-2-enoate
(3ai)
Prepared according to general procedure as a colorless oil (29.3 mg,
obtained from 0.1 mmol corresponding phenyl 2-pyridinesulfonate, 88%)
after purification by flash column chromatography using a mixture of
petroleum ether and ethyl acetate (3:1 v/v). 1H NMR (400MHz, CDCl3): δ
8.66 (d, J = 4.8 Hz, 1H), 7.87 – 7.32 (m, 2H), 7.56 – 7.45 (m, 1H), 7.39 –
7.14 (m, 4H), 7.08 (d, J = 7.6 Hz, 1H), 5.46 (s, 1H), 3.64 (s, 3H), 2.26 (s,
3H). 13C NMR (100MHz, CDCl3) δ 165.2, 152.6, 152.3, 149.5, 145.2,
137.1, 136.1, 128.7, 128.3, 126.9, 126.4, 123.0, 122.7, 121.3, 119.2,
50.1, 18.7. HRMS (ESI) m/z calcd for C16H15NO5SNa 356.0563 [M+Na]+;
found 356.0553. IR (KBr): 3083, 3045, 2948, 1721, 1637, 1472, 1326,
1205, 1089, 789 cm-1.
(E)-Methyl
3-(3-chloro-2-(pyridin-2-ylsulfonyloxy)phenyl)acrylate
(3fa) Prepared according to general procedure as a white solid (30.3 mg,
obtained from 0.1 mmol corresponding phenyl 2-pyridinesulfonate, 86%)
after purification by flash column chromatography using a mixture of
petroleum ether and ethyl acetate (3:1 v/v). m. p. = 112 – 113 oC. 1H
NMR (400MHz, CDCl3): δ 8.80 (d, J = 4.0 Hz, 1H), 8.22 – 7.96 (m, 2H),
7.66 – 7.62 (m, 2H), 7.60 – 7.42 (m, 2H), 7.35 – 7.23 (m, 1H), 6.30 (d, J
= 16.0 Hz, 1H), 3.75 (s, 3H).13C NMR (100MHz, CDCl3) δ 166.2, 153.8,
150.8, 144.7, 138.6, 137.4, 132.2, 131.1, 129.6, 128.4, 128.1, 126.0,
124.1, 121.2, 51.8. HRMS (ESI) m/z calcd for C15H12NO5ClSNa 376.0017
[M+Na]+; found 376.0012. IR (KBr): 3098, 1714, 1641, 1577, 1474, 1160,
1089, 825, 782, 711 cm-1. CCDC 1509678 contains the supplementary
crystallographic data for this paper. These data can be obtained free of
charge from the Cambridge Crystallographic Data Centre.
Dimethyl
2-(2-((pyridin-2-ylsulfonyl)oxy)phenyl)maleate
(3aj)
Prepared according to general procedure as a colorless oil (33.5 mg,
obtained from 0.1 mmol corresponding phenyl 2-pyridinesulfonate, 89%)
after purification by flash column chromatography using a mixture of
petroleum ether and ethyl acetate (3:1 v/v). 1H NMR (400 MHz, CDCl3) δ
8.71 - 8.68 (m, 1H), 8.04 – 8.01 (m, 1H), 7.97 – 7.92 (m, 1H), 7.63 – 7.58
(m, 1H), 7.45 – 7.38 (m, 2H), 7.35 – 7.25 (m, 2H), 6.19 (s, 1H), 3.78 (s,
3H), 3.75 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 166.7, 164.9, 153.3,
147.4, 138.3, 131.3, 130.4, 128.5, 128.3, 127.6, 124.6, 124.4, 123.3,
52.6, 52.1. HRMS (ESI) m/z calcd for C17H15NO7SNa 400.0461 [M+Na]+;
found 400.0462. IR (KBr): 3079, 3031, 2957, 2712, 1720, 1644, 1487,
1432, 1324, 1231, 1201, 1174, 831, 721 cm-1.
Methyl 3-(3-chloro-2-(pyridin-2-ylsulfonyloxy)phenyl)acrylate (3ga)
Prepared according to general procedure as a colorless oil (34.8 mg,
obtained from 0.1 mmol corresponding phenyl 2-pyridinesulfonate, 88%)
after purification by flash column chromatography using a mixture of
petroleum ether and ethyl acetate (3:1 v/v). 1H NMR (400MHz, CDCl3): δ
8.79 (d, J = 4.0 Hz, 1H), 8.19 – 7.91 (m, 2H), 7.63 – 7.60 (m, 4H), 7.21 –
7.17 (m, 1H), 6.28 (d, J = 16.0 Hz, 1H), 3.74 (s, 3H). 13C NMR (100MHz,
CDCl3) δ 166.1, 153.8, 150.8, 145.9, 138.6, 137.6, 135.4, 131.1, 128.5,
128.5, 126.8, 124.2, 121.1, 118.7, 51.8. HRMS (ESI) m/z calcd for
C15H12NO5BrSNa 419.9512 [M+Na]+; found 419.9498. IR (KBr): 3079,
1720, 1629, 1469, 1382, 1207, 1197, 1122, 1045, 997, 867, 707 cm-1.
Methyl 3-(4-tert-butyl-2-(pyridin-2-ylsulfonyloxy)phenyl)acrylate (3ha)
Prepared according to general procedure as a colorless oil (36.0 mg,
obtained from 0.1 mmol corresponding phenyl 2-pyridinesulfonate, 96%)
after purification by flash column chromatography using a mixture of
petroleum ether and ethyl acetate (3:1 v/v). 1H NMR (400MHz, CDCl3): δ
8.81 (d, J = 4.0 Hz, 1H), 8.14 – 7.86 (m, 2H), 7.76 – 7.57 (m, 2H), 7.52 –
7.42 (m, 1H), 7.35 – 7.26 (m, 1H), 6.25 (d, J = 16.0 Hz, 1H), 3.76 (s, 3H),
1.25 (s, 9H). 13C NMR (100MHz, CDCl3) δ 166.7, 155.6, 153.2, 150.7,
147.9, 138.4, 137.4, 128.2, 127.2, 125.1, 124.8, 124.3, 120.9, 119.2,
51.7, 35.0, 30.9. HRMS (ESI) m/z calcd for C19H22NO5SNa 398.1033
[M+Na]+; found 398.1030. IR (KBr): 3023, 2986, 1732, 1655, 1488, 1430,
1370, 1259, 1212, 1148, 985, 877, 825 cm-1.
Methyl 3-(3-methoxy-2-(pyridin-2-ylsulfonyloxy)phenyl)acrylate (3da)
Prepared according to general procedure as a colorless solid (33.1 mg,
obtained from 0.1 mmol corresponding phenyl 2-pyridinesulfonate, 95%)
after purification by flash column chromatography using a mixture of
petroleum ether and ethyl acetate (3:1 v/v). m. p. = 124 – 125 oC. 1H
NMR (400MHz, CDCl3): δ 8.84 (d, J = 4.0 Hz, 1H), 8.18 – 7.91 (m, 2H),
7.81 – 7.50 (m, 2H), 7.34 – 7.12 (m, 2H), 6.92 (d, J = 8.0 Hz, 1H), 6.29 (d,
J = 16.0 Hz, 1H), 3.76 (s, 3H), 3.68 (s, 3H). 13C NMR (100MHz, CDCl3) δ
166.5, 154.5 , 152.7 , 150.4 , 138.2, 137.8, 129.8, 127.8, 127.8, 123.7,
120.6, 118.8, 114.1, 56.1, 51.7. HRMS (ESI) m/z calcd for
C16H15NO6SNa 372.0512 [M+Na]+; found 372.0514. IR (KBr): 3097, 1720,
1650, 1583, 1440, 1382, 1276, 1199, 1068, 1022, 875, 792 cm-1. CCDC
1509677 contains the supplementary crystallographic data for this paper.
These data can be obtained free of charge from the Cambridge
Crystallographic Data Centre.
