Propargylation of 1,3-dicarbonyl compounds catalyzed by 2,3-dichloro-5,6-dicyano-1,4-benzoquinone and sodium nitrite in the presence of molecular oxygen and formic acid

Article abstract of DOI:10.1039/c6ra06704b

Catalyzed by 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and sodium nitrite, the coupling reaction of 1,3-diarylpropynes and 1,3-dicarbonyl compounds using molecular oxygen as a terminal oxidant was developed. The reaction was promoted dramatically in

Full text of DOI:10.1039/c6ra06704b

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Propargylation of 1, 3-dicarbonyl compounds catalyzed by 2,3-
dichloro-5,6-dicyano-1,4-benzoquinone and sodium nitrite in the
presence of molecular oxygen and formic acid†
Received 00th January 20xx,
Accepted 00th January 20xx
Dongping Cheng,a* Xiayi Zhou,a Xiaoliang Xub and Jizhong Yana
DOI: 10.1039/x0xx00000x
www.rsc.org/
Catalyzed by 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) functional groups. For example, the reaction of propargyl-
and sodium nitrite, the coupling reaction of 1,3-diarylpropynes substituted 1,3-dicarbonyl compound with phenylhydrazine
and 1,3-dicarbonyl compounds using molecular oxygen as a hydrochloride affords indazole which could be applied as
terminal oxidation was developed. The reaction was promoted further synthetic reagent for synthesize the pharmacologically
dramatically in the presence of HCOOH. The corresponding active compound.6 The condensation of propargyl-substituted
products were obtained within half an hour in 37-87% yields.
1,3-dicarbonyl compound with amine gives pyrrole which is an
common subsection in many pharmaceuticals.7-8 Sanz and
others
reported
propargyl-substituted
1,3-dicarbonyl
The C-C bond formation is one of the most useful and
fundamental processes in organic synthesis. In recent years,
the cross-dehydrogenative coupling reaction (CDC reaction) of
activated C–H bonds has become an attractive research topic.1-
compound could be transformed to substituted furans that
represents important building blocks in many pharmaceuticals,
flavours and fragrance compounds.8-11 DDQ as an effective
oxidant has been widely used for the cross-dehydrogenative
coupling.12-15 Recently, our group reported the coupling
reaction of allylic compounds and 1,3-dicarbonyls catalyzed by
DDQ/NaNO2 with molecular oxygen as the terminal oxidant.16
With HCOOH as an additive, unexpectedly, the reaction was
promoted dramatically. To explore further the role of HCOOH
and according to the similar reactivity between propargylic
and allylic compound, we tried to apply the catalytic system
for the reaction of propargylic compounds with 1,3-
dicarbonyls. Compared with the benzylation and allylation of
1,3-dicarbonyl compounds, the propargylation was little
studied.17-37 Although some results were achieved in the
propargylation of 1,3-dicarbonyl compounds, a good choice for
the transformation through the cross-dehydrogenative
coupling with molecular oxygen as the terminal oxidation has
not been reported. With the interest of the application of the
oxidative system of DDQ/O2 in organic synthesis, herein, we
report the propargylation of 1, 3-dicarbonyl compounds
catalyzed by DDQ and NaNO2 in the presence of molecular
oxygen and HCOOH.
2
From the point of green chemistry, molecular oxygen is an
ideal oxidant in the CDC transformation due to its naturalness,
inexpensiveness, and water as the sole by-product. It is well
known that, for fulfilling this kind of transformation, the
catalyst is necessary to overcome the barrier between the
triplet ground state of molecular oxygen and the singlet
ground state of common substrate. Great progresses have
been made in the development of excellent catalyst to achieve
this goal.3-5 However, the direct C–C coupling from Csp3–H
bonds with molecular oxygen as the terminal oxidant is still a
challenge task for organic chemists.
Propargylation of 1,3-dicarbonyl compound is an important C-
C bond forming method in organic synthesis because of the
alkyne and carbonyl group acting as the precursors of different
a
College of Pharmaceutical Science, Zhejiang University of Technology,
Hangzhou 310014, P. R. China. E-mail: chengdp@zjut.edu.cn
b
College of Chemical Engineering, Zhejiang University of Technology,
Hangzhou 310014, P. R. China.
