Carboxylative Cyclization of 2-Butenoates with Carbon Dioxide: Access to Glutaconic Anhydrides

Article abstract of DOI:10.1021/acs.joc.0c01717

Cyclic anhydrides are versatile synthons and functional comonomers. Herein, we reported an organic base-promoted carboxylative cyclization of 2-butenoates with carbon dioxide to produce important glutaconic anhydrides in good yields. This metal-free react

Full text of DOI:10.1021/acs.joc.0c01717

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Note
Carboxylative Cyclization of 2-Butenoates with
Carbon Dioxide: Access to Glutaconic Anhydrides
Ke Zhang, Wen-Zhen Zhang, Xue-Yan Tao, Min Zhang, Wei-Min Ren, and Xiao-Bing Lu
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.0c01717 • Publication Date (Web): 06 Aug 2020
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The Journal of Organic Chemistry
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Carboxylative Cyclization of 2-Butenoates with Carbon Dioxide: Access
to Glutaconic Anhydrides
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Ke Zhang, Wen-Zhen Zhang,* Xue-Yan Tao, Min Zhang, Wei-Min Ren, and Xiao-Bing Lu
State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024, P. R. China.
zhangwz@dlut.edu.cn
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O
R2
R2
DBU (3 equiv.)
O
CO2
O
+
CH3CN, r.t, 18 h
R1
LG
1.0 MPa
R1
O
31 examples
R = aryl, alkyl
68% to 95% yield
LG = OAr, Cl, NR2
Abstract: Cyclic anhydrides are versatile synthons and functional comonomers. Herein we reported an
organic base-promoted carboxylative cyclization of 2-butenoates with carbon dioxide to produce
important glutaconic anhydrides in good yields. This metal-free reaction showed broad substrate scopes
and proceeded under mild reaction conditions.
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Cyclic anhydrides are important acylating agents in organic synthesis1 and functional monomers for
the ring-opening copolymerization with epoxides2. Among their diverse derivatives, glutaconic
anhydrides are frequently used as formal cycloaddition partners and allenoate precursors to construct
various compounds of synthetic and biological interest.3,4 With regard to the preparation of glutaconic
anhydrides, traditional approach heavily relies on the dehydration of dicarboxylic acids4 (Scheme 1, a).
Despite its reliability, this method requires the synthesis of dicarboxylic acid in advance via laborious
multistep reactions using stoichiometric oxidants, strong base and other harsh reaction conditions.
Therefore, it is highly desirable to develop a more convenient and efficient synthetic route toward
glutaconic anhydride in terms of green chemistry.
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Scheme 1. Synthesis of Cyclic Anhydrides
(a) dehydration of dicarboxylic acids
Ac2O
or
O
O
R
O
O
TMS
OEt
HO
OH
R
O
(b) electrochemical or transtion-metal catalytic reaction using CO2
O
O
O
cathodic reduction
R
R
CO2
+
or Ni, Pd catalysis
R
R
(c) carboxylative cyclization of propenyl ketones using CO2
O
O
O C O
base
O
O
O
O
R
R
R
R
R
R
this work
(d)
: carboxylative cyclization of 2-butenoates using CO2
O
O
O C O
O
O
O
O
LG
R
LG
R
R
O
I
II
Utilization of carbon dioxide (CO2) as a renewable C1 building block in organic synthesis has been
extensively studied over the past decades.5 Compared with the previously reported many strategies to
convert CO2 into carboxylic acids, ester, amide and other heterocyclic compounds, direct synthesis of
cyclic anhydrides using CO2 has been less explored. Maleic anhydrides can be accessed by cathodic
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The Journal of Organic Chemistry
dicarboxylation of phenylacetylene with CO2 using aluminum as the anode6, or by Ni-catalyzed double
carboxylation of alkynes with CO2 using excess zinc powder as the reductant7 (Scheme 1, b). Isatoic and
other anhydrides can be synthesized by transition-metal catalyzed cyclization reactions with the combined
use of CO2 and CO under redox-neutral conditions8. In 2016, we developed a carboxylative cyclization
reaction of propenyl ketones with CO2,9 in which the cyclization step proceeded via an intramolecular
attack of enolate oxygen on the carboxylate group, thus only one oxygen atom of carbon dioxide was
incorporated into the α-pyrone product10 (Scheme 1, c). We envisioned that if 2-butenoates were used as
substrates for the base-promoted carboxylative cyclization reaction, the γ-carboxylation of in situ formed
enolate I with CO2 and the followed intramolecular cyclization of intermediate II via the nucleophilic
attack of the carboxylate oxygen would give glutaconic anhydride (Scheme 1, d). Herein, we describe the
realization of the above hypothesis via an organic base-promoted metal-free reaction to construct
glutaconic anhydride from carbon dioxide in excellent selectivity.
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The initial exploration selected the pentafluorophenyl 3-phenyl-2-butenoate (1aa) as the model
substrates to optimize the reaction conditions due to that pentafluorophenoxide should be a good leaving
group (Table 1). When 3.0 equivalent of DBU was used as base and acetonitrile as solvent, the
carboxylative cyclization reaction of 1aa with 1.0 MPa of CO2 proceeded successfully at the room
temperature in the absence of any metal catalyst, affording the desired product 4-phenyl glutaconic
anhydride (2a) in 90% yield (entry 1). DBN and MTBD were also found to be effective for this reaction
despite that the decreased yields of 2a were obtained (entries 2 and 3). Triethylamine, DMAP, and tested
inorganic bases such as cesium carbonate, cesium fluoride or sodium hydride could not promote the
reaction and no carboxylated product was observed (entries 4 to 8). THF and DMF were also suitable
solvent for this reaction (entries 9 and 10), while the reaction in toluene gave the moderate yields of 2a
(entry 11). The decrease of DBU amount to 1.0 equivalent resulted in the obviously lower yield (32%)
(entry 12). The combination use of 1.0 equivalent of DBU and 2.0 equivalent of Cs2CO3 gave the same
result as the only use of 1.0 equivalent of DBU (entry 13). When DBU amount was slightly increased to
1.5 equivalent, an enhanced yield (64%) of 2a was obtained (entry 14). This indicated that excess DBU
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would be crucial for the formation of anhydride product. It’s well-known that CO2 could be activated by
DBU and other strong organic bases by the formation of base–CO2 adducts.11 Probably, the excess DBU
in this reaction would also capture and activate CO2, and thus promote the carboxylative cyclization
reaction. It is noteworthy that the reaction using CO2 balloon still underwent efficiently although a slightly
decreased yield (84%) of 2a was obtained (entry 15).
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Table 1. Optimization of the reaction conditions a
O
O
Base (3 equiv.)
O
CO2
+
Ph
OC6F5
Solvent, r.t, 18 h
Ph
O
1aa
2a
Entry
1
Base
Solvent
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
THF
Yield (%)
90
DBU
DBN
MTBD
NEt3
2
77
3
60
4
<1
5
DMAP
Cs2CO3
CsF
<1
6
<1
7
<1
8
NaH
<1
9
DBU
DBU
DBU
DBU
DBU
DBU
DBU
78
10
11
12b
13c
14d
15e
DMF
80
Toluene
CH3CN
CH3CN
CH3CN
CH3CN
55
32
32
64
84
a Reaction conditions: 1aa (0.1 mmol), CO2 (1.0 MPa), base (0.3 mmol), solvent (2 mL ), r.t, 18 h. b 0.1 mmol
DBU was used. c 0.1 mmol DBU and 0.2 mmol Cs2CO3 were used. d 0.15 mmol DBU was used. e CO2 balloon
was used. DBU: 1,8-diazabicyclo [5.4.0]undec-7-ene. DBN: 1,5-diazabicyclo[4.3.0]non-ene. MTBD: 7-metyl-
1,5,7-triazabicyclo[4.4.0]dec-5-ene. DMAP: 4- dimethylaminopyridine.
Since the leaving group played a vital role in the formation of cyclic anhydride products, the
carboxylative cyclization of various 2-butenoates bearing different leaving groups were then tested
(Scheme 2). 2,4-Difluorophenyl (1ab), 4-trifluoromethylphenyl (1ae), 2,4-dinitrophenyl (1af) and
hexafluoroisopropanyl (1aj) esters participated in the carboxylative cyclization reaction smoothly and
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The Journal of Organic Chemistry
gave 86-90% yields comparable to pentafluorophenyl ester substrate 1aa. Mono fluorophenoxide (1ac,
1ad) and mononitrophenyloxide (1ag and 1ah) were found to be good leaving groups, while the
unsubstituted phenoxide proved to be less effective and only 68% yield of 2a was obtained when phenyl
3-phenyl-2-butenoate (1ai) was used. Another advantage for the use of those electron-deficient leaving
groups is to suppress the alcoholysis of the anhydride product to generate hemiesters by-product. 2-
Butenoyl chloride (1ak), imidazole (1al) and phthalimide (1am) were also verified as suitable substrates
for this reaction. Considering the easy availability of pentafluorophenyl esters, and facile recovery of
pentafluorophenol after the reaction, our explorations still selected pentafluorophenyl 2-butenoate as the
substrates.
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Scheme 2. Carboxylative Cyclization of Various 2-Butenoates with Carbon Dioxide a
O
O
DBU (3 equiv.)
CO2
O
+
Ph
LG
CH3CN, r.t, 18 h
Ph
O
O
1.0 MPa
1ab 1am
-
2a
F
F
O
O
O
Ph
Ph
O
Ph
O
F
F
1ac
1ad
1ab
, 83%
, 81%
, 87%
NO2
Ph
CF3
Ph
O
O
O
O
Ph
Ph
Ph
O
O
NO2
NO2
1ae
1ah
1ag
, 88%
1af
1ai
, 84%
, 90%
NO2
Ph
O
O
CF3
CF3
O
O
Ph
O
O
, 68%
1aj
, 85%
, 86%
O
O
O
N
O
Ph
N
Ph
Cl
O
, 85%
N
1ak
, 89%
1al
, 80%
1am
a Reaction conditions: 1a (0.1 mmol), CO2 (1.0 MPa), DBU (0.3 mmol), CH3CN (2 mL ), r.t, 18 h.