(E)-Methyl
3-(3-ethoxy-2-(pyridin-2-ylsulfonyloxy)phenyl)acrylate
Ethyl
4-(3-methoxy-3-oxoprop-1-enyl)-3-(pyridin-2-ylsulfonyloxy)
(3ea) Prepared according to general procedure as a colorless oil (31.9
mg, obtained from 0.1 mmol corresponding phenyl 2-pyridinesulfonate,
88%) after purification by flash column chromatography using a mixture
of petroleum ether and ethyl acetate (3:1 v/v). 1H NMR (400MHz, CDCl3):
δ 8.78 (d, J = 4.0 Hz, 1H), 8.11 – 7.93 (m, 2H), 7.73 (d, J = 16.0 Hz, 1H),
7.65 – 7.60 (m, 1H), 7.27 – 7.11 (m, 2H), 6.98 – 7.93 (m, 1H), 6.33 (d, J
= 16.0 Hz, 1H), 3.93 (q, J = 8.0 Hz, 2H), 3.73(s, 3H), 1.19 (t, J = 8.0 Hz,
3H). 13C NMR (100MHz, CDCl3) δ 166.5, 154.5, 152.0, 150.4, 138.4,
benzoate (3ia) Prepared according to general procedure as a colorless
oil (28.2 mg, obtained from 0.1 mmol corresponding phenyl 2-
pyridinesulfonate, 72%) after purification
by flash column
chromatography using a mixture of petroleum ether and ethyl acetate
(3:1 v/v). 1H NMR (400MHz, CDCl3): δ 8.82 (d, J = 4.0 Hz, 1H), 8.18 –
7.94 (m, 4H), 7.77 – 7.51 (m, 3H), 6.52 – 6.28 (m, 1H), 4.43 (q, J = 8.0
Hz, 2H), 3.83 (s, 3H), 1.44 (t, J = 8.0 Hz, 3H). 13C NMR (100MHz, CDCl3)
δ 166.2, 164.7, 153.2, 150.7, 147.8, 138.4, 136.5, 133.3, 132.3, 128.4,
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128.3, 127.5, 124.9, 124.3, 122.2, 61.7, 51.9, 14.3. HRMS (ESI) m/z
calcd for C18H17NO8SNa 414.0618 [M+Na]+; found 414.0622. IR (KBr):
3087, 2986, 1722, 1677, 1618, 1452, 1377, 1203, 1147, 857, 794 cm-1.
Methyl 3-(4-acetyl-2-(pyridin-2-ylsulfonyloxy)phenyl)acrylate (3ja)
Prepared according to general procedure as a colorless oil (34.6 mg,
obtained from 0.1 mmol corresponding phenyl 2-pyridinesulfonate, 96%)
after purification by flash column chromatography using a mixture of
petroleum ether and ethyl acetate (3:1 v/v). 1H NMR (400MHz, CDCl3): δ
8.79 (d, J = 4.0 Hz, 1H), 8.15 (d, J = 8.0 Hz, 1H), 8.03 – 8.00 (m, 2H),
7.88 (d, J = 8.0 Hz, 1H), 7.75 – 7.55 (m, 3H), 6.39 (d, J = 16.0 Hz, 1H),
3.82 (s, 3H), 2.64 (s, 3H). 13C NMR (100MHz, CDCl3) δ 195.9, 166.1,
153.1, 150.7, 148.1, 139.2, 138.5, 136.3, 132.4, 128.4, 127.8, 127.0,
124.3, 123.8, 122.4, 52.0, 26.7. HRMS (ESI) m/z calcd for
C17H15NO6SNa 384.0512 [M+Na]+; found 384.0508. IR (KBr): 3013, 1746,
1632, 1585, 1486, 1345, 1286, 1199, 1086, 878, 785 cm-1.
calcd for C15H12ClNO5SNa 376.0017 [M+Na]+; found 376.0012. IR (KBr):
3077, 2958, 1724,1641, 1587, 1438, 1380, 1317, 1261, 1187, 1116,
1079, 991, 852, 711 cm-1.
Methyl 3-(5-fluoro-2-(pyridin-2-ylsulfonyloxy)phenyl)acrylate (3na)
Prepared according to general procedure as a white solid (32.0 mg,
obtained from 0.1 mmol corresponding phenyl 2-pyridinesulfonate, 95%)
after purification by flash column chromatography using a mixture of
petroleum ether and ethyl acetate (3:1 v/v). m. p. = 109 – 110 oC. 1H
NMR (400MHz, CDCl3): δ 8.79 – 8.73 (m, 1H), 8.05 – 7.93 (m, 2H), 7.67
– 7.52 (m, 2H), 7.43 – 7.39 (m, 1H), 7.23 – 7.19 (m, 1H), 7.14 – 7.08 (m,
1H), 6.21 (d, J = 16.0 Hz, 1H), 3.78 (s, 3H). 13C NMR (100MHz, CDCl3) δ
166.1, 160.9（JC-F = 246.3 Hz）, 152.9, 150.7, 143.9 (JC-F = 2.8 Hz),
138.6, 136.3 (JC-F = 1.9 Hz), 129.9 (JC-F = 8.2 Hz), 128.4, 125.5 (JC-F = 8.8
Hz), 124.3, 121.3, 118.2 (JC-F = 23.8 Hz), 113.7 (JC-F = 24.3 Hz), 51.9.
HRMS (ESI) m/z calcd for C15H12FNO5SNa 360.0312 [M+Na]+; found
360.0316. IR (KBr): 3021, 1721, 1638, 1430, 1384, 1288, 1205, 1146,
969, 868, 801 cm-1. CCDC 1509679 contains the supplementary
crystallographic data for this paper. These data can be obtained free of
charge from the Cambridge Crystallographic Data Centre.
Ethyl
3-(3-methoxy-3-oxoprop-1-enyl)-4-(pyridin-2-ylsulfonyloxy)
benzoate (3ka) Prepared according to general procedure as a colorless
oil (37.1 mg, obtained from 0.1 mmol corresponding phenyl 2-
pyridinesulfonate, 95%) after purification
by flash column
chromatography using a mixture of petroleum ether and ethyl acetate
(3:1 v/v). 1H NMR (400MHz, CDCl3): δ 8.75 (d, J = 4.0 Hz, 1H), 8.23 (d, J
= 1.6 Hz, 1H), 8.11 – 7.93 (m, 3H), 7.70 – 7.57 (m, 2H), 7.52 (d, J = 8.4
Hz, 1H), 6.36 (d, J = 16.0 Hz, 1H), 4.39 (q, J = 8.0 Hz, 2H), 3.79 (s, 3H),
1.40 (t, J = 8.0 Hz,, 3H). 13C NMR (100MHz, CDCl3) δ 166.2, 164.9,
152.9, 150.9, 150.7, 138.6, 136.4, 132.3, 129.7, 129.1, 128.5, 128.1,
124.2, 123.8, 121.3, 61.6, 51.8, 14.3. HRMS (ESI) m/z calcd for
C18H17NO7SNa 414.0618 [M+Na]+; found 414.0624. IR (KBr): 3092, 2977,
1724, 1656, 1628, 1462, 1365, 1199, 1154, 861, 779 cm-1.
(E)-Methyl 3-(3-methoxy-5-methyl-2-(pyridin-2-ylsulfonyloxy) phenyl)
acrylate (3oa) Prepared according to general procedure as a colorless
oil (34.8 mg, obtained from 0.1 mmol corresponding phenyl 2-
pyridinesulfonate, 96%) after purification
by flash column
chromatography using a mixture of petroleum ether and ethyl acetate
(3:1 v/v). 1H NMR (400MHz, CDCl3): δ 8.78 (d, J = 4.0 Hz, 1H), 8.02 –
7.93 (m, 2H), 7.73 – 7.54 (m, 2H), 6.95 (s, 1H), 6.76 (s, 1H), 6.32 (d, J =
16.0 Hz, 1H), 3.74 (s, 3H), 3.59 (s, 3H), 2.32 (s, 3H). 13C NMR (100MHz,
CDCl3) δ 166.6, 154.5, 152.1, 150.4, 138.2, 138.1, 137.9, 135.6, 129.1,
127.9, 123.6, 120.3, 119.1, 115.1, 55.9, 51.7, 21.5. HRMS (ESI) m/z
calcd for C17H17NO6SNa 386.0669 [M+Na]+; found 386.0665. IR (KBr):
2940, 1589, 1471, 1380, 1311, 1147, 1083, 831, 773, 698 cm-1.
Methyl 3-(5-iodo-2-(pyridin-2-ylsulfonyloxy)phenyl)acrylate (3la)
Prepared according to general procedure as a white solid (40.4 mg,
obtained from 0.1 mmol corresponding phenyl 2-pyridinesulfonate, 91%)
after purification by flash column chromatography using a mixture of
petroleum ether and ethyl acetate (3:1 v/v). m. p. = 111 – 112 oC. 1H
NMR (400MHz, CDCl3): δ 8.82 (d, J = 4.0 Hz, 1H), 8.08 – 7.95 (m, 2H),
7.74 – 7.55 (m, 2H), 7.47 (d, J = 8.0 Hz, 2H), 7.16 (d, J = 8.0 Hz, 1H),
6.38 (d, J = 16.0 Hz, 1H), 3.79 (s, 3H). 13C NMR (100MHz, CDCl3) δ
166.1, 153.0, 150.7, 147.9, 140.1, 138.5, 136.4, 135.9, 130.2, 128.3,
125.7, 124.2, 121.3, 92.2, 51.9. HRMS (ESI) m/z calcd for
C15H12INO5SNa 467.9373 [M+Na]+; found 467.9369. IR (KBr): 3108,
2956, 1724, 1646, 1403, 1371, 1324, 1207, 1172, 1118, 985, 842, 786
cm-1.