†
Electronic supplementary information (ESI) available: Copies of 1H and
The coupling of 1,3-diphenyl-1,3-propanedione 1a and 1-
phenyl-3-(4-methoxyl)phenyl-1-propyne 2a was chosen as a
model reaction (Table 1). Referred to the optimized reaction
condition of allylic compounds and 1,3-dicarbonyls,16 it was
catalyzed by 1 mol % DDQ and 10 mol % NaNO2 in the
presence of oxygen balloon and HCOOH. To our delight, the
expected coupling product was obtained with 65% yield (entry
1). The yield was promoted to 82% when the catalytic amount
13C NMR spectra of compounds 3. See DOI:
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
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of DDQ was 10 mol % (entry 2). The reaction was completed
Journal Name
within half an hour. It was noteworthy that the reaction which Table 2. The Coupling Reaction of 1,3-Diarylpropyne with 1,3-Diphenyl-1,3-
was mediated by a stoichiometric of DDQ without additional propanedionea
reagent, need three hours to complete.24 To our surprise, the
coupling reaction could be performed only in the presence of
HCOOH and CH3NO2 and give the coupling product with 17%
yield (entry 3). However no expected coupling product was
obtained when allylic compounds reacted with 1,3-dicarbonyls
by HCOOH/CH3NO2.38 It indicated that the mechanism of the
Entry
1
Ar1
Ar2
3
Yield(%)b
82
coupling reaction should be different from the coupling
reaction of allylic compounds and 1,3-dicarbonyls. That was to
say that the C-C formation could be mediated not only by
DDQ. Another acid such as PhCOOH, CF3COOH, and CH3COOH
was surveyed, while no coupling product was obtained. To
probe further the possible mechanism, some control
experiments were performed. The coupling product was
obtained in 76% yield when DDQH2 (10 mol %) took place of
DDQ in the reaction (entry 4). It indicated that DDQH2 could
regenerate DDQ by NaNO2/HCOOH/O2. In the absence of
NaNO2, DDQ, or HCOOH, the yield was decreased to 23%, 20%
and 15%, respectively (entries 5-7). It gave the product with
35% yield when the reaction was performed in the presence of
nitrogen instead of molecular oxygen (entry 8). No product
was obtained when the reaction was performed only by
NaNO2/O2 (entry 9). The yield of coupling product was
decreased dramatically when TEMPO was added to the
mixture (entry 12). It showed that the reaction might proceed
through radical process. Based on the above results, it could
be concluded that DDQ and HCOOH mediated the coupling
reaction respectively. However the role of HCOOH was
unclear.
4-CH3OC6H4
C6H5
3a
2
3
4
4-CH3C6H4
C6H5
C6H5
C6H5
C6H5
3b
3c
3d
66
46
49
2-CH3C6H4
5
4-ClC6H4
C6H5
C6H5
3e
3f
37
57
6
4-CH3OC6H4
a
1a (0.5 mmol),
2 (0.6 mmol), DDQ (10 mol%), NaNO2 (10 mol%), HCOOH
(0.25 mL), CH3NO2 (2.5 mL), 0.5 hr, r.t..
b Isolation yield.
To obtain the different substrate effect on the reaction, the
coupling reaction of 1,3-diarylpropyne
propanedione 1a was firstly investigated. From Table 2, the
group on benzyl ring of compound had obvious effect on the
2 with 1,3-diphenyl-1,3-
2
reaction. The yield was higher relatively when the group such
as methyl and methoxyl was donating electron (entries 1-4).
The yield was lower when the group was chloro (entry 5). It
indicated that the reaction might generate the propargyl
cation and/or radical intermediacy. The donating electron
group was in favor of the stability of intermediacy and
facilitated the formation of coupling product. The methoxyl
group of benzene ring adjacent to alkynyl had little effect on
the reaction (entry 6).
Table 1. Control Experimenta
Table 3. The Coupling Reaction of 1-Phenyl-3-(4-methoxyl)phenyl-1-
propyne with 1,3-Propanedionea
Entry
1
DDQ(mol %)
NaNO2(mol %)
HCOOH(mL)
Yield(%)b
65
1
10
-
10
10
-
0.25
0.25
0.25
0.25
0.25
0.25
-
2
82
3
4c
17
Entry
1
R1
R2
3
Yield (%)b
85
-
10
-
76
4-CH3C6H4
C6H5
3g
5
10
-
23
2
3
4-CH3OC6H4
3-CH3C6H4
2-CH3C6H4
4-ClC6H4
4-BrC6H4
2-thienyl
2-furyl
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
C6H5
CH3
3h
3i
75
68
68
46
48
87
85
73
53
49
6
10
10
10
10
-
20
7
8d
10
10
-
15
4
3j
0.25
-
35
5
3k
3l
9
0
10d
11
12e
-
0.25
-
16
6
7
3m
3n
3o
3p
3q
10
-
16
10
10
0.25
18
8
a 1a (0.5 mmol), 2a (0.6 mmol), DDQ, NaNO2 , HCOOH, CH3NO2 (2.5 mL), 0.5
9
CH3
hr, r.t..
b Isolation yield.
10
11
CH3
OCH2CH3
C6H5
c DDQH2 (10 mol %) instead of DDQ.
d Nitrogen instead of molecular oxygen.
e TEMPO (0.5 mmol) was added to the mixture.
a
1
(0.5 mmol), 2a (0.6 mmol), DDQ (10 mol%), NaNO2 (10 mol%), HCOOH
(0.25 mL), CH3NO2 (2.5 mL), 0.5 hr, r.t..
b Isolation yield.