With the optimized reaction conditions in hands, we next investigated the substrate scopes with regard
to pentafluorophenyl 2-butenoate using 3.0 equivalent of DBU as base at room temperature in acetonitrile
(Scheme 3). 3-Aryl-2-butenoate (1) containing various functional groups such as electron-donating alkyl
and alkoxy substituents, electron-withdrawing fluoride, chloride, and bromide substituents all conducted
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the reaction smoothly to produce the corresponding cyclization products 2b−2l in good yields. The
structures of cyclic anhydride products 2b and 2e were further confirmed by X-ray crystallography (See
SI).12 4-Furanyl glutaconic anhydride (2m) and 4-thiophenyl glutaconic anhydride (2n) could be
synthesized by this reaction in 86% and 80% yields respectively. 3-Alkyl-2-butenoate gave the desired
products 2o−2p in satisfactory yields and cyclopropanyl group was tolerated (2q). Besides the mono-
substituted products, 3,4-disubstituted glutaconic anhydrides 2r and 2s were obtained in good yields.
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Scheme 3. Carboxylative Cyclization of Various 2-Butenoates with Carbon Dioxide a
O
R'
DBU (3 equiv.)
O
R'
R
CO2
O
+
CH3CN, r.t, 18 h
R
OC6F5
O
1.0 MPa
1
2
O
O
O
O
O
O
O
O
O
tBu
Cy
2c
, 92%
2d
, 92%
2b
, 91%
O
O
O
O
O
O
O
O
O
O
O
MeO
2g
, 78%
2f
2e
2h
2k
2n
, 94%
, 95%
O
O
O
O
O
O
O
O
O
Ph
Br
F
2j
, 92%
, 69%
2i
, 78%
O
O
O
O
O
O
O
O
O
O
Cl
2m
, 86%
, 88%
2l
, 75%
O
O
O
O
O
O
O
O
O
S
2p
2o
, 73%
, 89%
, 80%
O
O
O
O
O
O
O
O
Ph
O
O
2q
, 82%
2s
, 70%
2r
, 68%
a Reaction conditions: 1 (0.1 mmol), CO2 (1.0 MPa), DBU (0.3 mmol), CH3CN (2 mL ), r.t, 18 h.
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The Journal of Organic Chemistry
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The synthetic utility of this carboxylative cyclization reaction was firstly demonstrated through the
gram-scale synthesis of 2a in 84% yield (Scheme 4, up). Then the obtained cyclic anhydride 2a was
employed as a versatile intermediate to easily transform into other important compounds by simple
organic reactions (Scheme 4, down). The hydrolytic reaction of 2a under basic conditions generated
glutaconate 3a in 90% yield. The reduction of 2a with lithium aluminum hydride furnished 3-phenyl-2-
pentene-1,5-diol 4a in 70% yield. DMAP promoted cycloaddition of 2a and 4-nitrobenzaldehyde gave 3,
6-dihydro-6-oxo-2H-pyran-3-carboxylate 5a in moderated yield,13 while the reaction of 2a with excess
dimethyl acetylenedicarboxylate resulted in an unexpected compound 6a, which might formed by a
cycloaddition-nucleophilic addition reaction sequence. The structure of product 6a was determined by X-
ray crystallography.12 The hydrogenation of 2a with H2 using Pd/C as catalyst readily gave 3-
phenylglutaric anhydride 7a in good yield.
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Scheme 4. Gram-Scale Reaction and Synthetic Applications
O
O
DBU (3 equiv.)
O
CO2
+
Ph
OC6F5
, 6 mmol
CH3CN, r.t, 18 h
Ph
2a
O
1.0 MPa
1aa
, 84%, 0.95g
O
O
7a,
83%
O
Ph
O
Pd/C
1, 4-nitrobenzaldehyde
2, TMSCHN2
1, NaOH aq.
2, TMSCHN2
COOMe
COOMe
O
H2
Ph
Ph
COOMe
O
3a
, 90%
O2N
5a
, 68%
O
COOMe
COOMe
Ph
O
2a
OH
Ph
O
LiAlH4
THF
DMAD
COOMe
COOMe
Et3N
Ph
OH
, 70%
6a,
70%
4a
To illustrate which carbonyl group in the anhydride product come from CO2, the isotopic labelling
reaction was carried out (Scheme 5). According to the 13C{1H} NMR spectroscopy (See SI), the reaction
of 1aa with 13CO2 gave 2a’ and 2a’’ in 1:1 ratio, probably due to the rapid 1,3-hydrogen shift of in the
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presence of a base. For the reaction of 1ra with 13CO2, the more stable isomer 2r’’ was obtained according
to the 13C{1H} NMR and 1H-13C{1H} gHMBC spectroscopy (See SI), while 2r’ was not observed.
Scheme 5. Isotopic Labelling Reaction
1
2
3
4
5
6
7
8
9
O
13C
O
13C
13CO
2 (0.1 MPa)
O
O
O
DBU (3 equiv.)
+
Ph
OC6F5
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60
CH3CN, r.t, 18 h
Ph
O
Ph
O
1aa
2a''
2a'
2a' 2a''
+
(1:1), 80% yield
O
O
O
13CO
2 (0.1 MPa)
OC6F5
O
13C
O
13C
DBU (3 equiv.)
+
O
O
CH3CN, r.t, 18 h
O
2r'
1ra
O
2r''
42% yield
O
not observed
Based on the control experiments in Table 1, the above labelling experiments and previous reports,9,10
a possible mechanism for this carboxylative cyclization reaction was proposed (Scheme 6). The reaction
of pentafluorophenyl 2-butenoate with DBU would firstly form the substituted vinylketene A,14,15 which
continued to react with another DBU to generate zwitterionic dienolate B.14,15 Meanwhile, CO2 would be
activated by the formation of DBU-CO2 adduct. Then intermediate B would conduct γ-carboxylation with
DBU-CO2 to give glutaconate C, in which the intramolecular attack of carboxylate group to the carbonyl
next to DBU would finally yield the anhydride product.
Scheme 6. Possible Mechanism
O
O
DBU (3 equiv.)
O
+
CO2
CH3CN, r.t, 18 h
R
OC6F5
R
O
DBU
DBUH
CO
CO
DBU +
2
O
C6F5O
O
O
DBU
O
[DBU-
]
O
DBU
2
C
R
R
DBU
R
A
B
C
In conclusions, we have developed a straightforward access to synthetically important glutaconic
anhydrides via an organic base-promoted carboxylative cyclization of 2-butenoate with carbon dioxide.
A variety of 2-butenoates bearing electro-deficient leaving groups such as fluorophenoxide,
trifluoromethylphenoxide, and nitrophenoxide underwent this reaction smoothly and gave anhydride
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products in good yields. This metel-free reaction showed broad substrate scopes and proceeded under
very mild reaction conditions.
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EXPERIMENTAL SECTION
9
Unless otherwise stated, all manipulations were performed using standard Schlenk techniques under a
dry nitrogen or carbon dioxide atmosphere. CH3CN was distilled with P2O5. THF and toluene were
distilled from sodium/benzophenone. All of the solvents were stored over 4A molecular sieves before
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13
used. NMR spectra were recorded on 400M or 500M (1H NMR, 400 MHz or 500MHz; C NMR, 101
MHz or 126MHz) spectrometer in CDCl3 or DMSO at ambient temperature and chemical shifts are
expressed in parts per million (δ, ppm). Proton chemical shifts are referenced to 7.26 ppm (CHCl3) or
2.50 ppm (DMSO) and carbon chemicalshifts are referenced to 77.0 ppm (CHCl3) or 39.5 ppm (DMSO).
High resolution mass spectra (HRMS) were recorded on a Q-TOF mass spectrometry equipped with Z-
spray ionization source. Infrared spectra (IR) were measured using a Nicolet NEXUS FT-IR
spectrophotometer. Carbon dioxide (99.999%), and other commercially available chemicals were used
without further purification.
General Procedure for the Preparation of 2-Butenoate Substrate. Except 3-phenyl-2-butenoyl
chloride (1ak),14a 3-phenyl-2-butenoylimidazole (1al),16 3-phenyl-2-butenoyl phthalimide (1am)17 were
prepared according to the literature procedure, Other 2-butenoate substrates were prepared using the
following procedure.18
A mixture of carboxylic acid (5 mmol), pentafluorophenol or phenol derivatives (6 mmol), DMAP
(61.0 mg, 0.5 mmol), and EDCI (1.1 g, 5.5 mmol) in THF (20 mL) was stirred overnight at room
temperature. The mixture was diluted cautiously with saturated NaHCO3, and then extracted with EtOAc
(3 x 30 mL). The combined organic phase was washed with brine (100 mL). After drying over Na2SO4
and filtration, the solvent was removed under reduced pressure. The residue was purified by flash
chromatography on silica gel (hexanes /ethyl acetate) to afford the desired ester products.
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Perfluorophenyl (E)-3-phenylbut-2-enoate (1aa). white solid, 1.31 g, 80% yield, Rf = 0.50 (petroleum
ether/EtOAc 50:1). 1H NMR (400 MHz, CDCl3) δ 7.61–7.54 (m, 2H), 7.47–7.42 (m, 2H), 6.45–6.42 (m,
1H), 2.68–2.66 (m, 3H). 13C{1H} NMR (126 MHz, CDCl3) δ 162.4, 161.9, 141.4 (dm, J = 252.5 Hz),
141.2, 139.3 (dm, J = 252.9 Hz), 137.9 (dm, J = 252.5 Hz), 130.0, 128.7, 126.5, 125.2 (m),113.0, 18.6.
19F NMR (470 MHz, CDCl3) δ -152.53 – -153.60 (m), -158.70 (t, J = 21.7 Hz), -162.73 – -162.84 (m). IR
(neat cm-1) ν 2929, 2855, 1759, 1620, 1518, 1005, 896. HRMS (EI-TOF) m/z: [M]+ Calcd for C16H9F5O2
328.0523; Found 328.0515.