2-Methoxy-4-methyl-6-(2-(phenylsulfonyl)vinyl)phenyl
pyridine-2-
sulfonate (3og) Prepared according to general procedure as a white
solid (42.3 mg, obtained from 0.1 mmol corresponding phenyl 2-
pyridinesulfonate, 95%) after purification
by flash column
chromatography using a mixture of petroleum ether and ethyl acetate
(3:1 v/v). m. p. = 127 – 129 oC. 1H NMR (400MHz, CDCl3): δ 8.95 – 8.80
(m, 1H), 8.09 (d, J = 8.0 Hz, 1H), 8.04 – 8.00 (m, 1H), 7.97 – 7.88 (m,
2H), 7.80 (d, J = 16.0 Hz, 1H), 7.72 – 7.49 (m, 4H), 6.85 – 6.80 (m, 3H),
3.65 (s, 3H), 2.31 (s, 3H). 13C NMR (100MHz, CDCl3) δ 154.4, 152.4,
150.8, 140.3, 138.3, 138.2, 136.4, 135.9, 133.4, 129.7, 129.3, 128.2,
127.8, 127.4, 123.7, 119.7, 115.9, 56.1, 21.5. HRMS (ESI) m/z calcd for
C21H19NO6S2Na 468.0546 [M+Na+]; found 468.0544. IR (KBr): 2940,
1631, 1588, 1471, 1380, 1311, 1147, 1083, 985, 858, 811, 773, 701 cm-1.
Methyl 3-(3-tert-butyl-5-methoxy-2-(pyridin-2-ylsulfonyloxy) phenyl)
acrylate (3pa) Prepared according to general procedure as a white solid
(38.5 mg, obtained from 0.1 mmol corresponding phenyl 2-
Methyl 3-(5-chloro-2-(pyridin-2-ylsulfonyloxy)phenyl)acrylate (3ma)
Prepared according to general procedure as a colorless oil (32.7 mg,
obtained from 0.1 mmol corresponding phenyl 2-pyridinesulfonate, 93%)
after purification by flash column chromatography using a mixture of
petroleum ether and ethyl acetate (3:1 v/v). 1H NMR (400MHz, CDCl3): δ
8.76 – 8.72 (m, 1H), 8.06 – 8.02 (m, H), 7.98 – 7.93 (m, 1H), 7.64 – 7.46
(m, 3H), 7.42 – 7.33 (m, 2H), 6.23 (d, J = 16.0 Hz, 1H), 3.77 (s, 3H). 13
C
pyridinesulfonate, 95%) after purification
by flash column
NMR (100MHz, CDCl3) δ 166.1, 153.0, 150.7, 146.4, 138.5, 136.1, 133.3,
chromatography using a mixture of petroleum ether and ethyl acetate
(3:1 v/v). m. p. = 127 – 128 oC. 1H NMR (400MHz, CDCl3): δ 8.81 (d, J =
131.2, 129.6, 128.4, 127.3, 125.2, 124.3, 121.3, 51.9 .HRMS (ESI) m/z
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4.0 Hz, 1H), 7.98 – 7.94 (m, 2H), 7.61 – 7.57 (m, 1H), 7.37 (d, J = 8.0 Hz,
1H), 7.09 (d, J = 2.4 Hz, 1H), 6.81 (d, J = 2.4 Hz, 1H), 6.08 (d, J = 16.0
Hz, 1H), 3.80 (s, 3H), 3.67 (s, 3H), 1.51 (s, 9H). 13C NMR (100MHz,
CDCl3) δ 166.3, 157.5, 154.3, 150.8, 146.4, 140.9, 139.9, 138.3, 130.6,
127.9, 124.0, 119.2, 118.1, 109.1, 55.5, 51.5, 36.0, 31.7. HRMS (ESI)
m/z calcd for C20H23NO6SNa 428.1138 [M+Na]+; found 428.1132. IR
(KBr): 3099, 2942, 1724, 1628, 1593, 1486, 1384, 1270, 1201, 1147,
1083, 983, 860, 811, 794, 718 cm-1. CCDC 1509680 contains the
supplementary crystallographic data for this paper. These data can be
obtained free of charge from the Cambridge Crystallographic Data
Centre.
Methyl (E)-3-(2,3-bis((pyridin-2-ylsulfonyl)oxy)phenyl)acrylate (3ta)
Prepared according to general procedure as a colorless oil (45.2 mg,
obtained from 0.1 mmol corresponding phenyl 2-pyridinesulfonate, 95%)
after purification by flash column chromatography using a mixture of
petroleum ether and ethyl acetate (3:1 v/v). m. p. = 251 – 252 oC. 1H
NMR (100MHz, d6-DMSO): δ 8.77 (d, J = 4.0 Hz, 2H), 8.21 – 8.11 (m,
2H), 8.01 – 7.97 (m, 2H), 7.93 – 7.78 (m, 3H), 7.51 – 7.33 (m, 3H), 6.61
(d, J = 16.0 Hz, 1H), 3.71 (s, 3H). 13C NMR (100MHz, d6-DMSO) δ 166.2,
152.6, 152.5, 151.5, 151.2, 143.0, 140.1, 140.0, 139.9, 136.0, 130.7,
129.8, 129.0, 127.1, 126.2, 124.7, 124.6, 122.1, 52.2. HRMS (ESI) m/z
calcd for C20H16N2O8S2Na 499.0240 [M+Na]+; found 499.0237. IR (KBr):
3079, 2860, 1714, 1644, 1472, 1201, 1087,883, 774 cm-1
(E)-Methyl 3-(3-acetyl-5-chloro-2-(pyridin-2-ylsulfonyloxy) phenyl)
acrylate (3qa) Prepared according to general procedure as a colorless
oil (36.2 mg, obtained from 0.1 mmol corresponding phenyl 2-
4-Ethoxy-2-(2-(phenylsulfonyl)vinyl)phenyl pyridine-2-sulfonate (3ug)
Prepared according to general procedure as a colorless oil (41.7 mg,
obtained from 0.1 mmol corresponding phenyl 2-pyridinesulfonate, 94%)
after purification by flash column chromatography using a mixture of
petroleum ether and ethyl acetate (3:1 v/v). 1H NMR (400MHz, CDCl3): δ
8.83 (d, J = 4.0 Hz, 1H), 8.25 – 7.82 (m, 4H), 7.77 – 7.46 (m, 5H), 7.36 –
7.17 (m, 1H), 7.02 – 6.73 (m, 3H), 3.98 (q, J = 8.0 Hz, 2H), 1.36 (t, J =
8.0 Hz, 3H). 13C NMR (100MHz, CDCl3) δ 157.7, 153.0, 150.9, 141.7,
140.2, 138.7, 135.7, 133.6, 129.8, 129.4, 128.6, 127.8, 126.9, 124.9,
124.2, 118.2, 113.1, 64.2, 14.7. HRMS (ESI) m/z calcd for
C21H19NO6S2Na 468.0546 [M+Na]+; found 468.0543. IR (KBr): 3089,
1726, 1645, 1481, 1389, 1324, 1201, 1076, 1023, 801, 704 cm-1.
pyridinesulfonate, 92%) after purification
by flash column
chromatography using a mixture of petroleum ether and ethyl acetate
(3:1 v/v). 1H NMR (400MHz, CDCl3): δ 8.71 (d, J = 4.0 Hz, 1H), 8.03 –
7.93 (m, 2H), 7.63 – 7.58 (m, 3H), 7.43 (d, J = 16.0 Hz, 1H), 6.15 (d, J =
16.0 Hz, 1H), 3.77 (s, 3H), 2.66 (s, 3H). 13C NMR (100MHz, CDCl3) δ
196.8, 165.7, 152.4, 150.8, 143.4, 138.7, 137.5, 135.7, 133.7, 131.5,
131.1, 129.8, 128.6, 124.5, 121.8, 51.9, 29.9. HRMS (ESI) m/z calcd for
C17H14ClNO6SNa 418.0123 [M+Na]+; found 418.0121. IR (KBr): 3103,
1685, 1584, 1479, 1443, 1368, 1302, 1246, 1178, 1124, 1071, 884, 853,
804 cm-1.
Methyl 3-(3-(pyridin-2-ylsulfonyloxy)naphthalen-2-yl)acrylate (3ra)
Prepared according to general procedure as a white solid (34.3 mg,
obtained from 0.1 mmol corresponding phenyl 2-pyridinesulfonate, 93%)
after purification by flash column chromatography using a mixture of
petroleum ether and ethyl acetate (3:1 v/v). m. p. = 112 – 113 oC. 1H
NMR (400MHz, CDCl3): δ 8.72 (d, J = 4.0 Hz, 1H), 8.04-7.96 (m, 2H),
7.93 – 7.89 (m, 1H), 7.87 – 7.69 (m, 4H), 7.63 – 7.47 (m, 3H), 6.38 (d, J
= 16.0 Hz, 1H), 3.78 (s, 3H). 13C NMR (100MHz, CDCl3) δ 166.6, 153.3,
150.6, 145.3, 138.4, 138.0, 134.1, 131.7, 128.4, 128.2, 128.0, 127.8,
127.2, 126.7, 124.2, 121.4, 120.3, 51.8. HRMS (ESI) m/z calcd for
C19H15NO5SNa 392.0563 [M+Na]+; found 392.0567. IR (KBr): 2986, 1721,
1655, 1585, 1436, 1358, 1265, 1195, 1120, 1043, 887, 789, 723 cm-1.