2 | J. Name., 2012, 00, 1-3
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7.61 (t, J = 7.4 Hz, 1H), 7.52-7.45 (m, 5H), 7.32 (t, J = 7.8 Hz,
Next, a series of 1,3-propanedione was subject to the reaction 2H), 7.23-7.14 (m, 3H), 7.09 (d, J = 7.9 Hz, 2H), 7.02-7.01 (m,
and results were listed in Table 3. It gave the coupling product 2H), 5.92 (d, J = 10.1 Hz, 1H), 5.18 (d, J =10.1 Hz, 1H), 2.28 (s,
with 68-85% yield when 1,3-propanedione 1
, which contained 3H). 13C NMR (125 MHz, CDCl3/TMS): δ 193.5, 192.6, 137.09,
electron-donating substitute such as methyl, methoxyl on the 137.07, 136.6, 136.3, 133.5, 133.3, 131.4, 129.3, 129.1, 128.9,
benzene ring, reacted with 1-phenyl-3-(4-methoxyl) phenyl-1- 128.6, 128.5, 128.4, 127.9, 127.87, 123.0, 89.6, 85.0, 63.3,
propyne 2a (entries 1-4). The yield was relatively lower when 38.3, 21.0.
1,3-propanedione
1
bearing electron-withdrawing substitute 2-[1,3-diphenyl-2-propynyl]-1,3-diphenyl-1,3-propanedione
3c).24
such as chloro and bromo on the benzene ring was used as the
(
1
substrate (entries 5-6). Heterocyclic aryl groups such as furanyl White solid (95 mg, 46%), mp 145-147˚C. H NMR (500 MHz,
and thienyl were good candidates in the reaction and gave the CDCl3/TMS): δ 8.15 (d, J = 7.6 Hz, 2H), 7.78 (d, J = 7.7 Hz, 2H),
products in 85-87% yields (entries 7-8). Benzoylacetone was a 7.62-7.57 (m, 3H), 7.52-7.45 (m, 3H), 7.33-7.15 (m, 8H), 7.04
suitable partner here (entry 9). Acetylacetone and ethyl (d, J = 7.3 Hz, 2H), 5.93 (d, J = 10.1 Hz, 1H), 5.21 (d, J = 10.1 Hz,
benzoylacetate could be also applied despite the slightly lower 1H). 13C NMR (125 MHz, CDCl3/TMS): δ 193.4, 192.6, 139.3,
yields (entries 10-11).
137.0, 136.5, 133.5, 133.4, 131.4, 129.1, 128.9, 128.64, 128.59,
We have developed an efficient propargylation of 1, 3- 128.50, 128.0, 127.9, 127.5, 122.9, 89.4, 85.1, 63.2, 38.8.
dicarbonyl compounds catalyzed by DDQ and NaNO2 with 2-[1-(2-methylphenyl)-3-phenyl-2-propynyl]-1,3-diphenyl-1,3-
molecular oxygen as
a terminal oxidation. It promoted propanedione (3d).
1
dramatically in the presence of HCOOH. However the White solid (105 mg, 49%), mp 141-143˚C. H NMR (500 MHz,
mechanism of the reaction was unclear. The reaction system CDCl3/TMS): δ 8.19 (d, J = 7.3 Hz, 2H), 7.81 (d, J = 7.3 Hz, 2H),
will be continued to explore further in our lab.
7.63-7.45 (m, 5H), 7.33 (t, J = 7.9 Hz, 2H), 7.22-7.07 (m, 6H),
7.04-7.02 (m, 2H), 6.17 (d, J = 10.2 Hz, 1H), 5.34 (d, J = 10.2 Hz,
1H), 2.61 (s, 3H). 13C NMR (125 MHz, CDCl3/TMS): δ 193.8,
192.4, 137.4, 137.2, 136.4, 136.3, 133.5, 133.3, 131.4, 131.0,
129.1, 128.9, 128.6, 128.4, 127.9, 127.83, 127.76, 127.3, 126.3,
123.0, 89.6, 84.4, 61.6, 35.1, 19.9. HRMS (ESI-TOF) m/z: Calcd.
for C31H25O2 [M+H] + 429.1849; Found 429.1864.
Experimental
Column chromatography was carried out on silica gel (200-300
mesh). 1H NMR spectra were recorded on a 500 MHz
spectrometer. 13C NMR spectra were recorded on a 125 MHz
spectrometer. Chemical shifts were reported in parts per
million (δ) relative to the internal standard TMS (0 ppm) for
CDCl3. The coupling constants, J, are reported in Hertz (Hz).
High-resolution mass spectra (HRMS) were recorded on ESI-
TOF. Melting points were uncorrected. The reagents were
purchased from commercial chemical reagent companies and
used without further purification unless otherwise stated.