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2,4-Difluorophenyl (E)-3-phenyl but-2-enoate (1ab). white solid, 0.86 g, 63% yield, Rf = 0.50
(petroleum ether/EtOAc 50:1). 1H NMR (400 MHz, CDCl3) δ 7.56–7.54 (m, 1H), 7.43–7.41 (m, 4H),
7.19–7.13 (m, 2H), 6.98–6.87 (m, 1H), 6.39 (s, 1H), 2.64 (s, 3H). 13C{1H} NMR (126 MHz, CDCl3) δ
163.9, 160.0 (dd, J = 196.9, 10.5 Hz), 159.9, 154.3 (dd, J = 251.8, 12.5 Hz), 141.7, 134.5 (dd, J = 12.9,
4.0 Hz), 129.6, 128.6, 126.4, 124.5 (dd, J = 9.9, 2.0 Hz), 114.7, 111.1 (dd, J = 23.0, 3.8 Hz), 105.0 (dd, J
= 26.9, 22.5 Hz), 18.3. 19F NMR (470 MHz, CDCl3) δ -113.05 – -113.08 (m), -123.25 – -123.28 (m). IR
(neat cm-1) ν 2912, 2852, 1743, 1624, 1119, 850. HRMS (EI-TOF) m/z: [M]+ Calcd for C16H12F2O2
274.0805; Found 274.0807.
2-Fluorophenyl (E)-3-phenyl but-2-enoate (1ac). white solid, 0.67 g, 52% yield, Rf = 0.55 (petroleum
ether/EtOAc 50:1). 1H NMR (400 MHz, CDCl3) δ 7.57–7.55 (m, 2H), 7.43–7.41 (m, 3H), 7.23–7.16 (m,
4H), 6.41 (d, J = 1.2 Hz, 1H), 2.64 (d, J = 4.3 Hz, 3H). 13C{1H} NMR (101 MHz, CDCl3) δ 163.9, 159.4,
154.3 (d, J = 249.0 Hz), 141.7, 138.1 (d, J = 12.7 Hz), 129.5, 128.6, 126.8 (d, J = 7.2 Hz), 126.4, 124.4
(d, J = 3.8 Hz), 124.0, 116.6 (d, J = 18.4 Hz), 115.0, 18.3. 19F NMR (470 MHz, CDCl3) δ -128.20 (dd, J
= 14.0, 7.5 Hz). IR (neat cm-1) ν 2954, 2925, 2843, 1744, 1625, 1102, 996, 764. HRMS (EI-TOF) m/z:
[M]+ Calcd for C16H13FO2 256.0900; Found 256.0897.
4-Fluorophenyl (E)-3-phenyl but-2-enoate (1ad). white solid, 0.77 g, 60% yield, Rf = 0.55 (petroleum
ether/EtOAc 50:1). 1H NMR (400 MHz, CDCl3) δ 7.56–7.54 (m, 2H), 7.43–7.41 (m, 3H), 7.14–7.06 (m,
4H), 6.36 (d, J = 1.1 Hz, 1H), 2.65 (d, J = 1.0 Hz, 3H). 13C{1H} NMR (101 MHz, CDCl3) δ 165.0, 161.3,
158.9, 146.5 (d, J = 2.8 Hz), 141.8, 129.5, 128.6, 126.4, 123.1 (d, J = 8.4 Hz), 116.1, 115.8 (d, J = 13.9
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Hz), 18.2. 19F NMR (470 MHz, CDCl3) δ -117.35 (dd, J = 9.9, 5.6 Hz). IR (neat cm-1) ν 2949, 2925, 1732,
1625, 999, 868. HRMS (EI-TOF) m/z: [M]+ Calcd for C16H13FO2 256.0900; Found 256.0891.
4-Trifluoromethylphenyl (E)-3-phenylbut-2-enoate (1ae). white solid, 1.06 g, 69% yield, Rf = 0.50
(petroleum ether/EtOAc 50:1). 1H NMR (400 MHz, CDCl3) δ 7.68 (d, J = 8.5 Hz, 2H), 7.57–7.54 (m,
2H), 7.43–7.42 (m, 3H), 7.29 (d, J = 8.5 Hz, 1H)., 6.38 (d, J = 1.2 Hz, 1H), 2.65 (d, J = 1.2 Hz, 3H).
13C{1H} NMR (101 MHz, CDCl3) δ 164.4, 159.8, 153.3, 141.7, 129.6, 128.7, 127.8 (q, J = 32.8 Hz),
126.7 (q, J = 3.7 Hz), 126.4, 124.0 (q, J = 284.0 Hz), 122.3, 115.4, 18.3. 19F NMR (470 MHz, CDCl3) δ
-62.18 (s). IR (neat cm-1) ν 2954, 2913, 1737, 1626, 999, 865. HRMS (EI-TOF) m/z: [M]+ Calcd for
C17H13F3O2 306.0868; Found 306.0869.
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2,4-Dinitrophenyl (E)-3-phenylbut-2-enoate (1af). white solid, 1.23 g, 75% yield, Rf = 0.30 (petroleum
ether/EtOAc 50:1). 1H NMR (400 MHz, CDCl3) δ 8.96 (d, J = 2.6 Hz, 1H), 8.53 (dd, J = 8.9, 2.7 Hz, 1H),
7.59–7.54 (m, 3H), 7.45-7.43 (m, 3H), 6.42 (d, J = 1.0 Hz, 1H), 2.62 (d, J = 0.9 Hz, 3H). 13C{1H} NMR
(101 MHz, CDCl3) δ 162.8, 162.6, 148.8, 144.8, 142.1, 141.1, 132.0, 130.1, 128.8, 126.7, 126.5, 121.5,
113.6, 18.6. IR (neat cm-1) ν 1747, 1605, 1537, 1098, 986. HRMS (EI-TOF) m/z: [M]+ Calcd for
C16H12N2O6 328.0695; Found 328.0704.
2-Nitrophenyl (E)-3-phenylbut-2-enoate (1ag). white solid, 0.99 g, 70% yield, Rf = 0.35 (petroleum
ether/EtOAc 50:1).1H NMR (400 MHz, CDCl3) δ 8.10 (dd, J = 8.2, 1.6 Hz, 1H), 7.69–7.65 (m, 1H), 7.58–
7.56 (m, 2H), 7.44–7.38 (m, 4H), 7.31 (dd, J = 8.1, 1.2 Hz, 1H), 6.43 (d, J = 1.3 Hz, 1H), 2.64 (d, J = 1.2
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Hz, 3H). C{1H} NMR (101 MHz, CDCl3) δ 163.8, 160.5, 144.1, 142.2, 141.4, 134.5, 129.7, 128.6,
126.4, 126.3, 125.6, 125.3, 114.7, 18.3. IR (neat cm-1) ν 1744, 1625, 1529, 1349, 1113, 993. HRMS (ESI-
TOF) m/z: [M+Na]+ Calcd for C16H13NNaO4 306.0742; Found 306.0755.
4-Nitrophenyl (E)-3-phenylbut-2-enoate (1ah). white solid, 1.10 g, 78% yield, Rf = 0.40 (petroleum
ether/EtOAc 50:1). 1H NMR (400 MHz, CDCl3) δ 8.32–8.28 (m, 2H), 7.57–7.54 (m, 2H), 7.44–7.43 (m,
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3H), 7.37–7.33 (m, 2H), 6.37 (d, J = 1.3 Hz, 1H), 2.66 (d, J = 1.2 Hz, 3H). C{1H} NMR (101 MHz,
CDCl3) δ 164.8, 160.6, 155.6, 145.1, 141.5, 129.8, 128.7, 126.4, 125.1, 122.5, 114.9, 18.4. IR (neat cm-1)
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ν 2974, 2913, 2847, 1736, 1614, 1525, 997, 856. HRMS (ESI-TOF) m/z: [M+Na]+ Calcd for
C16H13NNaO4 306.0742; Found 306.0751.
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Phenyl (E)-3-phenylbut-2-enoate (1ai). white solid, 0.67 g, 56% yield, Rf = 0.50 (petroleum
ether/EtOAc 50:1). 1H NMR (400 MHz, CDCl3) δ 7.62–7.60 (m, 2H), 7.49–7.45 (m, 5H), 7.32–7.29 (m,
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MHz, CDCl3) δ 165.0, 158.5, 150.7, 141.9, 129.4, 129.3, 128.6, 126.4, 125.6, 121.7, 116.0, 18.2. IR (neat
cm-1) ν 2933, 1729, 1626, 1592, 994. HRMS (ESI-TOF) m/z: [M+Na]+ Calcd for C16H14NaO2 261.0891;
Found 261.0899.
1,1,1,3,3,3-Hexafluoropropan-2-yl (E)-3-phenylbut-2-enoate (1aj). white solid, 1.30 g, 83% yield, Rf
= 0.40 (petroleum ether/EtOAc 50:1). 1H NMR (400 MHz, CDCl3) δ 7.55–7.52 (m, 2H), 7.43–7.40 (m,
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3H), 6.26 (d, J = 0.9 Hz, 1H), 5.92–5.86 (m, 1H), 2.65 (d, J = 0.8 Hz, 3H). C{1H} NMR (101 MHz,
CDCl3) δ 162.6, 162.3, 141.2, 130.0, 128.7, 126.5, 120.7 (q, J = 284.7 Hz), 113.1, 66.0 (dt, J = 69.1, 34.5
Hz), 18.6. 19F NMR (470 MHz, CDCl3) δ -73.29 (d, J = 6.2 Hz). IR (neat cm-1) ν 2962, 1743, 1624, 1112,
926, 905, 765. HRMS (EI-TOF) m/z: [M]+ Calcd for C13H10F6O2 312.0585; Found 312.0579.