3-(2-(Phenylsulfonyl)vinyl)biphenyl-4-yl pyridine-2-sulfonate (3vg)
Prepared according to general procedure as a white solid (45.8 mg,
obtained from 0.1 mmol corresponding phenyl 2-pyridinesulfonate, 96%)
after purification by flash column chromatography using a mixture of
petroleum ether and ethyl acetate (3:1 v/v). m. p. = 119 – 120 oC. 1H
NMR (400MHz, CDCl3): δ 8.80 (d, J = 4.0 Hz, 1H), 8.13 (d, J = 8.0 Hz,
1H), 8.04 – 8.00 (m, 1H), 7.97 – 7.89 (m, 2H), 7.75 (d, J = 16.0 Hz, 1H),
7.67 – 7.58 (m, 4H), 7.57 – 7.40 (m, 7H), 7.40 – 7.35 (m, 1H), 6.89 (d, J
= 16.0 Hz, 1H). 13C NMR (100MHz, CDCl3) δ 153.2, 151.0, 147.6, 141.0,
140.2, 138.9, 138.8, 135.7, 133.6, 131.0, 130.0, 129.4, 129.0, 128.6,
128.2, 127.8, 127.1, 127.0, 126.3, 124.3, 124.2. HRMS (ESI) m/z calcd
for C25H19NO5S2Na 500.0597 [M+Na]+; found 500.0601. IR (KBr): 2954,
1603, 1583, 1434, 1382, 1238, 1186, 1110, 1022, 873, 815, 808, 765 cm-
1. CCDC 1509681 contains the supplementary crystallographic data for
this paper. These data can be obtained free of charge from the
Cambridge Crystallographic Data Centre.
Methyl
3-(4-acetyl-3-(pyridin-2-ylsulfonyloxy)
naphthalen-2-yl)
acrylate (3sa) Prepared according to general procedure as a colorless
oil (37.3 mg, obtained from 0.1 mmol corresponding phenyl 2-
pyridinesulfonate, 91%) after purification
by flash column
chromatography using a mixture of petroleum ether and ethyl acetate
Dimethyl 2-(4-(pyridin-2-ylsulfonyloxy)biphenyl-3-yl)maleate (3vh)
Prepared according to general procedure as a colorless oil (38.6 mg,
obtained from 0.1 mmol corresponding phenyl 2-pyridinesulfonate, 85%)
after purification by flash column chromatography using a mixture of
petroleum ether and ethyl acetate (3:1 v/v). m. p. = 126 – 127 oC. 1H
NMR (400MHz, CDCl3): δ 8.83 (d, J = 4.0Hz, 1H), 8.12 – 7.90 (m, 2H),
7.70 – 7.43 (m, 8H), 7.42 – 7.35 (m, 1H), 7.31 (s, 1H), 7.10 (s, 1H), 3.86
– 3.83 (s, 3H), 3.68 – 3.63 (s, 3H). 13C NMR (100MHz, CDCl3) δ 165.6,
164.7, 153.8, 150.6, 150.6, 146.3, 139.7, 139.6, 139.5, 138.2, 130.7,
129.8, 129.0, 128.8, 128.7, 128.5, 128.1, 128.1, 128.0, 127.8, 127.2,
1
(3:1 v/v). H NMR (400MHz, CDCl3): δ 8.78 (d, J = 4.0 Hz, 1H), 8.13 (s,
1H), 7.94 – 7.76 (m, 5H), 7.68 – 7.48 (m, 3H), 6.43 (d, J = 16.0 Hz, 1H),
3.79 (s, 3H), 2.70 (s, 3H). 13C NMR (100MHz, CDCl3) δ 201.0, 166.4,
152.8, 150.9, 141.7, 138.5, 137.9, 133.5, 132.0, 130.4, 129.8, 129.0,
128.9, 128.6, 127.6, 127.5, 125.1, 124.5, 120.8, 51.8, 32.7. HRMS (ESI)
m/z calcd for C21H17NO6SNa 434.0669 [M+Na]+; found 434.0667. IR
(KBr): 3103, 2986, 1799, 1697, 1585, 1431, 1368, 1283, 1195, 1120,
1074, 887, 804, 738 cm-1.
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124.1, 122.6, 122.4, 53.1, 52.0. HRMS (ESI) m/z calcd for
C23H19NO7SNa 476.0774 [M+Na]+; found 476.0778. IR (KBr): 2954, 1720,
1583, 1434, 1382, 1238, 1186, 1110, 1022, 873, 775 cm-1. CCDC
1509676 contains the supplementary crystallographic data for this paper.
These data can be obtained free of charge from the Cambridge
Crystallographic Data Centre.
after purification by flash column chromatography using a mixture of
petroleum ether and ethyl acetate (3:1 v/v). 1H NMR (400 MHz, CDCl3) δ
8.71 - 8.66 (m, 1H), 8.05 – 8.01 (m, 1H), 7.96 – 7.90 (m, 1H), 7.61 – 7.56
(m, 1H), 7.30 – 7.27 (m, 1H), 7.20 – 7.15 (m, 1H), 7.12 – 7.08 (m, 1H),
6.14 (s, 1H), 3.77 (s, 3H), 3.74 (s, 3H), 2.37 (s, 3H). 13C NMR (100 MHz,
CDCl3) δ 166.9, 165.0, 153.4, 150.3, 147.2, 138.2, 129.9, 128.4, 128.1
125.3, 124.4, 124.1, 123.6， 52.6, 52.0, 21.4. HRMS (ESI) m/z calcd for
C18H17NO7SNa 414.0618 [M+Na]+; found 414.0615. IR (KBr): 3111,3032,
2934, 1726, 1635, 1384, 1218, 1199, 1067, 1033, 886, 794, 695 cm-1.
Dimethyl
2-(4-((pyridin-2-ylsulfonyl)oxy)-[1,1'-biphenyl]-3-
yl)fumarate (3vj) Prepared according to general procedure as a white
solid (41.4 mg, obtained from 0.1 mmol corresponding phenyl 2-
pyridinesulfonate, 91%) after purification
by flash column
Dimethyl
2-(4-methoxy-2-(pyridin-2-ylsulfonyloxy)phenyl)maleate
chromatography using a mixture of petroleum ether and ethyl acetate
(3:1 v/v). m. p. = 129 – 130 oC. 1H NMR (400 MHz, CDCl3) δ 8.71 - 8.69
(m, 1H), 8.07 (d, J = 8.0Hz, 1H)), 7.97 – 7.93 (m, 1H), 7.63 – 7.59 (m,
2H), 7.53 – 7.50 (m, 4H), 7.45 – 7.41 (m, 2H), 7.39 – 7.36 (m, 1H), 3.80
(s, 3H), 3.80 (s, 3H), 3.76 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 166.7,
164.9, 153.4, 150.4, 146.7, 142.1, 140.8, 139.0, 138.3, 129.0, 128.9,
128.8, 128.3, 128.1, 127.1, 125.0, 124.5, 123.7, 52.8, 52.2. HRMS (ESI)
m/z calcd for C23H19NO7SNa 476.0774 [M+Na]+; found 476.0777. IR
(KBr): 2953, 1711, 1583, 1432, 1377, 1238, 1189, 1111, 1004, 875 cm-1.
CCDC 1515863 contains the supplementary crystallographic data for this
paper. These data can be obtained free of charge from the Cambridge
Crystallographic Data Centre.
(3yh) Prepared according to general procedure as a yellow oil (37.3 mg,
obtained from 0.1 mmol corresponding phenyl 2-pyridinesulfonate, 92%)
after purification by flash column chromatography using a mixture of
petroleum ether and ethyl acetate (3:1 v/v). 1H NMR (400MHz, CDCl3): δ
8.71 (d, J = 4.0 Hz, 1H), 7.99 – 7.84 (m, 2H), 7.64 – 7.51 (m, 1H) , 7.12
(d, J = 8.8 Hz, 1H), 6.98 – 6.84 (m, 2H), 6.84 – 6.70 (m, 1H), 3.73 (s, 6H),
3.58 (s, 3H). 13C NMR (100MHz, CDCl3) δ 165.8, 164.8, 160.7, 153.4,
150.5, 147.6, 139.6, 138.4, 131.8, 129.8, 128.2, 124.1, 119.6, 112.3,
108.1, 55.5, 53.0, 51.9. HRMS (ESI) m/z calcd for C18H17NO8SNa
430.0567 [M+Na]+; found 430.0554. IR (KBr): 3083, 1711, 1635, 1581,
1470, 1362, 1143, 1093, 1032, 843, 783 cm-1. cm-1.