General procedure: To a mixture of 1,3-dicarbonyl compound
2-[1-(4-chlorophenyl)-3-phenyl-2-propynyl]-1,3-diphenyl-1,3-
propanedione (3e).24
1
White solid (83 mg, 37%), mp 121-123˚C. H NMR (500 MHz,
CDCl3/TMS): δ 8.15 (d, J =7.5 Hz, 2H), 7.79 (d, J =7.5 Hz, 2H),
7.62 (t, J =7.4 Hz, 1H), 7.53-7.47 (m, 5H), 7.34 (t, J =7.8 Hz, 2H),
7.26-7.16 (m, 5H), 7.02 (d, J =7.2 Hz, 2H), 5.88 (d, J =10.1 Hz,
1H), 5.18 (d, J =10.1 Hz, 1H). 13C NMR (125 MHz, CDCl3/TMS): δ
193.2, 192.4, 137.9, 136.9, 136.3, 133.6, 133.3, 131.4, 130.0,
129.1, 128.9, 128.8, 128.5, 128.1, 128.0, 122.7, 88.8, 85.5,
63.1, 38.1.
1
(0.5 mmol) and 1,3-diarylpropyne 2 (0.6 mmol) in CH3NO2
(2.5 mL), DDQ (11.3 mg, 0.05 mmol), NaNO2 (3.5 mg, 0.05
mmol), HCOOH (0.25 mL) were added. It was carried out at
room temperature in the presence of oxygen atmosphere
(oxygen balloon) within half an hour. The resulting mixture
was concentrated under reduced pressure and purified by
flash column chromatography on silica gel (petroleum ether-
2-[1-phenyl-3-(4-methoxylphenyl)-2-propynyl]-1,3-diphenyl-
1,3-propanedione (3f).24
1
Yellow solid (127 mg, 57%), mp 158-159˚C. H NMR (500 MHz,
CDCl3/TMS): δ 8.16 (d, J =7.4 Hz, 2H), 7.78 (d, J =7.4 Hz, 2H),
7.62-7.57 (m, 3H), 7.52-7.44 (m, 3H), 7.33-7.26 (m, 4H), 7.19 (t,
J =7.3 Hz, 1H), 6.98 (d, J =8.8 Hz, 2H), 6.70 (d, J =8.9 Hz, 2H),
5.94 (d, J =10.1 Hz, 1H), 5.20 (d, J =10.1 Hz, 1H), 3.75 (s, 3H).
13C NMR (125 MHz, CDCl3/TMS): δ 193.4, 192.6, 159.3, 139.5,
137.1, 136.5, 133.4, 133.3, 132.8, 129.1, 128.8, 128.60, 128.58,
128.55, 128.45, 127.4, 115.1, 113.6, 87.9, 85.0, 63.2, 55.2,
38.8.
ethyl acetate = 10:1-20:1) to give the desired pure product 3.
2-[1-(4-methoxylphenyl)-3-phenyl-2-propynyl]-1,3-diphenyl-
1,3-propanedione (3a).24
1
Yellow solid (182 mg, 82%), mp 117-118˚C. H NMR (500 MHz,
CDCl3/TMS): δ 8.21-8.19 (m, 2H), 7.85-7.83 (m, 2H), 7.60 (t, J =
7.4 Hz, 1H), 7.56-7.43 (m, 5H), 7.31 (t, J = 7.8 Hz, 2H), 7.22-7.15
(m, 3H), 7.07 (d, J = 7.0 Hz, 2H), 6.84 (d, J = 8.7 Hz, 2H), 6.02 (d,
J = 10.1 Hz, 1H), 5.24 (d, J = 10.1 Hz, 1H), 3.72 (s, 3H); 13C NMR
(125 MHz, CDCl3/TMS): δ 193.4, 192.6, 158.7, 136.9, 136.4,
133.4, 133.3, 131.3, 131.1, 129.5, 128.9, 128.8, 128.5, 128.3,
127.9, 127.8, 122.8, 113.9, 89.6, 84.9, 63.2, 55.0, 38.0.