(E)-2-(3-phenylbut-2-enoyl)isoindoline-1,3-dione (1am). white solid, 0.67g, 68% yield, Rf = 0.30
(petroleum ether/EtOAc 5:1). 1H NMR (400 MHz, CDCl3) δ 8.01–7.99 (m, 2H), 7.80–7.78 (m, 2H), 7.64–
7.62 (m, 2H), 7.45–7.43 (m, 3H), 6.96–6.94 (m, 1H), 2.70 (d, J = 1.1 Hz, 3H). 13C{1H} NMR (101 MHz,
DMSO-d6) δ 169.6, 165.9, 163.3, 157.4, 141.4, 135.8, 134.6, 132.7, 131.3, 130.2, 129.0, 126.7, 124.2,
123.2, 120.0, 18.4. IR (neat cm-1) ν 2910, 2860, 1734, 1689, 1281, 1052, 712. HRMS (ESI-TOF) m/z:
[M+Na]+ Calcd for C18H13NNaO3 314.0793; Found 314.0803.
Perfluorophenyl (E)-3-(p-tolyl)but-2-enoate (1ba). white solid, 1.28 g, 75% yield, Rf = 0.50 (petroleum
ether/EtOAc 50:1). 1H NMR (400 MHz, CDCl3) δ 7.50 (d, J = 8.2 Hz, 2H), 7.27 (d, J = 8.2 Hz, 2H), 6.44
(s, 1H), 2.67 (s, 3H), 2.43 (s, 3H). 13C{1H} NMR (101 MHz, CDCl3) δ 162.3, 162.1, 141.5 (dm, J = 253.4
Hz), 140.5, 138.2, 139.4, 139.1 (dm, J = 252.0 Hz), 137.9 (dm, J = 253.4 Hz), 126.4, 125.3 (m), 112.0,
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21.2, 18.4. F NMR (470 MHz, CDCl3) δ -152.58 – -152.64 (m), -158.88 (t, J = 21.6 Hz), -162.84 – -
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162.95 (m). IR (neat cm-1) ν 2962, 2929, 2864, 1756, 1619, 1517, 1098, 896. HRMS (EI-TOF) m/z: [M]+
Calcd for C17H11F5O2 342.0679; Found 342.0675.
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Perfluorophenyl (E)-3-(4-(tert-butyl)phenyl)but-2-enoate (1ca). white solid, 1.50 g, 78% yield, Rf =
0.50 (petroleum ether/EtOAc 50:1). 1H NMR (400 MHz, CDCl3) δ 7.53 (d, J = 8.1 Hz, 2H), 7.46 (d, J =
8.1 Hz, 2H), 6.43 (d, J = 1.1 Hz, 1H), 2.66 (d, J = 1.1 Hz, 3H), 1.36 (s, 9H). 13C{1H} NMR (126 MHz,
CDCl3) δ 162.2, 162.1, 153.7, 141.5 (dm, J = 252.8 Hz), 139.3 (dm, J = 252.7 Hz), 138.1, 137.9 (dm, J =
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252.8 Hz), 126.3, 125.7, 125.3 (m), 112.1, 34.8, 31.2, 18.4. F NMR (470 MHz, CDCl3) δ -152.52 – -
152.58 (m), -158.82 (t, J = 21.7 Hz), -162.79 – -162.90 (m). IR (neat cm-1) ν 2966, 2872, 1757, 1619,
1007, 832. HRMS (EI-TOF) m/z: [M]+ Calcd for C20H17F5O2 384.1149; Found 384.1157.
Perfluorophenyl (E)-3-(4-cyclohexylphenyl)but-2-enoate (1da). white solid, 1.33 g, 65% yield, Rf =
0.50 (petroleum ether/EtOAc 50:1). 1H NMR (400 MHz, CDCl3) δ 7.52 (d, J = 8.3 Hz, 2H), 7.28 (d, J =
8.3 Hz, 2H), 6.42 (d, J = 1.0 Hz, 1H), 2.65 (d, J = 1.0 Hz, 3H). 2.56 (t, J = 8.1 Hz, 1H), 1.92–1.77 (m,
5H), 1.51–1.27 (m, 5H). 13C{1H} NMR (126 MHz, CDCl3) δ 162.4, 162.1, 150.6, 141.4 (dm, J = 251.7
Hz), 139.3 (dm, J = 252.4 Hz), 138.5, 137.9 (dm, J = 251.7 Hz), 127.2, 126.5, 125.3 (m), 112.0, 44.4,
34.3, 26.8, 26.1, 18.4. 19F NMR (470 MHz, CDCl3) δ -152.55 (d, J = 17.8 Hz), -158.83 (t, J = 21.6 Hz), -
162.80 – -162.89 (m). IR (neat cm-1) ν 2928, 2853, 1759, 1618, 1606, 1518, 1100, 896. HRMS (EI-TOF)
m/z: [M-C6F5O]+ Calcd for C16H19O 227.1430; Found 227.1437.
Perfluorophenyl (E)-3-(4-methoxyphenyl) but-2-enoate (1ea). white solid, 1.52 g, 85% yield, Rf = 0.40
(petroleum ether/EtOAc 50:1). 1H NMR (400 MHz, CDCl3) δ 7.58–7.54 (m, 2H), 6.97–6.93 (m, 2H), 6.40
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(d, J = 1.2 Hz, 1H), 3.87 (s, 3H), 2.65 (d, J = 1.2 Hz, 3H). C{1H} NMR (126 MHz, CDCl3) δ 162.2,
161.4, 141.5 (dm, J = 252.4 Hz), 139.2 (dm, J = 252.5 Hz), 137.9 (dm, J = 252.4 Hz), 133.2, 128.1, 125.4
(m), 114.1, 110.8, 55.4, 18.2. 19F NMR (470 MHz, CDCl3) δ -152.60 – -152.68 (m), -158.95 (t, J = 21.6
Hz), -162.88 – -162.98 (m). IR (neat cm-1) ν 2937, 2831, 1754, 1600, 1518, 1098, 896. HRMS (EI-TOF)
m/z: [M]+ Calcd for C17H11F5O3 358.0628; Found 358.0648.
Perfluorophenyl (E)-3-(2,3-dihydrobenzo[b] [1,4] dioxin-6-yl) but-2-enoate (1fa). white solid, 1.58 g,
82% yield, Rf = 0.35 (petroleum ether/EtOAc 50:1). 1H NMR (400 MHz, CDCl3) δ 7.12–7.10 (m, 2H),
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6.91–6.89 (m, 1H), 6.37 (d, J = 1.2 Hz, 1H), 4.32–4.28 (m, 4H), 2.60 (d, J = 1.2 Hz, 3H). 13C{1H} NMR
(101 MHz, CDCl3) δ 162.1, 161.5, 145.5, 143.5, 141.4 (dm, J = 253.8 Hz), 139.2 (dm, J = 252.5 Hz),
137.9 (dm, J = 253.9 Hz), 134.2, 125.3 (m), 120.0, 117.4, 115.7, 111.3, 64.6, 64.3, 18.2. 19F NMR (470
MHz, CDCl3) δ -152.56 – -152.62 (m), -158.91 (t, J = 21.7 Hz), -162.85 – -162.96 (m). IR (neat cm-1) ν
2978, 2933, 2880, 1751, 1604, 1578, 1007, 891. HRMS (EI-TOF) m/z: [M]+ Calcd for C18H11F5O4
386.0577; Found 386.0574.
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Perfluorophenyl (E)-3-(naphthalen-2-yl) but-2-enoate (1ga). white solid, 1.23 g, 65% yield, Rf = 0.45
(petroleum ether/EtOAc 50:1). 1H NMR (400 MHz, CDCl3) δ 8.06 (s, 1H), 7.93–7.86 (m, 3H), 7.68 (d, J
= 8.6 Hz, 1H), 7.57–7.54 (m, 2H), 6.58 (s, 1H), 2.77 (s, 3H). 13C{1H} NMR (126 MHz, CDCl3) δ 164.4,
161.6, 141.4 (dm, J = 251.1 Hz), 141.1, 139.3 (dm, J = 252.3 Hz), 137.9 (dm, J = 252.8 Hz), 133.8, 129.7,
128.9, 128.6, 126.7, 126.2, 125.3 (m), 125.2, 125.0, 124.3, 116.8, 22.4. 19F NMR (470 MHz, CDCl3) δ -
152.50 – -152.56 (m), -158.49 (t, J = 21.7 Hz), -162.60 – -162.69 (m). IR (neat cm-1) ν 2966, 2925, 1761,
1630, 1519, 1130, 1003, 899. HRMS (EI-TOF) m/z: [M]+ Calcd for C20H11F5O2 378.0679; Found
378.0690.
Perfluorophenyl (E)-3-(naphthalen-1-yl) but-2-enoate (1ha). white solid, 1.66 g, 88% yield, Rf = 0.40
(petroleum ether/EtOAc 50:1). 1H NMR (400 MHz, CDCl3) δ 7.94–7.89 (m, 2H), 7.87 (s, 1H), 7.59–7.52
(m, 2H), 7.52–7.49 (m, 1H), 7.38 (d, J = 7.0 Hz, 1H), 6.32 (d, J = 1.3 Hz, 1H), 2.74 (d, J = 1.3 Hz, 3H).
13C{1H} NMR (101 MHz, CDCl3) δ 162.1, 162.0, 141.4 (dm, J = 250.9 Hz), 139.3 (dm, J = 252.6 Hz),
138.2, 137.9 (dm, J = 253.7 Hz), 134.0, 133.0, 128.7, 127.6, 127.3, 126.7, 126.6, 125.2 (m), 123.6, 113.2,
18.5. 19F NMR (470 MHz, CDCl3) δ -152.38 – -152.44 (m), -158.68 (t, J = 21.6 Hz), -162.70 – -162.80
(m). IR (neat cm-1) ν 2921, 1748, 1613, 1517, 1098, 990, 894. HRMS (EI-TOF) m/z: [M]+ Calcd for
C20H11F5O2 378.0679; Found 378.0669.