Dimethyl 2-(4-(dimethylamino)-2-(pyridin-2-ylsulfonyloxy) phenyl)
maleate (3zh) Prepared according to general procedure as a white solid
(38.2 mg, obtained from 0.1 mmol corresponding phenyl 2-
Dimethyl 2-(3-(ethoxycarbonyl)-2-(pyridin-2-ylsulfonyloxy) phenyl)
maleate (3wh) Prepared according to general procedure as a colorless
oil (39.6 mg, obtained from 0.1 mmol corresponding phenyl 2-
pyridinesulfonate, 91%) after purification
by flash column
pyridinesulfonate, 88%) after purification
by flash column
chromatography using a mixture of petroleum ether and ethyl acetate
(3:1 v/v). m. p. = 136 – 137 oC. 1H NMR (400MHz, CDCl3): δ 8.73 (d, J =
4.0 Hz, 1H), 8.01 – 7.82 (m, 2H), 7.63 – 7.46 (m, 1H), 7.12 – 7.01 (m,
1H), 6.78 (s, 1H), 6.60 – 6.51 (m, 2H), 3.76 (s, 3H), 3.64 (s, 3H), 2.92 (s,
6H). 13C NMR (100MHz, CDCl3) δ 166.6, 165.2, 153.6, 151.6, 150.4,
148.0, 140.1, 138.1, 131.8, 128.1, 127.9, 124.3, 113.9, 109.7, 105.4,
52.9, 51.8, 40.0. HRMS (ESI) m/z calcd for C19H20N2O7SNa 443.0883
[M+Na]+; found 443.0889. IR (KBr): 2915, 1725, 1623, 1535, 1440, 1380,
1263, 1172, 1087, 1027, 910, 802 cm-1.
chromatography using a mixture of petroleum ether and ethyl acetate
(3:1 v/v). 1H NMR (400MHz, CDCl3): δ 8.72 (d, J = 4.0 Hz, 1H), 8.05 –
7.85 (m, 3H), 7.68 – 7.56 (m, 1H), 7.45 – 7.35 (m, 2H), 6.83 (s, 1H), 4.32
(q, J = 8.0 Hz, 2H), 3.80 (s, 3H), 3.66 (s, 3H), 1.41 (t, J = 8.0 Hz, 3H).13
C
NMR (100MHz, CDCl3) δ 165.1, 164.9, 164.4, 154.2, 150.4, 145.3, 139.4,
137.9, 134.9, 132.7, 132.4, 130.7, 129.6, 128.0, 127.8, 126.8, 126.3,
123.8, 61.7, 53.1, 52.0, 14.0. HRMS (ESI) m/z calcd for C20H19NO9SNa
472.0673 [M+Na]+; found 472.0663. IR (KBr): 3099, 2960, 1722, 1643,
1575, 1472, 1378, 1203, 1197, 1147, 1120, 869, 782 cm-1.
Dimethyl 2-(5-methyl-2-(pyridin-2-ylsulfonyloxy)phenyl) maleate
(3a’h) Prepared according to general procedure as a colorless oil (34.3
mg, obtained from 0.1 mmol corresponding phenyl 2-pyridinesulfonate,
88%) after purification by flash column chromatography using a mixture
of petroleum ether and ethyl acetate (3:1 v/v). 1H NMR (400MHz, CDCl3):
δ 8.75 (d, J = 4.0 Hz, 1H), 7.98 – 7.83 (m, 2H), 7.59 – 7.55 (m, 1H), 7.16
– 7.12 (m, 2H), 7.05 – 6.92 (m, 2H), 3.77 (s, 3H), 3.60 (s, 3H), 2.32 (s,
3H). 13C NMR (100MHz, CDCl3) δ 165.6, 164.7, 153.7, 150.5, 144.8,
139.9, 138.2, 136.4, 131.4, 130.7, 130.3, 128.0, 127.5, 124.1, 121.8,
53.0, 51.9, 20.9. HRMS (ESI) m/z calcd for C18H17NO8SNa 414.0618
[M+Na]+; found 414.0622. IR (KBr): 3087, 3005, 2929, 1721, 1617, 1385,
1212, 1199, 1059, 1031, 917, 847, 801 cm-1.
Dimethyl 2-(4-methyl-2-(pyridin-2-ylsulfonyloxy)phenyl)maleate (3xh)
Prepared according to general procedure as a colorless oil (37.5 mg,
obtained from 0.1 mmol corresponding phenyl 2-pyridinesulfonate, 96%)
after purification by flash column chromatography using a mixture of
petroleum ether and ethyl acetate (3:1 v/v). 1H NMR (400MHz, CDCl3): δ
8.77 (d, J = 4.0 Hz, 1H), 8.04 – 7.86 (m, 2H), 7.65 – 7.51 (m, 1H), 7.16 (s,
2H), 6.95 (s, 1H), 3.75 (s, 3H), 3.60 (s, 3H), 2.34 (s, 3H). 13C NMR
(100MHz, CDCl3) δ 165.7, 164.7, 153.6, 150.5, 146.7, 140.8, 139.9,
138.2, 130.8, 130.1, 128.1, 127.4, 124.7, 124.1, 122.7, 53.0, 52.0, 21.3.
HRMS (ESI) m/z calcd for C18H17NO7SNa 414.0618 [M+Na]+; found
414.0604. IR (KBr): 3097,3021, 2919, 1723, 1628, 1378, 1208, 1188,
1069, 1035, 935, 837, 794 cm-1.
Dimethyl
2-(5-methoxy-2-(pyridin-2-ylsulfonyloxy)phenyl)maleate
Dimethyl
2-(4-methyl-2-((pyridin-2-ylsulfonyl)oxy)phenyl)maleate
(3b’h) Prepared according to general procedure as a colorless oil (36.0
mg, obtained from 0.1 mmol corresponding phenyl 2-pyridinesulfonate,
89%) after purification by flash column chromatography using a mixture
(3xj) Prepared according to general procedure as a colorless oil (34.0 mg,
obtained from 0.1 mmol corresponding phenyl 2-pyridinesulfonate, 87%)
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of petroleum ether and ethyl acetate (3:1 v/v). 1H NMR (400MHz, CDCl3):
δ 8.76 (d, J = 4.0Hz, 1H), 7.92 (s, 2H), 7.59 (s, 1H), 7.31 (s, 1H), 7.20 (d,
J = 8.8 Hz, 1H), 7.01 (s, 1H), 6.87 – 6.70 (m, 2H), 3.83 – 3.70 (m, 6H),
3.62 (s, 3H).13C NMR (100MHz, CDCl3) δ 165.4, 164.5, 157.4, 153.6,
150.6, 150.5, 140.3, 139.5, 138.2, 130.6, 128.8, 128.0, 124.3, 123.2,
116.2, 114.8, 55.6, 53.1, 52.0. HRMS (ESI) m/z calcd for C18H17NO8SNa
430.0567 [M+Na]+; found 430.0563. IR (KBr): 3087, 1715, 1644， 1585,
1506, 1488, 1374,, 1160, 1089, 845, 789 cm-1.
122.8, 20.7. HRMS (ESI) m/z calcd for C13H10ClNO5SNa 349.9860
[M+Na]+; found 349.9866. IR (KBr): 3089, 1776, 1585, 1385, 1196, 1012,
862, 754 cm-1.
4-(tert-Butyl)-2-((pyridin-2-ylsulfonyl)oxy)phenyl
acetate
(4h)
Prepared according to general procedure as a colorless oil (29.0 mg,
obtained from 0.1 mmol corresponding phenyl 2-pyridinesulfonate, 83%)
after purification by flash column chromatography using a mixture of
petroleum ether and ethyl acetate (2:1 v/v). 1H NMR (400 MHz, CDCl3) δ
8.82 (d, J = 4.8 Hz, 1H), 7.94 (d, J = 4.0 Hz, 2H), 7.73 – 7.59 (m, 1H),
7.35 – 7.24 (m, 1H), 7.14 (d, J = 2.0 Hz, 1H), 7.05 (d, J = 8.8 Hz, 1H),
2.2(s, 3H), 1.2 (s, 9H). 13C NMR (100MHz, CDCl3) δ 168.5, 153.6, 150.6,
150.3, 140.5, 140.3, 138.3, 128.3, 124.9, 124.3, 123.3, 121.1, 34.6, 31.1,
20.7. HRMS (ESI) m/z calcd for C17H19NO5SNa 372.0876 [M+Na]+; found
372.0871. IR (KBr): 3394, 1705, 1612, 1427, 1365, 1281, 1165, 945, 856,
762 cm-1.