2-[1-(4-methylphenyl)-3-phenyl-2-propynyl]-1,3-diphenyl-1,3-
propanedione (3b).24
2-[-1-(4-methoxylphenyl)-3-phenyl-2-propynyl]-1-(4-
methylphenyl)-3-phenyl-1,3-propanedione (3g).24
1
Yellow solid (195 mg, 85%), mp 109-111˚C. H NMR (500 MHz,
CDCl3/TMS): δ 8.14 (d, J = 7.3 Hz, 1H), 8.05 (d, J = 8.3 Hz, 1H),
7.79 (d, J = 7.3 Hz, 1H), 7.70 (d, J = 8.3 Hz, 1H), 7.60 (t, J = 7.4
Hz, 1/2×1H), 7.51-7.45 (m, 3+1/2×1H), 7.34-7.29 (m, 2H), 7.21-
7.11 (m, 4H), 7.04-7.02 (m, 2H), 6.81 (d, J = 8.5 Hz, 2H),
5.873,5.870 (dd, J1 = 10.2 Hz, J2 = 10.1 Hz, 1H), 5.16, 5.14 (dd,
J1 = 10.1 Hz, J2 = 10.1 Hz, 1H), 3.75 (s, 3H), 2.43 (s, 1/2×3H),
1
White solid (141 mg, 66%), mp 132-133˚C. H NMR (500 MHz,
CDCl3/TMS): δ 8.16 (d, J = 7.5 Hz, 2H), 7.79 (d, J = 7.5 Hz, 2H),
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2.33 (s, 1/2×3H). 13C NMR (125 MHz, CDCl3/TMS): δ 193.6, 7.79-7.77 (m, 2/3×2H), 7.74-7.71 (m, 1/3×2H), 7.62 (t, J = 7.4
193.0, 192.8, 192.1, 158.8, 144.5, 144.4, 137.1, 136.6, 134.6, Hz, 1/3×1H), 7.52-7.45 (m, 4+2/3×1H), 7.36-7.28 (m, 2H), 7.24-
134.1, 133.4, 133.3, 131.43, 131.41, 131.36, 129.6, 129.5, 7.15 (m, 3H), 7.08-7.03 (m, 2H), 6.82- 6.80 (m, 2H), 5.83, 5.81
129.3, 129.27, 129.1, 128.8, 128.7, 128.6, 128.5, 128.0, 127.9, (t, J1 = 9.5 Hz, J2 = 9.9 Hz, 1H), 5.14 (d, J = 10.0 Hz, 1H), 3.76 (s,
127.85, 127.83, 123.1, 123.0, 114.0, 89.8, 84.90, 84.88, 63.4, 1/3×3H), 3.75 (s, 2/3×3H). 13C NMR (125 MHz, CDCl3/TMS): δ
55.2, 38.0, 21.65, 21.56.
193.2, 192.5, 192.3, 191.6, 158.9, 140.1, 140.0, 136.9, 136.5,
135.4, 134.9, 133.6, 133.5, 131.41, 131.38, 131.1, 130.0, 130.4,
129.9, 129.6, 129.2, 129.0, 128.99, 128.94, 128.7, 128.5, 128.1,
2-[1-(4-methoxylphenyl)-3-phenyl-2-propynyl]-1-(4-
methoxylphenyl)-3-phenyl-1,3-propanedione (3h).24
1
Yellow solid (178 mg, 75%), mp 160-161˚C. H NMR (500 MHz, 127.99, 127.96, 122.9, 122.8, 114.1, 89.51, 89.46, 85.2, 85.1,
CDCl3/TMS): δ 8.16-8.13 (m, 2H), 7.81 (d, J = 8.6 Hz, 2H), 7.64- 63.8, 63.6, 55.2, 38.1, 38.0.
7.57 (m, 1/3×2H), 7.51-7.48 (m, 2+2/3×2H), 7.32 (t, J = 7.8 Hz, 2-[1-(4-methoxylphenyl)-3-phenyl-2-propynyl]-1-(4-
1H), 7.21-7.15 (m, 3H), 7.07-7.05 (m, 2H), 6.98-6.96 (m, bromophenyl)-3-phenyl-1,3-propanedione (3l).24
1+1/3×1H), 6.82-6.78 (m, 2+2/3×1H), 5.853, 5.849 (dd, J1
=
Yellow Oil (125 mg, 48%). 1H NMR (500 MHz, CDCl3/TMS): δ
10.1 Hz, J2 = 10.1 Hz, 1H), 5.17, 5.16 (dd, J1 = 10.1 Hz, J2 = 10.1 8.14-8.12 (m, 1H), 8.00-7.98 (m, 1H), 7.78-7.77 (m, 1H), 7.66-
Hz, 1H), 3.86 (s, 2/3×3H), 3.78 (s, 1/3×3H), 3.74 (s, 3H). 13C 7.60 (m, 2+1/2×1H), 7.53-7.46 (m, 4+1/2×1H), 7.36-7.33 (m,
NMR (125 MHz, CDCl3/TMS): δ 193.7, 192.9, 191.8, 190.9, 1H), 7.25-7.15 (m, 3H), 7.07-7.02 (m, 2H), 6.82-6.80 (m, 2H),
163.9, 163.7, 158.8, 137.1, 136.6, 133.7, 133.34, 133.26, 131.5, 5.83, 5.81 (dd, J1 =10.0 Hz, J2 =10.0 Hz, 1H), 5.13 (d, J =10.1 Hz,
131.40, 131.39, 131.34, 130.9, 130.2, 130.0, 129.6, 129.0, 1H), 3.76 (s, 1/2×3H), 3.75 (s, 1/2×3H). 13C NMR (125 MHz,
128.8, 128.6, 128.4, 127.93, 127.92, 127.8, 123.1, 123.0, CDCl3/TMS): 193.2, 192.6, 192.5, 191.8, 158.91, 158.89, 136.9,
114.05, 113.97, 113.95, 113.8, 89.9, 89.8, 84.9, 84.8, 63.4, 136.4, 135.7, 135.2, 133.7, 133.6, 132.2, 132.0, 131.40, 131.37,
55.5, 55.4, 55.2, 38.0.
131.03, 130.96, 130.5, 129.9, 129.6, 129.0, 128.94, 128.88,
128.79, 128.7, 128.5, 128.1, 127.99, 127.97, 122.9, 122.8,
114.1, 114.0, 89.5, 89.4, 85.2, 85.1, 63.7, 63.5, 55.2, 38.1, 38.0.
