Cul-catalysed synthesis of (E)-arylvinyl aryl ethers

Article abstract of DOI:10.3184/174751914X13866881990651

(E)-Arylvinyl aryl ethers have been synthesised from (E)-arylvinyl bromide and phenols in 1,4-dioxan in high yield catalysed by CuI/N,N-dimethylglycine in the presence of Cs₂CO₃.

Full text of DOI:10.3184/174751914X13866881990651

58 RESEARCH PAPER
JANUARY, 58–59
JOURNAL OF CHEMICAL RESEARCH 2014
CuI-catalysed synthesis of (E)-arylvinyl aryl ethers
Wensheng Zhanga*, Wenjing Xua and Guirong Qub
aSchool of Science, Jiaozuo Teachers’ College, Shanyang Road 998, Jiaozuo 454001, P.R. China
bCollege of Chemical and Environmental Engineering, Henan Normal University, Xinxiang 453007, P.R. China
(E)-Arylvinyl aryl ethers have been synthesised from (E)-arylvinyl bromide and phenols in 1,4-dioxan in high yield catalysed by
CuI/N,N-dimethylglycine in the presence of Cs2CO3.
Keywords: aryl vinyl ether, synthesis, Ullmann-ether reaction, (E)-arylvinyl bromide, phenol, CuI, N,N-dimethylglycine,
stereoselectivity
Aryl vinyl ethers are intermediates in a variety of reactions
including cycloaddition, cyclopropanation, and metathesis
processes, as well as in the synthesis of polymers. In addition,
aryl vinyl ethers have found applications in the construction
of natural products and compounds which exhibit interesting
biological activities.1 Over the past decade, attention has been
devoted to the development of copper-catalysed Ullmann-ether
coupling reactions for the synthesis of aryl ethers.2–10 However,
only a few methods have appeared for the copper-catalysed
synthesis of vinyl ethers of synthetic, polymeric, or biological
importance.11–14 The most efficient methods for the synthesis
of aryl vinyl ethers are based upon Hg-15,16 and Pd-mediated
good to excellent yields (Scheme 1, Table 1). Electron-donating
and electron-withdrawing group on the aromatic ring of the
(E)-arylvinyl bromides or phenols had virtually no effect on
the outcome of the reaction. For example, compounds with
substituentssuchasMe,Bu-t,OMe,FandClonthearomaticring
could be smoothly transformed to the corresponding arylvinyl
aryl ethers in high yields under these reaction conditions. The
results are listed in Table 1 (entries 2–7). The reaction was
found to be equally efficient for phenols bearing Me on the
o-position of the aromatic ring, affording the products in good
yields (Table 1, entries 3 and 4). The stereochemical assignment
of the configuration of the products was made on the basis of 1H
NMR spectroscopy. This showed that the stereoselectivity was
good, as determined by the coupling constant of the “=C–H”
(J=12.4 Hz).
17,18
coupling reactions of phenols with different vinyl sources.
These suffer from either the toxicity of mercury or the high cost
of Pd, as well as the latter’s air sensitivity, potentially limiting
their use for many industrial applications. Reports of the
Cu-catalysed vinylation of phenols have appeared recently.19–26
Ma and co-workers reported α- and β-amino acids can
accelerate Ullmann-type aryl amination whilst the coupling
reactions of phenols with aryl halides can be carried out at
relatively low temperatures.27–31 We now report a Ullmann-type
of reaction between (E)-arylvinyl bromides and phenols using
Ma’s CuI-N,N-dimethylglycine catalytic system.29 This affords
(E)-arylvinyl aryl ethers efficiently (Scheme 1).
Table 1 Synthesis of arylvinyl aryl ethersa
Entry
R1
R2
Product 3
Yields of 3/%b
1
2
3
4
5
6
7
4-Me
4-Me
4-Me
4-Me
4-Me
4-F
4-Me
4-Bu-t
2-Me
2,4-Me2
4-MeO
4-Me
4-Me
3a
3b
3c
3d
3e
3f
94
91
89
90
94
91
92
4-Cl
3g
aReaction conditions: (E)-arylvinyl bromide (1 mmol), phenol (1.2 mmol),
Cs2CO3 (2.2 mmol), CuI (0.1 mmol), N,N-dimethylglycine (0.3 mmol),
1,4-dioxane (4 mL), 100 °C, 24 h.
Results and discussion
The Ullmann-ether reaction of (E)-arylvinyl bromides (1)
and phenols (2) was carried out at 100 °C for 24 h under N2
atmosphere(Scheme1).(E)-1-(2-bromovinyl)-4-methylbenzene
and p-cresol were initially chosen as the model substrates using
catalytic amount of CuI and N,N-dimethylglycine and 5 mL
of 1,4-dioxan as the solvent. The expected 4-methylphenyl-E-
(4-methyl)-styryl ether 3a was obtained in 94% yield (Table 1,
entry 1). Using the same conditions, we have examined the
substrate scope of this reaction. Our experiments indicate that a
range of (E)-arylvinyl bromides underwent the cross-coupling