Dimethyl 2-(1-(pyridin-2-ylsulfonyloxy)naphthalen-2-yl)maleate (3c’h)
Prepared according to general procedure as a colorless oil (43.7 mg,
obtained from 0.1 mmol corresponding phenyl 2-pyridinesulfonate, 92%)
after purification by flash column chromatography using a mixture of
petroleum ether and ethyl acetate (3:1 v/v). m. p. = 115 – 116 oC. 1H
NMR (400MHz, CDCl3): δ 8.87 (d, J = 4.0 Hz, 1H), 8.11 (d, J = 8.0 Hz,
1H), 7.96 – 7.71 (m, 4H), 7.73 – 7.45 (m, 3H), 7.38 (d, J = 8.0 Hz, 2H),
7.03 (s, 1H), 3.82 (s, 3H), 3.61 (s, 3H). 13C NMR (100MHz, CDCl3) δ
165.7, 165.6, 164.6, 154.0, 150.6, 144.9, 144.1, 142.8, 140.5, 138.1,
134.7, 134.3, 132.0, 130.7, 128.1, 127.7, 127.4, 127.3, 127.2, 127.1,
126.6, 125.3, 125.2, 123.9, 122.9, 120.3, 53.1, 52.0. HRMS (ESI) m/z
calcd for C21H17NO7SNa 500.0597 [M+Na]+; found 500.0601. IR (KBr):
2956, 1729, 1650, 1585, 1378, 1265, 1195, 1120, 1072, 894, 798, 713
cm-1.
Ethyl 3-acetoxy-4-((pyridin-2-ylsulfonyl)oxy)benzoate (4k) Prepared
according to general procedure as a colorless oil (30.3 mg, obtained from
0.1 mmol corresponding phenyl 2-pyridinesulfonate, 83%) after
purification by flash column chromatography using a mixture of petroleum
ether and ethyl acetate (2:1 v/v). 1H NMR (400 MHz, CDCl3) δ 8.84 - 8.78
(m, 1H), 8.01 - 7.92 (m, 3H), 7.82 (d, J = 2.0 Hz, 1H), 7.66 – 7.63 (m, 1H),
7.45 (d, J = 8.4 Hz, 1H), 4.37 (q, J = 8.0 Hz, 2H), 2.24 (s, 1H), 1.37 (t, J =
6.8 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 168.1, 164.7, 153.5, 150.7,
144.7, 142.7, 138.4, 130.3, 128.4, 128.2, 125.4, 124.1, 123.8, 61.6, 20.6,
14.3. HRMS (ESI) m/z calcd for C16H15NO7SNa 388.0461 [M+Na]+; found
388.0463. IR (KBr): 2985, 1720, 1588, 1379, 1265, 1093, 933, 769 cm-1.
5-Iodo-2-((pyridin-2-ylsulfonyl)oxy)phenyl acetate (4l) Prepared
according to general procedure as a colorless oil (33.2 mg, obtained from
0.1 mmol corresponding phenyl 2-pyridinesulfonate, 84%) after
purification by flash column chromatography using a mixture of petroleum
ether and ethyl acetate (2:1 v/v). 1H NMR (400 MHz, CDCl3) δ 8.85 –
8.77 (m, 1H), 8.04 – 7.91 (m, 2H), 7.69 – 7.61 (m, 1H), 7.56 – 7.51 (m,
1H), 7.48 (s, 1H), 7.09 (d, J = 8.4 Hz, 1H), 2.2 (s, 3H).13C NMR (100MHz,
CDCl3) δ 167.9, 153.4, 150.7, 143.4, 141.4, 138.5, 136.0, 133.1 128.5,
125.5, 124.1, 91.1, 20.6. HRMS (ESI) m/z calcd for C13H10INO5SNa
418.9324 [M+Na]+; found 418.9319. IR (KBr): 2960, 1722, 1579, 1427,
1367, 1196, 924, 781, cm-1.
General procedure for acetoxylation of phenyl pyridine-2-sulfonate
synthesis:
DCE (2 ml) and AcOH (2 ml) were added to a round bottom flask
containing the phenyl pyridine-2-sulfonate derivative 1 (1.0 mmol),
Pd(OAc)2 (10 mol%) and potassium persulfate (2.0 mmol). Then the
mixture was heated to 80 ºC for 12 - 24 h. It was allowed to reach room
temperature and concentrated under reduced pressure. Purification by
flash chromatography afforded the acetoxylated phenyl pyridine-2-
sulfonate derivative 4.
2-((Pyridin-2-ylsulfonyl)oxy)phenyl acetate (4a) Prepared according to
general procedure as a colorless oil (26.1 mg, obtained from 0.1 mmol
corresponding phenyl 2-pyridinesulfonate, 89%) after purification by flash
column chromatography using a mixture of petroleum ether and ethyl
1
acetate (2:1 v/v). H NMR (400 MHz, CDCl3) δ 8.76 (d, J = 4.8 Hz, 1H),
8.03 – 7.85 (m, 2H), 7.62-7.57 (m, 1H), 7.35 – 7.25 (m, 2H), 7.25 – 7.15
(m, 1H), 7.12 – 7.09 (m, 1H), 2.18 (s, 3H). 13C NMR (100MHz, CDCl3) δ
168.2, 153.4, 150.7, 142.9, 141.2, 138.5, 128.5, 128.1, 126.9, 124.1,
124.1, 123.9, 20.6. HRMS (ESI) m/z calcd for C13H11NO5SNa 316.0250
[M+Na]+; found 316.0259. IR (KBr): 3070, 1772, 1581, 1493, 1381, 1200,
1159, 1005, 879, 773 cm-1.
3-(t-Butyl)-5-methoxy-2-((pyridin-2-ylsulfonyl)oxy)phenyl
acetate
(4p) Prepared according to general procedure as a colorless oil (32.2 mg,
obtained from 0.1 mmol corresponding phenyl 2-pyridinesulfonate, 85%)
after purification by flash column chromatography using a mixture of
petroleum ether and ethyl acetate (2:1 v/v). 1H NMR (400 MHz, CDCl3) δ
8.83 - 8.82 (m, 1H), 8.08 - 8.06 (m, 1H), 8.01 - 7.977.54 (m, 1H), 7.64 –
7.60 (m, 1H), 6.83 (d, J = 4.0 Hz, 1H), 6.58 (d, J = 4.0 Hz, 1H), 3.76 (s,
3H), 2.01 (s, 3H), 1.24 (s, 9H) . 13C NMR (100 MHz, CDCl3) δ 168.6,
157.2, 155.7, 150.4, 144.8, 143.9, 138.3, 134.9, 127.9, 123.0, 112.1,
106.3, 55.6, 35.2, 30.5, 20.7. HRMS (ESI) m/z calcd for C18H21NO6SNa
402.0982 [M+Na]+; found 402.0987. IR (KBr): 2962, 1774, 1587, 1371,
1198, 1020, 850, 611 cm-1.
3-Chloro-2-((pyridin-2-ylsulfonyl)oxy)phenyl acetate (4f) Prepared
according to general procedure as a colorless oil (24.3 mg, obtained from
0.1 mmol corresponding phenyl 2-pyridinesulfonate, 75%) after
purification by flash column chromatography using a mixture of petroleum
ether and ethyl acetate (2:1 v/v). 1H NMR (400 MHz, CDCl3) δ 8.82 –
8.79 (m, 1H), 8.08 – 8.05 (m, 1H), 8.02 – 7.97 (m, 1H), 7.67 – 7.62 (m,
1H), 7.29 – 7.15 (m, 3H), 2.25 (s, 3H) 13C NMR (100MHz, CDCl3) δ 168.1,
154.3, 150.5, 145.0, 138.8, 138.4, 128.8, 128.4, 127.82, 127.81, 123.8,
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4-Acetyl-3-((pyridin-2-ylsulfonyl)oxy)naphthalen-2-yl acetate (4s)
Prepared according to general procedure as a colorless oil (30.3 mg,
obtained from 0.1 mmol corresponding phenyl 2-pyridinesulfonate, 79%)
after purification by flash column chromatography using a mixture of
petroleum ether and ethyl acetate (2:1 v/v). 1H NMR (400 MHz, CDCl3) δ
8.84 - 8.79 (m, 1H), 7.98 - 7.89 (m, 2H), 7.82 - 7.78 (m, 2H), 7.70 - 7.61
(m, 2H), 7.55 - 7.45 (m, 2H), 2.47 (s, 3H), 2.37 (s, 3H). 13C NMR (100
MHz, CDCl3) δ 200.7, 168.7, 153.3, 150.8, 140.9, 138.5, 136.7, 133.4,
132.4, 128.6, 128.1, 127.8, 127.6, 127.4, 124.8, 124.2, 123.5, 32.7, 20.9.