2-[1-(4-methoxylphenyl)-3-phenyl-2-propynyl]-1-(3-
methylphenyl)-3-phenyl-1,3-propanedione (3i).
1
Yellow solid (156 mg, 68%), mp 120-123˚C. H NMR (500 MHz, 2-[1-(4-methoxylphenyl)-3-phenyl-2-propynyl]-1-thienyl-3-
CDCl3/TMS): δ 8.14 (d, J = 7.2 Hz, 1H), 7.95 (d, J = 7.0 Hz, phenyl-1,3-propanedione (3m).24
1
1/2×1H), 7.90 (s, 1/2×1H), 7.78 (d, J = 7.3 Hz, 1H), 7.62-7.57 Yellow solid (196 mg, 87%), mp 103-105˚C. H NMR (500 MHz,
(m, 1+1/2×H), 7.52-7.38 (m, 4+1/2×1H), 7.34-7.31 (m, 1H), CDCl3/TMS): δ 8.20-8.18 (m, 1H), 7.99-7.98 (m, 1/2×1H), 7.88-
7.27-7.15 (m, 4H), 7.06-7.03 (m, 2H), 6.82-6.80 (m, 2H), 5.88 7.86 (m, 1H), 7.71-7.70 (m, 1/2×1H), 7.63-7.47 (m, 5H), 7.37-
(d, J = 10.1 Hz, 1H), 5.15, 5.14 (dd, J1 = 10.1 Hz, J2 = 10.0 Hz 7.34 (m, 1H), 7.24-7.11 (m, 4+1/2×1H), 7.06-7.04 (m, 1H), 6.99-
,1H), 3.751 (s, 1/2×3H), 3.747 (s, 1/2×3H), 2.38 (s, 1/2×3H), 6.97 (m, 1/2×1H), 6.83-6.81 (m, 2H), 5.68, 5.63 (dd, J1 = 10.4
2.28 (s, 1/2×3H). 13C NMR (125 MHz, CDCl3/TMS): δ 193.6, Hz, J2 = 10.3 Hz , 1H), 5.16, 5.13 (dd, J1 = 10.3 Hz, J2 = 10.4 Hz
193.5, 192.81, 192.79, 158.8, 138.7, 138.5, 137.1, 136.63, ,1H), 3.75 (s, 1/2×3H), 3.74 (s, 1/2×3H). 13C NMR (125 MHz,
136.58, 134.3, 134.2, 133.4, 133.3, 131.44, 131.42, 131.36, CDCl3/TMS): δ 193.1, 192.3, 185.7, 184.9, 158.88, 158.86,
131.33, 129.7, 129.2, 129.1, 128.8, 128.6, 128.51, 128.46, 144.1, 143.7, 137.0, 136.6, 135.0, 134.9, 133.6, 133.5, 133.4,
128.0, 127.9, 126.3, 125.7, 123.1, 123.0, 114.0, 89.8, 84.9, 132.9, 131.5, 131.4, 131.1, 130.9, 129.6, 129.1, 128.9, 128.7,
63.6, 55.2, 38.04, 38.01, 21.3, 21.2. HRMS (ESI-TOF) m/z: 128.6, 128.5, 128.2, 128.00, 127.97, 127.93, 123.0, 122.9,
Calcd. for C32H26NaO3 [M+Na]+ 481.1774; Found 481.1782.
114.0, 89.5, 89.3, 85.3, 84.9, 65.8, 65.1, 55.2, 38.2, 38.1.