Perfluorophenyl (E)-3-([1,1'-biphenyl]-4-yl) but-2-enoate (1ia). white solid, 1.66 g, 82% yield, Rf =
0.40 (petroleum ether/EtOAc 50:1). 1H NMR (400 MHz, CDCl3) δ 7.68–7.65 (m, 6H), 7.52–7.48 (m, 2H),
7.44–7.40 (m, 1H), 6.51 (d, J = 1.0 Hz, 1H), 2.71 (d, J = 0.9 Hz, 3H). 13C{1H} NMR (101 MHz, CDCl3)
δ 161.7, 143.0, 141.4 (dm, J = 250.7 Hz), 140.0, 139.8, 139.3 (dm, J = 252.8 Hz), 137.9 (dm, J = 253.5
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Hz), 128.9, 127.9, 127.3, 127.1, 127.0, 125.3 (m), 112.7, 18.4. 19F NMR (470 MHz, CDCl3) δ -152.50 –
-152.56 (m), -158.68 (t, J = 21.6 Hz), -162.70 – -162.80 (m). IR (neat cm-1) ν 2917, 2880, 1753, 1603,
1518, 1031, 1002, 898. HRMS (EI-TOF) m/z: [M]+ Calcd for C22H13F5O2 404.0836; Found 404.0844.
Perfluorophenyl (E)-3-(4-fluorophenyl) but-2-enoate (1ja). white solid, 1.35 g, 78% yield, Rf = 0.50
(petroleum ether/EtOAc 50:1). 1H NMR (400 MHz, CDCl3) δ 7.58–7.55 (m, 2H), 7.14–7.10 (m, 2H), 6.38
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(s, 1H), 2.64 (s, 3H). C{1H} NMR (126 MHz, CDCl3) δ 163.9 (d, J = 251.0 Hz), 161.8, 161.0, 141.4
(dm, J = 251.1 Hz), 139.3 (dm, J = 252.7 Hz), 137.9 (dm, J = 253.5 Hz), 137.2 (d, J = 3.3 Hz), 128.5 (d,
J = 8.5 Hz), 125.2 (m), 115.8 (d, J = 21.7 Hz), 112.9, 18.5. 19F NMR (470 MHz, CDCl3) δ -110.55 (s), -
152.60 – -152.67 (m), -158.58 – -158.68 (m), -162.70 – -162.82 (m). IR (neat cm-1) ν 2958, 2929, 2851,
1759, 1624, 1518, 1025, 1009, 834. HRMS (EI-TOF) m/z: [M]+ Calcd for C16H8F6O2 346.0428; Found
346.0419.
Perfluorophenyl (E)-3-(4-chlorophenyl) but-2-enoate (1ka). white solid, 1.51 g, 83% yield, Rf = 0.45
(petroleum ether/EtOAc 50:1). 1H NMR (400 MHz, CDCl3) δ 7.51 (d, J = 8.5 Hz, 2H), 7.41 (d, J = 8.5
Hz, 2H), 6.40 (s, 1H), 2.63 (s, 3H). 13C{1H} NMR (126 MHz, CDCl3) δ 161.7, 160.8, 141.4 (dm, J =
251.1 Hz), 139.5, 139.3 (dm, J = 252.8 Hz), 137.9 (dm, J = 252.8 Hz), 136.2, 129.0, 127.8, 125.2 (m),
113.4, 18.4. 19F NMR (470 MHz, CDCl3) δ -152.53 – -152.59 (m), -158.50 (t, J = 21.6 Hz), -162.61 – -
162.73 (m). IR (neat cm-1) ν 2958, 2913, 2847, 1758, 1622, 1520, 1025, 894. HRMS (EI-TOF) m/z: [M]+
Calcd for C16H8ClF5O2 362.0133; Found 362.0128.
Perfluorophenyl (E)-3-(4-bromophenyl) but-2-enoate (1la). white solid, 1.42 g, 70% yield, Rf = 0.45
(petroleum ether/EtOAc 50:1). 1H NMR (400 MHz, CDCl3) δ 7.58–7.54 (m, 2H), 7.45–7.41 (m, 2H), 6.41
(d, J = 1.3 Hz, 1H), 2.63 (d, J = 1.3 Hz, 3H). 13C{1H} NMR (126 MHz, CDCl3) δ 161.7, 160.8, 141.4
(dm, J = 251.6 Hz), 140.0, 139.4 (dm, J = 253.2 Hz), 137.9 (dm, J = 253.5 Hz), 132.0, 128.0, 124.5,
125.1 (m), 113.4, 18.4. 19F NMR (470 MHz, CDCl3) δ -152.52 – -152.57 (m), -158.46 (t, J = 21.6 Hz), -
162.59 – -162.68 (m). IR (neat cm-1) ν 2962, 2917, 2843, 1757, 1621, 1518, 1025, 902. HRMS (EI-TOF)
m/z: [M]+ Calcd for C16H8BrF5O2 405.9628; Found 405.9625.
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Perfluorophenyl (E)-3-(furan-2-yl) but-2-enoate (1ma). white solid, 1.18 g, 74% yield, Rf = 0.40
(petroleum ether/EtOAc 50:1). 1H NMR (400 MHz, CDCl3) δ 7.54 (d, J = 1.5 Hz, 1H), 6.83 (d, J = 3.5
Hz, 1H), 6.63 (d, J = 1.0 Hz, 1H), 6.53 (dd, J = 3.5, 1.8 Hz, 1H), 2.52 (d, J = 1.1 Hz, 3H). 13C{1H} NMR
(126 MHz, CDCl3) δ 162.4, 153.7, 147.7, 145.1, δ 141.5 (dm, J = 251.0 Hz), 139.3 (dm, J = 252.5 Hz),
137.9 (dm, J = 253.2 Hz), 125.3 (m), 113.6, 112.5, 108.1, 15.3. 19F NMR (470 MHz, CDCl3) δ -152.59 –
-152.64 (m), -158.93 (t, J = 21.6 Hz), -162.89 – -162.99 (m). IR (neat cm-1) ν 1752, 1615, 1519, 1022,
1006, 890. HRMS (EI-TOF) m/z: [M]+ Calcd for C14H7F5O3 318.0315; Found 318.0322.
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Perfluorophenyl (E)-3-(thiophen-2-yl) but-2-enoate (1na). white solid, 1.47 g, 88% yield, Rf = 0.40
(petroleum ether/EtOAc 50:1). 1H NMR (400 MHz, CDCl3) δ 7.48–7.45 (m, 2H), 7.13–7.11 (m, 1H), 6.51
(d, J = 0.9 Hz, 1H), 2.68 (d, J = 1.0 Hz, 3H). 13C{1H} NMR (101 MHz, CDCl3) δ 162.0, 154.0, 144.5,
141.4 (dm, J = 250.9 Hz), 139.3 (dm, J = 252.8 Hz), 137.9 (dm, J = 253.9 Hz), 128.9, 128.4, 128.31,
125.2 (m), 109.7, 17.9. 19F NMR (470 MHz, CDCl3) δ -152.54 – -152.60 (m), -158.76 (t, J = 21.6 Hz), -
162.77 – -162.88 (m). IR (neat cm-1) ν 2929, 2847, 1754, 1606, 1518, 1003, 947. HRMS (EI-TOF) m/z:
[M]+ Calcd for C14H7F5O2S 334.0087; Found 334.0084.
Perfluorophenyl 3-methyl but-2-enoate (1oa). colorless oil, 0.89 g, 67% yield, Rf = 0.30 (petroleum
ether/EtOAc 100:1). 1H NMR (400 MHz, CDCl3) δ 5.98 (s, 1H), 2.25 (d, J = 1.1 Hz, 3H), 2.04 (d, J = 1.2
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Hz, 3H). C{1H} NMR (101 MHz, CDCl3) δ 164.3, 161.6, 141.4 (dm, J = 250.8 Hz), 139.2 (dm, J =
252.3 Hz), 137.9 (dm, J = 253.8 Hz), 125.3 (m), 112.7, 27.7, 20.8. 19F NMR (470 MHz, CDCl3) δ -152.86
– -153.90 (m), -159.15 (t, J = 21.6 Hz), -163.07 – -163.18 (m). IR (neat cm-1) ν 2986, 2921, 1763, 1644,
1519, 1001, 909. HRMS (EI-TOF) m/z: [M-C6F5O]+ Calcd for C5H7O 83.0491; Found 83.0491.
Perfluorophenyl (E)-3,7-dimethylocta-2,6-dienoate (1pa). colorless oil, 1.39 g, 83% yield, Rf = 0.30
(petroleum ether/EtOAc 100:1). 1H NMR (400 MHz, CDCl3) δ 5.96 (s, 1H), 5.14–5.09 (m, 1H), 2.31–
2.17 (m, 7H), 1.72–1.68 (m, 3H), 1.64–1.61 (m, 3H). 13C{1H} NMR (101 MHz, CDCl3) δ 167.7, 161.8,
141.4 (dm, J = 250.8 Hz), 139.2 (dm, J = 252.6 Hz), 137.9 (dm, J = 253.8 Hz), 133.1, 125.3 (m), 122.4,
112.1, 41.3, 26.0, 19.6, 17.7. 19F NMR (470 MHz, CDCl3) δ -152.74 – -153.80 (m), -159.03 (t, J = 22.3
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Hz), -162.96 – -163.07 (m). IR (neat cm-1) ν 2978, 2917, 2855, 1762, 1634, 1519, 1099, 1003, 902. HRMS
(EI-TOF) m/z: [M]+ Calcd for C16H15F5O2 334.0992; Found 334.0981.