HRMS (ESI) m/z calcd for C19H15NO6SNa 408.0512 [M+Na]+; found
408.0514. IR (KBr): 3373, 3062, 1697, 1427, 1363, 1209, 922, 804 cm-1.
(m, 1H), 7.51 - 7.48 (m, 1H), 2.58 (s, 3H), 2.24 (s, 3H). 13C NMR (100
MHz, CDCl3) δ 195.8, 168.1, 153.6, 150.7, 143.0, 136.5, 128.4, 127.0,
124.12, 124.07, 124.05, 26.6, 20.6. HRMS (ESI) m/z calcd for
C15H13NO6SNa 358.0356 [M+Na]+; found 358.0353. IR (KBr): 3435, 3084,
2920, 1782, 1683, 1365, 1198, 1149, 850, 621 cm-1.
Removing the directing group.
A suspension of alkenylated phenyl pyridine-2-sulfonate derivative (0.1
mmol) and activated Zn powder (327 mg, 5.0 mmol) in a 1:1 mixture of
THF and saturated NH4Cl solution in water (5 mL) was stirred at room
temperature until consumption of the starting material (monitored by
TLC). The mixture was filtered over a pad of celite to remove the Zn. The
filtrate was extracted with EtOAc (15 mL) and washed with a saturated
aqueous solution of ammonium chloride and brine. The combined
organic phase was dried over MgSO4 and concentrated to dryness. The
residue was purified by flash chromatography to afford the corresponding
alkenylated phenol derivatives 5.
(E)-Methyl 3-(2-hydroxyphenyl)acrylate (5aa)[21] Prepared according to
general procedure as a white solid (15.1 mg, obtained from 0.1 mmol
corresponding alkenlated phenyl 2-pyridinesulfonate, 85%) after
purification by flash column chromatography using a mixture of petroleum
ether and ethyl acetate (4:1 v/v). m. p. = 241 – 242 oC. 1H NMR (400MHz,
CDCl3): δ 10.27 (s, 1H), 7.90 (d, J = 16.0 Hz, 1H), 7.66 – 7.52 (m, 1H),
7.31 – 7.11 (m, 1H), 6.93 (d, J = 8.0 Hz, 1H), 6.89 – 6.85 (m, 1H), 6.62 (d,
J = 16.0 Hz, 1H), 3.71 (s, 3H). 13C NMR (100 MHz, d6-DMSO) δ 167.6,
157.3, 140.6, 132.2, 129.3, 121.1, 119.9, 117.3, 116.6, 51.8. HRMS (ESI)
m/z calcd for C10H10O3Na 201.0522 [M+Na]+; found 201.0518. IR (KBr):
3046, 2958, 1695, 1627, 1457, 1174,
4-((Pyridin-2-ylsulfonyl)oxy)-[1,1'-biphenyl]-3-yl
acetate
(4v)
Prepared according to general procedure as a colorless oil (28.4 mg,
obtained from 0.1 mmol corresponding phenyl 2-pyridinesulfonate, 77%)
after purification by flash column chromatography using a mixture of
petroleum ether and ethyl acetate (2:1 v/v). 1H NMR (400 MHz, CDCl3) δ
8.85 – 8.81 (m, 1H), 8.09 – 7.91 (m, 2H), 7.66 – 7.59 (m, 1H), 7.54 –
7.48 (m, 2H), 7.45 – 7.32 (m, 6H), 2.24 (s, 3H). 13C NMR (100MHz,
CDCl3) δ 168.3, 153.8, 150.7, 143.0, 141.5, 140.4, 139.1, 138.3, 128.9,
128.3, 128.0, 127.2, 125.4, 124.2, 124.1, 122.6, 20.7. HRMS (ESI) m/z
calcd for C19H15NO5SNa 392.0563 [M+Na]+; found 392.0558. IR (KBr):
3069, 2927, 1772, 1579, 1485, 1379, 1198, 833, 769 cm-1.
Ethyl 3-acetoxy-2-((pyridin-2-ylsulfonyl)oxy)benzoate (4w) Prepared
according to general procedure as a colorless oil (29.5 mg, obtained from
0.1 mmol corresponding phenyl 2-pyridinesulfonate, 81%) after
purification by flash column chromatography using a mixture of petroleum
ether and ethyl acetate (2:1 v/v). 1H NMR (400 MHz, CDCl3) δ 8.80 - 8.76
(m, 1H), 7.99 - 7.96 (m, 2H), 7.83 - 7.78 (m, 1H), 7.65 - 7.61 (m, 1H),
7.37 - 7.28 (m, 2H), 4.20 (q, J = 7.2 Hz, 2H), 2.09 (s, 3H), 1.31 (t, J = 7.2
Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 168.0, 164.3, 154.4, 150.5, 143.7,
138.3, 129.0, 128.1, 127.7, 127.6, 127.4, 123.8, 61.7, 20.5, 14.0. HRMS
(ESI) m/z calcd for C16H15NO7SNa 388.0461 [M+Na]+; found 388.0463.
IR (KBr): 3413, 2960, 1722, 1382, 1292, 1120, 565 cm-1.
995, 869, 760, 622 cm-1.
(E)-Methyl 3-(2-hydroxy-3-methoxyphenyl)acrylate (5da)[22] Prepared
according to general procedure as a white solid (15.5 mg, obtained from
0.1 mmol corresponding alkenlated phenyl 2-pyridinesulfonate, 87%)
after purification by flash column chromatography using a mixture of
petroleum ether and ethyl acetate (4:1 v/v). m. p. = 247 – 248 oC. 1H
NMR (400MHz, CDCl3): δ 7.96 (d, J = 16.0 Hz, 1H), 7.10 – 7.06 (m, 1H),
6.90 – 6.78 (m, 2H), 6.61 (d, J = 16.0 Hz, 1H), 6.22 (s, 1H), 3.90 (s, 3H),
3.80 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 168.0, 146.8, 145.4, 139.8,
120.9, 120.8, 119.7, 118.8, 111.8, 77.4, 77.1, 76.7, 56.2, 51.6. HRMS
(ESI) m/z calcd for C10H10O3Na 201.0522 [M+Na]+; found 201.0518. IR
(KBr): 1714, 1635, 1492, 1457, 1324, 1272, 1238, 1184, 1089, 985, 917,
788 cm-1.
5-Methyl-2-((pyridin-2-ylsulfonyl)oxy)phenyl acetate (4a’) Prepared
according to general procedure as a colorless oil (24.6 mg, obtained from
0.1 mmol corresponding phenyl 2-pyridinesulfonate, 80%) after
purification by flash column chromatography using a mixture of petroleum
ether and ethyl acetate (2:1 v/v). 1H NMR (400 MHz, CDCl3) δ 8.85 - 8.79
(m, 1H), 7.99 - 7.90 (m, 2H), 7.65 - 7.59 (m, 1H), 7.19 - 7.15 (m, 1H),
7.03 - 6.97 (m, 1H), 6.95 - 6.92 (m, 1H), 2.32 (s, 3H), 2.21 (s, 3H). 13C
NMR (100 MHz, CDCl3) δ 168.4, 153.8, 150.6, 138.2, 128.1, 127.4,
124.4, 124.1, 123.5, 21.0, 20.7. HRMS (ESI) m/z calcd for
C14H13NO5SNa 330.0407 [M+Na]+; found 330.0404. IR (KBr): 3425, 3076,
2920, 2555, 1955, 1579, 1373, 1192, 822, 592 cm-1.
General procedure for coumarin synthesis:
To a solution of 1.0 mmol methyl 2-hydroxycinnamat with different
substituent groups in 10mL methanol was added 2.0 mmol Bu3P. The
mixture was stirred at 60℃ overnight. The solvent was removed by
distillation and the mixture was purified by column chromatography to
give the product 6 as white solid.