2-[1-(4-methoxylphenyl)-3-phenyl-2-propynyl]-1-furanyl-3-
phenyl-1,3-propanedione (3n).24
2-[1-(4-methoxylphenyl)-3-phenyl-2-propynyl]-1-(2-
methylphenyl)-3-phenyl-1,3-propanedione (3j).24
1
Yellow solid (156 mg, 68%), mp 113-115˚C. H NMR (500 MHz, Yellow solid (184 mg, 85%), mp 94-96˚C. 1H NMR (500 MHz,
CDCl3/TMS): δ 8.07 (d, J = 7.3 Hz, 1H), 7.96 (d, J = 7.4 Hz, CDCl3/TMS): δ 8.20 (d, J = 7.3 Hz, 1H), 7.88 (d, J = 7.2 Hz, 1H),
1/2×1H), 7.72 (d, J = 7.3 Hz, 1H), 7.59-7.53 (m, 1+1/2×1H), 7.67-7.59 (m, 1H), 7.51-7.45 (m, 4H), 7.40-7.34 (m, 1+1/2×1H),
7.48-7.44 (m, 2+1/2×1H), 7.38-7.36 (m, 1/2×1H), 7.30-7.11 (m, 7.23-7.11 (m, 4+1/2×1H), 7.03-7.02 (m, 1H), 6.83-6.79 (m, 2H),
8H), 7.03 (d, J = 7.0 Hz, 1H), 6.89 (d, J = 8.7 Hz, 1H), 6.79 (d, J = 6.59-6.58 (m, 1/2×1H), 6.42-6.41 (m, 1/2×1H), 5.79, 5.78 (dd, J1
8.7 Hz, 1H), 5.89, 5.87 (dd, J1 = 10.4 Hz, J2 = 10.3 Hz, 1H), 5.16, = 10.4 Hz, J2 = 10.4 Hz,1H), 5.11, 5.08 (dd, J1 = 10.3 Hz, J2 = 10.4
5.14 (dd, J1 = 10.3 Hz, J2 = 10.3 Hz,, 1H), 3.78 (s, 1/2×3H), 3.72 Hz, 1H), 3.75 (s, 1/2×3H), 3.73 (s, 1/2×3H). 13C NMR (125 MHz,
(s, 1/2×3H), 2.38 (s, 1/2×3H), 2.19 (s, 1/2×3H). 13C NMR (125 CDCl3/TMS): δ 193.2, 192.3, 182.0, 181.1, 158.8, 158.78, 152.4,
MHz, CDCl3/TMS): δ 196.1, 195.7, 193.3, 192.7, 158.9, 158.8, 152.0, 147.0, 146.8, 137.1, 136.6, 133.5, 133.4, 131.5, 131.4,
139.0, 138.4, 138.2, 138.0, 137.2, 136.8, 133.4, 133.3, 131.9, 131.1, 130.9, 129.6, 129.0, 128.8, 128.6, 128.5, 128.0, 127.91,
131.7, 131.51, 131.48, 131.34, 131.31, 130.8, 129.7, 129.6, 127.88, 127.85, 123.0, 122.9, 118.8, 118.5, 113.93, 113.91,
128.9, 128.7, 128.5, 128.4, 128.3, 128.0, 127.93, 127.90, 127.8, 113.0, 112.7, 89.5, 89.1, 84.7, 84.6, 63.6, 63.1, 55.18, 55.16,
127.4, 125.7, 125.5, 123.0, 122.9, 114.0, 113.9, 90.0, 89.6, 37.7, 37.6.
84.7, 84.4, 66.5, 66.3, 55.2, 55.1, 38.3, 38.1, 20.7, 20.3.
2-[1-(4-methoxylphenyl)-3-phenyl-2-propynyl]-1-phenyl-1,3-
butanedione (3o).24
2-[1-(4-methoxylphenyl)-3-phenyl-2-propynyl]-1-(4-
chlorophenyl)-3-phenyl-1,3-propanedione (3k).24
1
Yellow solid (110 mg, 46%), mp 120-121˚C. H NMR (500 MHz, CDCl3/TMS): δ 8.11 (d, J = 7.3 Hz, 2/5×2H), 7.87 (d, J = 7.3 Hz,
Yellow solid (139 mg, 73%), mp 93-94˚C. 1H NMR (500 MHz,
CDCl3/TMS): δ 8.13-8.11 (m, 1/3×2H), 8.07-8.06 (m, 2/3×2H), 3/5×2H), 7.65-7.62 (m, 2/5×1H), 7.55-7.51 (m, 1+3/5×1H),
4 | J. Name., 2012, 00, 1-3
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DOI: 10.1039/C6RA06704B
Journal Name
COMMUNICATION
15 I. B. Krylov, V. A. Vil, A. O. Terent'ev. Beilstein J. Org. Chem.
2015, 11, 92.
16 D. Cheng, K. Yuan, X. Zhou, J. Yan. Tetrahedron Lett. 2015,
56, 1641.
17 X. Yao, C. J. Li. J. Org. Chem. 2005, 70, 5752.
18 Z. Li, C. J. Li. J. Am. Chem. Soc. 2006, 128, 56.
19 Y. Zhang, C. J. Li. Angew. Chem. 2006, 118, 1983.
20 Z. Li, L. Cao, C. J. Li. Angew. Chem. Int. Ed. 2007, 46, 6505.
7.44-7.30 (m, 6H), 7.21-7.14 (m, 3/5×2H), 7.08-7.06 (m,
2/5×2H), 6.91-6.90 (m, 2/5×2H), 6.79-6.77 (m, 3/5×2H), 5.14
(d, J = 10.4 Hz, 2/5×1H), 5.02 (d, J = 10.8, 3/5×1H), 4.96 (d, J =
10.8 Hz, 3/5×1H), 4.87 (d, J = 10.5 Hz, 2/5×1H), 3.82 (s,
2/5×3H), 3.73 (s, 3/5×3H), 2.40 (s, 3/5×3H), 2.01 (s, 2/5×3H).
13C NMR (125 MHz, CDCl3/TMS): δ 201.6, 200.8, 193.9, 193.4,
159.1, 158.9, 137.2, 136.6, 133.8, 133.7, 131.7, 131.5, 130.60,
130.57, 129.43, 129.37, 129.0, 128.9, 128.8, 128.7, 128.3,
128.0, 127.9, 122.9, 122.7, 114.3, 114.1, 89.2, 88.7, 85.2, 84.4,
71.2, 69.2, 55.3, 55.2, 37.8, 37.5, 29.7, 27.6.