process to produce the corresponding arylvinyl aryl ethers in
bIsolated yields based on arylvinyl bromide.
Conclusion
In summary, (E)-arylvinyl aryl ethers can be synthesised by
an Ullmann-ether reaction between (E)-arylvinyl bromides
and phenols in the presence of a catalytic amount of CuI and
N,N-dimethylglycine using 1,4-dioxan as the solvent. The
stereoselectivity was good, as determined by the coupling
constant of the “=C–H” (J=12.4 Hz) in the 1H NMR spectra.
CuI
N,N-dimethylglycine
OH
O
Br
+
R2
R1
R1
Cs2CO3, 1, 4-dioxane
100 oC
R2
2
3
1
Scheme 1
* Correspondent. E-mail: tongjizws@163.com
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JOURNAL OF CHEMICAL RESEARCH 2014 59
NMR (100 MHz, CDCl3): δ 20.6, 116.4, 117.0, 126.7, 128.8, 130.2, 131.9,
133.0, 133.9, 144.6, 154.9. HRMS calcd for C15H13ClO2. m/z 260.0604;
found m/z 260.0601.
Experimental
1H NMR and 13C NMR spectra were recorded using a Bruker DPX-
400 spectrometer with SiMe4 as an internal standard. High resolution
mass spectra were determined using a Finnigan-NAT GC/MS/
DS 8430 spectrometer. All reactions were monitored by TLC with
HuanghaiGF254 silica gel coated plates. Column chromatography was
carried out using 300–400 mesh silica gel at medium pressure.
This work was supported by the National Natural Science
Foundation of China (No. 21172059), Program for Science
& Technology Innovation Talents in Universities of He’nan
Province (No. 2011HASTIT032), Foundation of He’nan
Scientific and Technological Committee (Nos 132300410206
and 132300410167), Foundation of He’nan Educational
Committee (No. 2013C150001) and Foundation of Jiaozuo
Scientific and Technological Bureau (No. 2012017).
Synthesis of (E)-arylvinyl aryl ethers 3; general procedure
A stirred solution of (E)-arylvinyl bromide 1 (1 mmol) and phenol 2
(1.2 mmol) in 1,4-dioxane (4 mL) was treated with Cs2CO3 (2.2 mmol),
CuI (0.1 mmol), N,N-dimethylglycine (0.3 mmol) under a nitrogen
atmosphere. The reaction mixture was stirred at 100 °C for 24 h.
After the completion of the reaction, monitored by TLC, the reaction
system was cooled to room temperature, diluted with EtOAc (20 mL)
and filtered. The filtrate was washed with saturated brine (20 mL) and
water (20 mL), dried over Na2SO4, and concentrated. The residue was
chromatographed to afford the corresponding (E)-arylvinyl aryl ethers
3.
Received 8 October 2013; accepted 23 November 2013
Paper 1302220 doi: 10.3184/174751914X13866881990651
Published online: 8 January 2014
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1
89%; light yellow viscous liquid. H NMR (400 MHz, CDCl3): δ 2.34
(3H, s), 2.37 (3H, s), 6.28 (1H, d, J=12.4 Hz), 7.02–7.25 (9H, m). 13C NMR
(100 MHz, CDCl3): δ 16.1, 21.1, 112.6, 116.4, 123.3, 125.5, 127.0, 128.18,
129.4, 131.2, 132.4, 136.2, 143.6, 155.3. HRMS calcd for C16H16O m/z
224.1201; found m/z 224.1204.
2,4-Dimethylphenyl-E-(4-methyl)-styryl ether (3d, Table 1, entry 4):
Yield 90%; light yellow viscous liquid. 1H NMR (400 MHz, CDCl3): δ
2.28 (3H, s), 2.32 (3H, s), 2.34 (3H, s), 6.20 (1H, d, J=12.4 Hz), 6.89–7.21
(8H, m). 13C NMR (100 MHz, CDCl3): δ 16.0, 20.6, 21.1, 111.8, 116.7,
125.4, 127.4, 128.0, 129.4, 131.9, 132.5, 132.9, 136.0, 144.3, 153.1. HRMS
calcd for C17H18O m/z 238.1358; found m/z 238.1360.
4-Methoxylphenyl-E-(4-methyl)-styryl ether (3e, Table 1, entry 5):
Yield 94%; light yellow viscous liquid. 1H NMR (400 MHz, CDCl3): δ
2.32 (3H, s), 3.79 (3H, s), 6.23 (1H, d, J=12.4 Hz), 6.88 (2H, d, J=8.8 Hz),
6.99 (2H, d, J=8.8 Hz), 7.05–7.11 (3H, m), 7.18 (2H, d, J=8.0 Hz). 13C
NMR (100 MHz, CDCl3): δ 20.6, 21.1, 113.0, 116.8, 125.5, 129.3, 130.1,
132.3, 132.6, 136.2, 143.3, 155.1. HRMS calcd for C16H16O2 m/z 240.1150;
found m/z 240.1154.
4-Methylphenyl-E-(4-fluro)-styryl ether (3f, Table 1, entry 6): Yield
91%; light yellow viscous liquid. H NMR (400 MHz, CDCl3): δ 2.34
(3H, s), 6.25 (1H, d, J=12.4 Hz), 6.93–7.24 (9H, m). 13C NMR (100 MHz,
CDCl3): δ 20.6, 115.0, 116.9, 126.9, 127.0, 130.1, 130.2, 130.2, 132.8,
143.8, 155.0. HRMS calcd for C15H13FO2 m/z 244.0900; found m/z
244.0906.
1
4-Methylphenyl-E-(4-chloro)-styryl ether (3g, Table 1, entry 7): Yield
92%. Yellow vicious liquid. 1H NMR (400 MHz, CDCl3): δ 2.31 (3H, s),
6.21 (1H, d, J=12.4 Hz), 6.92 (2H, d, J=8.4 Hz), 7.09–7.24 (9H, m). 13
C
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