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Perfluorophenyl (E)-3-cyclopropyl but-2-enoate (1qa). colorless oil, 1.17 g, 80% yield, Rf = 0.35
(petroleum ether/EtOAc 100:1). 1H NMR (400 MHz, CDCl3) δ 5.99 (d, J = 3.8 Hz, 1H), 2.02 (d, J = 0.9
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Hz, 3H), 1.66 (d, J = 1.0 Hz, 1H), 0.97–0.91 (m, 2H), 0.89–0.81 (m, 2H). C{1H} NMR (101 MHz,
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CDCl3) δ 169.8, 161.6, 141.5 (dm, J = 250.8 Hz), 139.1 (dm, J = 252.6 Hz), 137.9 (dm, J = 252.7 Hz),
125.4 (m), 109.6, 20.8, 15.4, 7.9. 19F NMR (470 MHz, CDCl3) δ -152.78 – -152.89 (m), -159.28 (td, J =
21.6, 7.3 Hz), -163.13 – -163.24 (m). IR (neat cm-1) ν 2925, 2851, 1758, 1621, 1521, 1025, 1005, 930,
837. HRMS (EI-TOF) m/z: [M-C6F5O]+ Calcd for C7H9O 109.0648; Found 109.0645.
Perfluorophenyl (E)-2-(chroman-4-ylidene) acetate (1ra). white solid, 1.30 g, 73% yield, Rf = 0.35
(petroleum ether/EtOAc 50:1). 1H NMR (400 MHz, CDCl3) δ 7.72–7.70 (m, 1H), 7.38–7.34 (m, 1H),
7.00–6.92 (m, 2H), 6.60 (s, 1H), 4.28 (t, J = 6.2 Hz, 2H), 3.42–3.39 (m, 2H). 13C{1H} NMR (101 MHz,
CDCl3) δ 162.0, 157.4, 154.0, 141.4 (dm, J = 250.9 Hz), 139.3 (dm, J = 252.8 Hz), 137.9 (dm, J = 253.7
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Hz), 133.3, 125.2 (m), 124.9, 121.3, 120.0, 118.5, 105.5, 65.3, 27.3. F NMR (470 MHz, CDCl3) δ -
152.57 – -152.63 (m), -158.61 (t, J = 21.6 Hz), -162.68 – -162.78 (m). IR (neat cm-1) ν 2994, 2884, 1753,
1602, 1518, 1002, 874. HRMS (EI-TOF) m/z: [M]+ Calcd for C17H9F5O3 356.0472; Found 356.0465.
Perfluorophenyl (E)-3-phenylpent-2-enoate (1sa). white solid, 1.37 g, 80% yield, Rf = 0.50 (petroleum
ether/EtOAc 50:1). 1H NMR (500 MHz, CDCl3) δ 7.55–7.45 (m, 5H), 6.32 (s, 1H), 3.16 (q, J = 7.5 Hz,
2H), 1.14 (t, J = 7.5 Hz, 3H). 13C{1H} NMR (101 MHz, CDCl3) δ 168.9, 161.5, 141.4 (dm, J = 251.1 Hz),
140.1, 139.3 (dm, J = 252.8 Hz), 137.9 (dm, J = 254.0 Hz), 129.9, 128.8, 126.8, 125.3 (m), 112.5, 25.0,
13.4. 19F NMR (470 MHz, CDCl3) δ -152.53 – -152.59 (m), -158.77 (t, J = 21.6 Hz), -162.77 – -162.87
(m). IR (neat cm-1) ν 2937, 2872, 1763, 1615, 1518, 1097, 1026, 955. HRMS (EI-TOF) m/z: [M]+ Calcd
for C17H11F5O2 342.0679; Found 342.0689.
General Procedure for Carboxylative Cyclization of 2-Butenoates with CO2. A 20 mL oven dried
autoclave containing a stir bar was charged with 2-butenoate (0.10 mmol), DBU (46 mg, 0.30 mmol) and
2 mL dry CH3CN in a glove box. After removal from the glove box, the autoclave was purged three times,
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and then pressurized to appropriate pressure with carbon dioxide. The reaction mixture was stirred at
room temperature for 18 h, and the remaining carbon dioxide was vented slowly. The reaction mixture
was then directly loaded into silica gel column, and the products were isolated by flash column
chromatography using EtOAc or EtOAc/acetic acid as the eluent.
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4-Phenyl-2H-pyran-2,6(3H)-dione (2a). white solid, 16.9 mg, 90% yield, Rf = 0.35 (EtOAc/acetic acid
30:1). 1H NMR (400 MHz, CDCl3) δ 7.57–7.51 (m, 5H), 6.62 (s, 1H), 3.92 (s, 2H). 13C{1H} NMR (126
MHz, CDCl3) δ 164.7, 160.2, 152.7, 133.8, 132.1, 129.5, 126.1, 112.1, 33.4. IR (neat cm-1) ν 2956, 2922,
2854, 1794, 1726, 1466, 1122, 974, 767. HRMS (ESI-TOF) m/z: [M+H]+ Calcd for C11H9O3 189.0552;
Found 189.0552..
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4-(p-Tolyl)-2H-pyran-2,6(3H)-dione (2b). white solid, 18.4 mg, 91% yield, Rf = 0.35 (EtOAc/acetic
acid 30:1). 1H NMR (400 MHz, CDCl3) δ 7.46 (d, J = 8.2 Hz, 2H), 7.30 (d, J = 8.2 Hz, 2H), 6.58 (s, 1H),
3.90 (s, 2H), 2.42 (s, 3H). 13C{1H} NMR (126 MHz, CDCl3) δ 164.9, 160.4, 152.6, 142.9, 130.8, 130.1,
126.1, 110.9, 33.3, 21.4. IR (neat cm-1) ν 2923, 2852, 1787, 1728, 1143, 999, 818, 621. HRMS (ESI-TOF)
m/z: [M+H]+ Calcd for C12H11O3 203.0708; Found 203.0705.
4-(4-(tert-Butyl)phenyl)-2H-pyran-2,6(3H)-dione(2c). white solid, 22.5 mg, 92% yield, Rf = 0.35
(EtOAc/acetic acid 30:1). 1H NMR (400 MHz, CDCl3) δ 7.51 (s, 4H), 6.59 (s, 1H), 3.91 (s, 2H), 1.35 (s,
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9H). C{1H} NMR (126 MHz, CDCl3) δ 164.9, 160.4, 156.0, 152.6, 130.8, 126.4, 126.0, 111.0, 35.0,
33.2, 31.0. IR (neat cm-1) ν 2960, 2924, 1790, 1723, 1629, 1125, 970, 868, 620. HRMS (ESI-TOF) m/z:
[M+H]+ Calcd for C15H17O3 245.1178; Found 245.1174.
4-(4-Cyclohexylphenyl)-2H-pyran-2,6(3H)-dione (2d). white solid, 24.8 mg, 92% yield, Rf = 0.35
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(EtOAc/acetic acid 30:1). H NMR (400 MHz, CDCl3) δ 7.49 (d, J = 8.3 Hz, 2H), 7.33 (d, J = 8.3 Hz,
2H), 6.58 (s, 1H), 3.91 (s, 2H), 2.56 (d, J = 2.6 Hz, 1H), 1.88–1.76 (m, 6H), 1.44–1.39 (m, 6H). 13C{1H}
NMR (126 MHz, CDCl3) δ 165.1, 160.6, 152.9, 152.8, 131.1, 128.0, 126.2, 110.8, 44.5, 34.1, 33.3, 26.7,
26.0. IR (neat cm-1) ν 2925, 2852, 1795, 1737, 1607, 1448, 1122, 1016, 996, 825, 618. HRMS (ESI-TOF)
m/z: [M+H]+ Calcd for C17H19O3 271.1334; Found 271.1326.
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4-(4-Methoxyphenyl)-2H-pyran-2,6(3H)-dione (2e). white solid, 20.7 mg, 95% yield, Rf = 0.25
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(EtOAc/acetic acid 30:1). H NMR (400 MHz, CDCl3) δ 7.53 (d, J = 8.9 Hz, 2H), 7.00 (d, J = 8.9 Hz,
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2H), 6.53 (s, 1H), 3.89–3.88 (m, 5H). C{1H} NMR (126 MHz, CDCl3) δ 165.0, 162.8, 160.5, 151.9,
127.9, 125.8, 114.8, 109.4, 55.6, 33.2. IR (neat cm-1) ν 2924, 2852, 1791, 1732, 16256, 1515, 1185, 868,
619. HRMS (ESI-TOF) m/z: [M+H]+ Calcd for C12H11O4 219.0657; Found 219.0652.
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4-(2,3-dihydrobenzo[b][1,4]dioxin-6-yl)-2H-pyran-2,6(3H)-dione (2f). white solid, 23.2 mg, 94%
yield, Rf = 0.25 (EtOAc/acetic acid 30:1). 1H NMR (400 MHz, DMSO-d6) δ 7.36–7.32 (m, 2H), 6.95 (d,
J = 8.5 Hz, 1H), 6.70 (s, 1H), 4.29 (d, J = 6.1 Hz, 4H), 4.10 (s, 2H). 13C{1H} NMR (126 MHz, DMSO-
d6) δ 166.2, 161.4, 153.5, 146.4, 143.5, 64.4, 63.9, 33.3. IR (neat cm-1) ν 2924, 2853, 1786, 1732, 1626,
1127, 975, 887, 609. HRMS (ESI-TOF) m/z: [M+H]+ Calcd for C13H11O5 247.0606; Found 247.0604.
4-(Naphthalen-2-yl)-2H-pyran-2,6(3H)-dione (2g). white solid, 18.6 mg, 78% yield, Rf = 0.35
(EtOAc/acetic acid 30:1). 1H NMR (400 MHz, DMSO-d6) δ 8.42 (s, 1H), 8.04–7.97 (m, 4H), 7.62 (s, 2H),
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6.98 (s, 1H), 4.30 (s, 2H). C{1H} NMR (101 MHz, DMSO-d6) δ 166.2, 161.4, 153.7, 134.0, 132.5,
131.2, 129.0, 128.5, 128.0, 127.7, 127.5, 126.9, 123.2, 111.0, 33.4. IR (neat cm-1) ν 2973, 2929, 1784,
1723, 1622, 1384, 1122, 975, 814, 618. HRMS (ESI-TOF) m/z: [M+H]+ Calcd for C15H11O3 239.0708;
Found 239.0701.