21 O. Baslé, C. J. Li. Green Chem. 2007, 9, 1047.
22 Z. Li, R. Yu, H. Li. Angew. Chem. Int. Ed. 2008, 47, 7497.
23 N. Borduas, D. A. Powell. J. Org. Chem. 2008, 73, 7822.
24 D. Cheng, W. Bao. J. Org. Chem. 2008, 73, 6881.
25 D. Cheng, W. Bao. Adv. Synth. Catal. 2008, 350, 1263.
26 M. F. Ali, R. Çalışkan, E. Şahin, M. Balci. Tetrahedron 2009,
65, 1430.
27 C. A. Correia, C. J. Li. Tetrahedron Lett. 2010, 51, 1172.
28 D. Ramesh, U. Ramulu, S. Rajaram, P. Prabhakar, Y.
Venkateswarlu. Tetrahedron Lett. 2010, 51, 4898.
29 C. G. Piscopo, S. Bühler, G. Sartori, R. Maggi. Catal. Sci.
2-[1-(4-methoxylphenyl)-3-phenyl-2-propynyl]-2,4-
pentanedione (3p).24
Yellow solid (85 mg, 53%), mp 83-84˚C. 1H NMR (500 MHz,
CDCl3/TMS): δ 7.39-7.28 (m, 7H), 6.88 (d, J = 8.7 Hz, 2H), 4.64
(d, J = 10.9 Hz, 1H), 4.20 (d, J = 10.9 Hz, 1H), 3.80 (s, 3H),
2.39(s, 3H), 1.96 (s, 3H). 13C NMR (125 MHz, CDCl3/TMS): δ
201.7, 159.1, 131.63, 131.59, 130.2, 129.2, 128.4, 128.3, 128.2,
127.8, 122.8, 114.3, 114.0, 88.4, 84.8, 75.8, 55.3, 37.3, 31.1,
28.7.
Technol. 2012, 2, 2449.
30 D. Cheng, X. Ye, W. Cui, R. Sun, J. Yan. J. Chem. Res. 2012, 36
729.
,
31 S. Pan, J. Liu, Y. Li, Z. Li. Chin. Sci. Bull. 2012, 57, 2382.
32 Á. Pintér, M. Klussmann. Adv. Synth. Catal. 2012, 354, 701.
4-carboethoxy-1,5-diphenyl-3-(4-methoxylphenyl)-1-pentyn-5-
one (3q).24
33 D. Cheng, K. Yuan, X. Zhou, J. Yan. J. Chem. Res. 2014, 38
751.
,
Yellow oil (101 mg, 49%). 1H NMR (500 MHz, CDCl3/TMS): δ
8.15-8.13 (m, 2H), 7.64-7.61 (m, 1H), 7.54-7.50 (m, 2H), 7.47-
7.44 (m, 2H), 7.23-7.15 (m, 3H), 7.12-7.10 (m, 2H), 6.92-6.89
(m, 2H), 4.90 (d, J = 10.7 Hz, 1H), 4.82 (d, J = 10.7 Hz, 1H), 3.99-
3.93 (m, 2H), 3.82 (s, 3H), 1.03 (t, J = 7.2 Hz, 3H). 13C NMR (125
MHz, CDCl3/TMS): δ 192.9, 166.9, 159.1, 136.9, 133.6, 131.5,
130.6, 129.6, 129.0, 128.8, 128.0, 127.9, 123.0, 114.0, 89.3,
84.1, 61.6, 61.4, 55.3, 37.7, 13.8.
34 M. Xiang, Q. Y. Meng, J. X. Li, Y. W. Zheng, C. Ye, Z. J. Li, B.
Chen, C. H. Tung, L. Z. Wu. Chem. Eur. J. 2015, 21, 18080.
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2015, 13, 5710.
36 K. Yang, Q. Song. Org. Lett. 2015, 17, 548.
37 M. Xiang, Q. Y. Meng, X. W. Gao, T. Lei, B. Chen, C. H Tung, L.
Z. Wu. Org. Chem. Front. 2016,
a
3, 486.
38 To mixture of 1,3-diphenylpropene (0.6 mmol), 1,3-
diphenyl-1,3-propanedione (0.5 mmol) in CH3NO2 (2.5 mL),
HCOOH (0.25 mL ) was added. No coupling product was
isolated within half an hour or longer.
Acknowledgements
This work was supported by Natural Science Foundation of
Zhejiang Provincial (LY15B020004).
Notes and references
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This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 5
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DOI: 10.1039/C6RA06704B
The coupling reaction of 1,3-diarylpropyne and 1,3-dicarbonyl compounds using molecular
oxygen as a terminal oxidation was developed. It catalyzed by DDQ and NaNO2 in the
presence of HCOOH. The corresponding product was obtained within half an hour in
37-87%.