2H-Chromen-2-one (6aa)[23] Prepared according to general procedure
as a white solid (10.7 mg, obtained from 0.1 mmol corresponding
alkenlated phenyl 2-pyridinesulfonate, 70%) after purification by flash
column chromatography using a mixture of petroleum ether and ethyl
5-acetyl-2-((pyridin-2-ylsulfonyl)oxy)phenyl acetate (4d’) Prepared
according to general procedure as a colorless oil (27.8 mg from 0.1 mmol
corresponding phenyl pyridine-2-sulfonate, 83%) after purification by
flash column chromatography using a mixture of petroleum ether and
1
ethyl acetate (2:1 v/v). H NMR (400 MHz, CDCl3) δ 8.84 - 8.79 (m, 1H),
8.04 - 7.96 (m, 2H), 7.84 - 7.81 (m, 1H), 7.75 - 7.70 (m, 1H), 7.67 - 7.63
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o
1
acetate (4:1 v/v). m. p. = 69–70 C. H NMR (400MHz, CDCl3): δ 7.76 -
7.70 (d, J = 9.6 Hz, 1H), 7.57 - 7.47 (m, 2H), 7.35 - 7.25 (m, 2H), 6.42 (d,
J = 9.6 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 160.8, 154.0, 143.5, 131.9,
127.9, 124.5, 118.8, 116.8, 116.6, HRMS (ESI) m/z calcd for C9H6O2Na
169.0260 [M+Na]+; found 169.0256. IR (KBr): 1729, 1617, 1457, 1403,
1267, 1184, 1122, 937, 835, 763 cm-1.
purification by flash column chromatography using a mixture of petroleum
ether and ethyl acetate (4:1 v/v). m. p. = 203 – 204 oC. 1H NMR (400MHz,
d6-DMSO): δ 7.64 (s, 1H), 7.33 – 7.27 (m, 1H), 7.26 -7.21 (m, 1H), 7.08 –
7.04 (m, 1H), 4.23 (q, J = 8.0 Hz, 2H), 1.42 (t, J = 8.0 Hz, 3H). 13C NMR
(100 MHz, d6-DMSO) δ 160.5, 146.6, 145.1, 145.0, 128.9, 125.1, 115.0,
114.2, 110.3, 64.5, 15.1. HRMS (ESI) m/z calcd for C11H10O4Na
229.0471 [M+Na]+; found 229.0467. IR (KBr): 3484, 2991, 2940. 1702,
1592, 1494, 1433, 1328, 1270, 1203, 1089, 1020, 941, 904, 652, 779,
730cm-1.
7-Phenyl-2-(phenylsulfonyl)benzofuran (7vf)[26] Prepared according to
general procedure as a white solid (18.4 mg, obtained from 0.1 mmol
corresponding alkenlated phenyl 2-pyridinesulfonate, 55%) after
purification by flash column chromatography using a mixture of petroleum
ether and ethyl acetate (4:1 v/v). m. p. = 240 – 241 oC. 1H NMR (400MHz,
CDCl3): δ 8.13 - 8.08 (m, 2H), 7.86 - 7.83 (m, 1H), 7.68 - 7.56 (m, 8H),
7.48 - 7.44 (m, 2H). 7.38 - 7.33 (m, 1H),13C NMR (100 MHz, CDCl3) δ
157.0, 152.2, 140.5, 139.3, 138.1, 134.3, 129.6, 129.0, 128.3, 127.9,
127.6, 127.4, 126.6, 121.4, 113.7, 112.6. HRMS (ESI) m/z calcd for
C20H14O3SNa 357.0556 [M+Na]+; found 357.0554. IR (KBr): 1546, 1452,
1338, 1164, 1097, 937, 894, 815, 761, 725, 692, 622cm-1.
8-Methoxy-2H-chromen-2-one (6da)[24] Prepared according to general
procedure as
a white solid (12.8 mg, obtained from 0.1 mmol
corresponding alkenlated phenyl 2-pyridinesulfonate, 68%) after
purification by flash column chromatography using a mixture of petroleum
ether and ethyl acetate (4:1 v/v). m. p. = 114 – 115 oC. 1H NMR (400MHz,
CDCl3): δ 7.70 (d, J = 9.6 Hz, 1H), 7.23 – 7.19 (m, 1H), 7.10 – 7.06 (m,
2H), 6.43 (d, J = 9.6 Hz, 1H), 3.96 (s, 3H). 13C NMR (100 MHz, CDCl3) δ
160.2, 147.2, 143.7, 143.7, 124.3, 119.5, 119.5, 116.9, 113.7, 56.2.
HRMS (ESI) m/z calcd for C11H9O3Na 212.1766 [M+Na]+; found
212.1764. IR (KBr): 3246, 1726, 1619, 1452, 1418, 1267, 1184, 1120,
935, 835, 763cm-1.
7-tert-Butyl-2H-chromen-2-one (6ha)[25] Prepared according to general
procedure as
a white solid (14.9 mg, obtained from 0.1 mmol
corresponding alkenlated phenyl 2-pyridinesulfonate, 74%) after
purification by flash column chromatography using a mixture of petroleum
ether and ethyl acetate (4:1 v/v). m. p. = 129 – 130 oC. 1H NMR (400MHz,
CDCl3): δ 7.70 (d, J = 9.6 Hz, 1H), 7.45 -7.41 (m, 1H), 7.34- 7.29 (m, 2H),
6.36 (d, J = 9.6 Hz, 1H), 1.35 (s, 9H). 13C NMR (100 MHz, CDCl3) δ
161.2, 156.3, 154.1, 143.3, 127.4, 122.0, 116.4, 115.6, 113.6, 35.2, 31.0.
HRMS (ESI) m/z calcd for C13H14O2Na 225.0886 [M+Na]+; found
225.0884. IR (KBr): 3258, 1721, 1618, 1458, 1399, 1267, 1179, 1123,
934, 831, 763 cm-1.
2-Hydroxyphenyl pyridine-2-sulfonate (8a) DCE (2 ml), TFA (1 ml) and
trifluoroacetic anhydride (1 ml) were added to a round bottom flask
containing the phenyl pyridine-2-sulfonate 1 (0.1 mmol), Pd(OAc)2 (10
mol%) and potassium persulfate (0.2 mmol). Then the mixture was
heated to 80 ºC for 15 h. It was allowed to reach room temperature and
concentrated under reduced pressure. The residue was purified by flash
chromatography (petroleum ether : ethyl acetate, 3:1 v/v) to afford the
hydroxylated phenyl 2-pyridinesulfonate (8a, 22.1 mg, 88%). 1H NMR
(400 MHz, CDCl3) δ 9.85 (s, 1H), 8.70 - 8.65 (m, 1H), 8.09 - 8.04 (m, 1H),
7.98 - 7.93 (m, 1H), 7.61 - 7.56 (m, 1H), 7.30 - 7.25 (m, 1H), 7.19 - 7.14
(m, 1H), 7.03 - 6.98 (m, 1H), 6.87 - 6.81 (m, 1H). 13C NMR (100 MHz,
CDCl3) δ 154.3, 149.5, 149.2, 139.6, 137.0, 129.0, 128.7, 124.1, 123.8,
120.3, 118.9. HRMS (ESI) m/z calcd for C11H9NO4SNa 274.0144
[M+Na]+; found 274.0141. IR (KBr): 3445, 3082, 1577, 1495, 1199, 1157,
1120, 781, 675 cm-1.
General procedure for benzofuran synthesis.
To
a
solution of 1.0 mmol methyl 2-hydroxycinnamat or 2-
(phenylsulfonylvinyl)phenol with different substituent groups in 10mL
DMF was added 1.5 mmol Cesium carbonate and 0.5 mmol dihydrated
copper (II) chloride. The mixture was stirred at 100℃ overnight. The
mixture was poured into water, extracted with EtOAc and washed with
brine. The combined organic phase was dried over MgSO4 and
concentrated to dryness. The residue was purified by flash
chromatography to afford the corresponding benzofuran derivatives 7
Benzofuran-2-carboxylic acid (7aa)[26] Prepared according to general
Acknowledgements
procedure as
a white solid (10.1 mg, obtained from 0.1 mmol
This research was supported by National Natural Science
Foundation of China (NSFC-21272185, 21572178).
corresponding alkenlated phenyl 2-pyridinesulfonate, 62%) after
purification by flash column chromatography using a mixture of petroleum
ether and ethyl acetate (3:1 v/v). m. p. = 191 – 192 oC. 1H NMR (400MHz,
d6-DMSO): δ 7.79 (d, J = 7.6 Hz, 1H), 7.76 – 7.64 (m, 2H), 7.52 – 7.47
(m, 1H), 7.37 – 7.34 (m, 1H). 13C NMR (100 MHz, d6-DMSO) δ 160.6,
155.4, 146.7, 128.0, 127.3, 124.3, 123.6, 113.9, 112.5. HRMS (ESI) m/z
calcd for C9H6O3Na 185.0209 [M+Na]+; found 185.0212. IR (KBr): 3457,
1695, 1581, 1430, 1301, 1232, 1187, 944, 819, 748 cm-1.
Keywords:
phenol
·
regioselectivity
·
C-H
activation · olefination · acetoxylation
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corresponding alkenlated phenyl 2-pyridinesulfonate, 63%) after
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10.1002/asia.201601413
Chemistry - An Asian Journal
FULL PAPER
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Text for Table of Contents
Bin Li, Dong-Dong Guo, Shi-Huan Guo,
Gao-Fei Pan, Ya-Ru Gao, Yong-Qiang
Wang*
Palladium-catalyzed ortho
allkenylation and acetoxylation of
phenols: The reaction proceeds via a
seven-membered cyclopalladated
intermediate and shows complete regio-
and diastereoselectivity.
Page No. – Page No.
Palladium-Catalyzed C-H
Functionalization of Phenyl 2-
Pyridylsulfonate
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