4-(Naphthalen-1-yl)-2H-pyran-2,6(3H)-dione (2h). white solid, 16.4 mg, 69% yield, Rf = 0.25
(EtOAc/acetic acid 30:1). 1H NMR (400 MHz, CDCl3) δ 7.97–793 (m, 2H), 7.88–7.85 (m, 1H), 7.60–7.57
(m, 2H), 7.56–7.52 (m, 1H), 7.39–7.37 (m, 1H), 6.45 (t, J = 1.7 Hz, 1H), 3.94 (d, J = 1.7 Hz, 2H). 13C{1H}
NMR (101 MHz, CDCl3) δ 164.6, 159.8, 155.0, 133.8, 133.6, 130.7, 129.4, 129.0, 127.6, 126.8, 125.1,
124.8, 123.9, 117.8, 36.8. IR (neat cm-1) ν 2964, 2926, 2876, 1794, 1739, 1684, 1519, 1207, 776, 700.
HRMS (ESI-TOF) m/z: [M-H]- Calcd for C15H9O3 237.0552; Found 237.0553.
4-([1,1'-Biphenyl]-4-yl)-2H-pyran-2,6(3H)-dione (2i). white solid, 20.6 mg, 78% yield, Rf = 0.30
(EtOAc/acetic acid 30:1). 1H NMR (400 MHz, DMSO-d6) δ 7.91 (d, J = 8.1 Hz, 2H), 7.82–7.75 (m, 4H),
7.50 (t, J = 7.5 Hz, 2H), 7.42 (t, J = 7.2 Hz, 1H), 6.87 (s, 1H), 4.21 (s, 2H). 13C{1H} NMR (101 MHz,
DMSO-d6) δ 166.2, 161.4, 153.6, 142.9, 138.8, 132.9, 129.1, 128.2, 127.5, 127.0, 126.8, 110.5, 33.4. IR
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(neat cm-1) ν 2953, 2923, 2851, 1788, 1723, 1630, 1165, 797, 769, 622. HRMS (ESI-TOF) m/z: [M+H]+
Calcd for C17H13O3 265.0865; Found 265.0859.
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4-(4-Fluorophenyl)-2H-pyran-2,6(3H)-dione (2j). white solid, 19.1 mg, 92% yield, Rf = 0.30
(EtOAc/acetic acid 30:1). 1H NMR (500 MHz, CDCl3) δ 7.57 (dd, J = 8.2, 5.2 Hz, 2H), 7.20 (t, J = 8.3
Hz, 2H), 6.57 (s, 1H), 3.89 (s, 2H). 13C{1H} NMR (126 MHz, CDCl3) δ 164.8 (d, J = 255.4 Hz), 164.4,
160.0, 151.4, 129.9, 128.3 (d, J = 8.9 Hz), 116.8 (d, J = 22.1 Hz), 111.9 (d, J = 1.4 Hz), 33.4. IR (neat
cm-1) ν 2952, 2854, 1793, 1738, 1635, 1416, 873, 836, 619. HRMS (ESI-TOF) m/z: [M+H]+ Calcd for
C11H8FO3 207.0457; Found 207.0448.
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4-(4-Chlorophenyl)-2H-pyran-2,6(3H)-dione (2k). white solid, 19.6 mg, 88% yield, Rf = 0.30
(EtOAc/acetic acid 30:1). 1H NMR (500 MHz, CDCl3) δ 7.49 (s, 4H), 6.60 (s, 1H), 3.88 (s, 2H). 13C{1H}
NMR (126 MHz, CDCl3) δ 164.3, 159.9, 151.2, 138.5, 132.1, 129.8, 127.4, 33.2. IR (neat cm-1) ν 2960,
2920, 2850, 1800, 1740, 970, 829. HRMS (ESI-TOF) m/z: [M+H]+ Calcd for C11H8ClO3 223.0162; Found
223.0156.
4-(4-Bromophenyl)-2H-pyran-2,6(3H)-dione (2l). yellow solid, 20.0 mg, 75% yield, Rf = 0.35
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(EtOAc/acetic acid 30:1). H NMR (400 MHz, CDCl3) δ 7.65 (d, J = 8.5 Hz, 2H), 7.42 (d, J = 8.5 Hz,
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2H), 6.61 (s, 1H), 3.89 (s, 2H). C{1H} NMR (101 MHz, CDCl3) δ 164.2, 159.9, 151.4, 132.8, 132.6,
131.5, 127.5, 126.8, 112.5, 33.2. IR (neat cm-1) ν 2959, 2917, 2851, 1796, 1741, 1458, 1379, 822, 725.
HRMS (ESI-TOF) m/z: [M+H]+ Calcd for C11H8BrO3 266.9657; Found 266.9654.
4-(Furan-2-yl)-2H-pyran-2,6(3H)-dione (2m). white solid, 15.3 mg, 86% yield, Rf = 0.35
(EtOAc/acetic acid 30:1). 1H NMR (400 MHz, DMSO-d6) δ 8.00 (s, 1H), 7.29 (s, 1H), 6.74 (s, 1H), 6.42
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(s, 1H), 4.04 (s, 2H). C{1H} NMR (126 MHz, DMSO-d6) δ 165.6, 161.3, 148.8, 147.4, 142.8, 116.1,
113.2, 105.9, 31.5. IR (neat cm-1) ν 2925, 2854, 1790, 1733, 1629, 1562, 1004, 971, 841, 617. HRMS
(ESI-TOF) m/z: [M+H]+ Calcd for C9H7O4 179.0344; Found 179.0339.
4-(Thiophen-2-yl)-2H-pyran-2,6(3H)-dione (2n). white solid, 15.5 mg, 80% yield, Rf = 0.35
(EtOAc/acetic acid 30:1). 1H NMR (400 MHz, DMSO-d6) δ 7.91 (s, 1H), 7.77 (s, 1H), 7.24 (s, 1H), 6.52
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(s, 1H), 4.16 (s, 2H). C{1H} NMR (126 MHz, DMSO-d6) δ 165.6, 161.1, 148.0, 138.0, 131.8, 130.7,
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128.9, 33.6. IR (neat cm-1) ν 2954, 2924, 2852, 1684, 1610, 1459, 1377, 855, 703. HRMS (ESI-TOF) m/z:
[M+H]+ Calcd for C9H7O3S 195.0116; Found 195.0119.
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4-Methyl-2H-pyran-2,6(3H)-dione (2o). white solid, 11.3 mg, 89% yield, Rf = 0.25 (EtOAc/acetic acid
50:1). 1H NMR (500 MHz, CDCl3) δ 6.07 (s, 1H), 3.44 (s, 2H), 2.07 (s, 3H). 13C{1H} NMR (101 MHz,
CDCl3) δ 164.7, 159.7, 155.4, 114.7, 36.3, 22.2. IR (neat cm-1) ν 2955, 2925, 2854, 1794, 1733, 1659,
1114, 961, 847, 594. HRMS (ESI-TOF) m/z: [M+H]+ Calcd for C6H7O3 127.0395; Found 127.0389.
4-(4-Methylpent-3-en-1-yl)-2H-pyran-2,6(3H)-dione (2p). white solid, 14.2 mg, 73% yield, Rf = 0.25
(EtOAc/acetic acid 50:1). 1H NMR (500 MHz, CDCl3) δ 6.06 (s, 1H), 5.03 (t, J = 6.4 Hz, 1H), 3.43 (s,
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2H), 2.34 (t, J = 7.2 Hz, 2H), 2.28–2.24 (m, 2H), 1.70 (s, 3H), 1.62 (s, 3H). C{1H} NMR (126 MHz,
CDCl3) δ 164.9, 159.9, 159.1, 134.4, 121.3, 113.9, 35.7, 35.2, 25.6, 25.0, 17.8. IR (neat cm-1) ν 2960,
2929, 2855, 1799, 1741, 1653, 1380, 1278, 1118, 966, 598. HRMS (ESI-TOF) m/z: [M+H]+ Calcd for
C11H15O3 195.1021; Found 195.1018.
4-Cyclopropyl-2H-pyran-2,6(3H)-dione (2q). white solid, 12.5 mg, 82% yield, Rf = 0.25 (EtOAc/acetic
acid 30:1). 1H NMR (400 MHz, CDCl3) δ 5.94 (t, J = 1.5 Hz, 1H), 3.34–3.32 (m, 2H), 1.69–1.62 (m, 1H),
1.13–1.08 (m, 2H), 0.88–0.84 (m, 2H). 13C{1H} NMR (101 MHz, CDCl3) δ 164.9, 162.0, 159.8, 110.1,
33.2, 16.6, 9.3. IR (neat cm-1) ν 2954, 2918, 2852, 1792, 1734. HRMS (ESI-TOF) m/z: [M+H]+ Calcd for
C8H9O3 153.0552; Found 153.0546.
4a,5-Dihydro-2H,4H-pyrano[3,4-c]chromene-2,4-dione (2r). white solid, 14.7 mg, 68% yield, Rf =
0.25 (EtOAc/acetic acid 30:1). 1H NMR (400 MHz, CDCl3) δ7.40 (t, J = 7.8 Hz, 1H), 7.21 (d, J = 7.8 Hz,
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1H), 7.05 (t, J = 7.6 Hz, 1H), 6.97 (d, J = 8.2 Hz, 1H), 5.09 (s, 2H), 3.86 (s, 2H). C{1H} NMR (126
MHz, CDCl3) δ 163.7, 158.8, 155.8, 141.8, 134.3, 124.8, 122.4, 118.6, 117.4, 113.4, 30.8. IR (neat cm-1)
ν 2929, 2854, 1796, 1723, 1603, 758, 734. HRMS (ESI-TOF) m/z: [M+H]+ Calcd for C12H9O4 217.0501;
Found 217.0495.
3-Methyl-4-phenyl-2H-pyran-2,6(3H)-dione (2s). white solid, 14.2 mg, 70% yield, Rf = 0.25
(EtOAc/acetic acid 30:1). 1H NMR (400 MHz, CDCl3) δ 7.46–7.45 (m, 2H), 7.39–7.37 (m, 3H), 6.06 (s,
1H), 3.12 (q, J = 7.4 Hz, 1H), 1.08 (t, J = 7.4 Hz, 3H). 13C{1H} NMR (101 MHz, CDCl3) δ 171.4, 164.7,
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140.9, 129.1, 128.6, 127.1, 116.1, 24.5, 13.6. IR (neat cm-1) ν 2969, 2926, 2871, 1798, 1739, 1684, 1616,
1515, 767, 700. HRMS (ESI-TOF) m/z: [M+H]+ Calcd for C12H11O3 203.0708; Found 203.0700.
Gram-Scale Synthesis of 2a. A 60 mL oven dried autoclave containing a stir bar was charged with
pentafluorophenyl 2-butenoate 1aa (1.97 g, 6.0 mmol), DBU (2.70 g, 18.0 mmol) and 40 mL dry CH3CN
in a glove box. After removal from the glove box, the autoclave was purged three times, and then
pressurized to appropriate pressure with carbon dioxide. The reaction mixture was stirred at room
temperature for 18 h, and the remaining carbon dioxide was vented slowly. Then the pH of reaction
mixture was adjusted to 3~4 with 0.5 M HCl and extracted with EtOAc (3 × 100 mL). The combined
organic layer was washed with brine, dried over Na2SO4, filtered, concentrated in vacuo and then
subjected to column chromatography using EtOAc/acetic acid to afford 2a as a pale yellow solid. 0.95 g,
84% yield.
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Hydrolytic Reaction of 2a. A 25 mL round-bottom flask was charged with 2a (0.3 mmol, 56 mg) and
MeOH (5 mL), then NaOH (2 M, 4 mL) was added with stirring. The reaction mixture was stirred at room
temperature until no starting material was detected by TLC. Then the pH of reaction mixture was adjusted
to 1.0 with HCl (1 M). The mixture was extracted with diethyl ether (3 × 30 mL). The combined organic
layer was washed with brine, dried over Na2SO4 and filtration. The solvent was removed under reduced
pressure. To the crude product in a mixture solvent (MeOH/DCM=1:1, 6 mL) at room temperature was
added TMSCHN2 (1M in hexane, 1 mL) and the reaction mixture was stirred at room temperature for 1
h. The mixture was carefully quenched with HCl (1 M). The organics were extracted EtOAc (5 × 15 mL),
dried over Na2SO4, filtered, concentrated in vacuo and then subjected to column chromatography using
EtOAc-hexane to afford the diester 3a as a pale yellow oil. 63.2 mg, 90% yield, Rf = 0.25 (petroleum
ether/EtOAc 20:1). 1H NMR (400 MHz, CDCl3) δ 7.46–7.42 (m, 2H), 7.39–7.36 (m, 3H), 4.18 (s, 1H),
3.75 (s, 3H), 3.68 (s, 3H). 13C{1H} NMR (101 MHz, CDCl3) δ 170.7, 166.6, 151.2, 140.5, 129.3, 128.7,
126.4, 119.5, 52.1, 51.4, 36.8. HRMS (ESI-TOF) m/z: [M+H]+ Calcd for C13H14O4 235.0970; Found
235.0957.
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Reduction of 2a with Lithium Aluminum Hydride.19 The 2a (0.3 mmol, 56 mg) was dissolved in
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THF (10 mL) under nitrogen and the reaction mixture was cooled to 0 °C. LiAlH4 (1 M in THF, 0.6 mL)
was added dropwise with stirring. After the addition was complete, the reaction mixture was heated by
oil bath at reflux overnight. The mixture was carefully quenched with EtOAc. Then the pH was adjusted
to 4.0 with HCl (1 M). The reaction mixture were extracted with EtOAc (3 × 20 mL), dried over Na2SO4,
filtered, concentrated in vacuo and then subjected to column chromatography using EtOAc-hexane to
afford the diol product 4a as yellow oil. 37.4 mg, 70% yield, Rf = 0.20 (petroleum ether/EtOAc 1:1). 1H
NMR (500 MHz, CDCl3) δ 7.37–7.36 (m, 2H), 7.36–7.30 (m, 2H), 7.28–7.25 (m, 1H), 6.13 (t, J = 7.4 Hz,
1H), 4.23 (d, J = 7.4 Hz, 2H), 3.59 (t, J = 5.9 Hz, 2H), 3.33 (bs, 2H), 2.81 (t, J = 5.9 Hz, 2H). 13C{1H}
NMR (126 MHz, CDCl3) δ 141.5, 141.0, 128.9, 128.4, 127.5, 126.5, 59.8, 58.2, 32.8. HRMS (ESI-TOF)
m/z: [M+H]+ Calcd for C11H15O2 179.1072; Found 179.1068.
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DMAP Promoted Cycloaddition of 2a and 4-Nitrobenzaldehyde.13 To a mixture of 2a (0.2 mmol,
37.5 mg) and p-nitrobenzaldehyde (0.22 mmol, 33 mg) in dry chloroform (2 ml), DMAP (0.2 mmol, 25
mg) was added. The reaction mixture was stirred at room temperature for 15 h. The mixture was added
TMSCHN2 (1M in hexane, 1 mL) and the reaction mixture was stirred at room temperature for 1 h. The
mixture was carefully quenched with HCl (1 M) and extracted with EtOAc (3 × 20 mL), dried over
Na2SO4, filtered, concentrated in vacuo and then subjected to column chromatography using EtOAc-
hexane to afford 5a as a yellow solid. 48.1 mg, 68% yield, Rf = 0.25 (petroleum ether/EtOAc 4:1).1H
NMR (400 MHz, CDCl3) δ 8.66 (d, J = 16.8 Hz, 1H), 8.18 (d, J = 7.6 Hz, 2H), 7.61 (d, J = 7.6 Hz, 2H),
7.45–7.35 (m, 5H), 6.64 (d, J = 16.8 Hz, 1H), 5.93 (s, 1H), 3.81 (d, J = 5.1 Hz, 3H). 13C{1H} NMR (101
MHz, CDCl3) δ 166.6, 155.0, 147.5, 143.0, 139.1, 136.7, 130.1, 128.9, 128.9, 128.5, 127.9, 123.8, 119.7,
51.5. HRMS (ESI-TOF) m/z: [M+H]+ Calcd for C19H15NO6 354.0978; Found 354.0972.
Reaction of 2a with Excess Dimethyl Acetylenedicarboxylate.20 The 2a (0.3 mmol, 56 mg) was
dissolved in dry DCM (15 mL) under nitrogen atmosphere and then Et3N (0.06 mmol, 6 mg) was added,
and the mixture was stirred for 5 min. DMAD (0.7 mmol, 99 mg) was added dropwise and the mixture
was stirred overnight. The mixture was quenched with HCl (1 M) and extracted with ethyl acetate (3 × 20
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mL), dried over Na2SO4, filtered, concentrated in vacuo and then subjected to column chromatography
using EtOAc-hexane to afford 6a as a white solid. 89.8 mg, 70% yield, Rf = 0.30 (petroleum ether/EtOAc
10:1). 1H NMR (400 MHz, CDCl3) δ 8.14 (d, J = 1.6 Hz, 1H), 7.60–7.56 (m, 3H), 7.50–7.43 (m, 3H),
5.25 (s, 1H), 3.96 (s, 3H), 3.93 (s, 3H), 3.93 (s, 3H), 3.68 (s, 3H). 13C{1H} NMR (126 MHz, CDCl3) δ
165.7, 165.3, 165.0, 159.6, 150.4, 144.5, 137.8, 130.8, 129.2, 128.9, 127.2, 127.1, 126.5, 100.9, 53.17,
53.0, 52.9, 51.8. HRMS (ESI-TOF) m/z: [M+H]+ Calcd for C22H21O9 429.1186; Found 429.1178.
Hydrogenation of 2a with H2. A 100 mL oven dried autoclave containing a stir bar was charged with
2a (0.14 g, 0.76 mmol), Pd/C (5%, 36 mg) and 30 mL dry EtOAc. The autoclave was purged three times
with nitrogen, degased at 0 oC, and then pressurized to 2.0 MPa with H2. The reaction mixture was stirred
at room temperature for 15 h, and the remaining H2 was vented slowly. After Pd/C was filtered off, the
organic solution was concentrated in vacuo and then subjected to column chromatography using
EtOAc/hexane to afford 7a as a white solid. 0.12 g, 83% yield, Rf = 0.25 (petroleum ether/EtOAc 1:1).
1H NMR (400 MHz, CDCl3) δ 7.43–7.36 (m, 2H), 7.36–7.30 (m, 1H), 7.21 (d, J = 7.8 Hz, 2H), 3.47–3.39
(m, 1H), 3.11 (dd, J = 17.3, 4.5 Hz, 2H), 2.87 (dd, J = 17.3, 11.4 Hz, 2H). 13C{1H} NMR (101 MHz,
CDCl3) δ 165.8, 139.1, 129.36, 128.1, 126.2, 37.1, 34.1. IR (neat cm-1) ν 1800, 1758, 1078, 957, 766, 704.
HRMS (ESI-TOF) m/z: [M+Na]+ Calcd for C11H10NaO3 213.0528; Found 213.0517.
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X-ray Crystallography. Single crystals of 2b and 2e were obtained by recrystallization from
EtOAc/hexane at room temperature. Recrystallization from EtOAc at 5-10 oC afforded the single crystal
of 6a. The intensities were collected on a Bruker SMART APEX CCD diffractometer equipped with a
graphitemonochromated Mo−Kα (λ = 0.71073 Å) radiation source; the data were acquired using the
SMART and SAINT programs. The structures were solved by direct methods and refined on F2 by
fullmatrix least-squares methods using the SHELXTL version 5.1 software.
ASSOCIATED CONTENT
Supporting Information.
The Supporting Information is available free of charge via the Internet at http://pubs.acs.org.
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X-ray crystallographic data (CIF)
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Copies of 1H NMR, 13C{1H} NMR, 19F NMR spectra for substrates and products
Thermal ellipsoid plots of 2b, 2e and 6a
Spectra of labelled products
AUTHOR INFORMATION
Corresponding Author
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* E-mail: zhangwz@dlut.edu.cn
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENT
Financial supports from the National Natural Science Foundation of China (21878038), the
Fundamental Research Funds for the Central Universities (DUT19LK56), and the Program for
Changjiang Scholars and Innovative Research Team in University (IRT-17R14) are gratefully
acknowledged.
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