CN110483291A - One kind (E)-beta-aromatic-β, γ-beta-unsaturated esters compound synthetic method - Google Patents
One kind (E)-beta-aromatic-β, γ-beta-unsaturated esters compound synthetic method Download PDFInfo
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- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/06—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by conversion of non-aromatic six-membered rings or of such rings formed in situ into aromatic six-membered rings, e.g. by dehydrogenation
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- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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Abstract
The invention belongs to technical field of organic synthetic chemistry, disclose a kind of using ethyl diazoacetate and fragrant boric acid as coupling reagent, copper is catalyzed 1, the 1- virtue alkylated reaction of alkynes, one-step synthesis it is important (E)‑βAryl-β,γThe method of beta-unsaturated esters, specifically: by alkynes compound, solvent, ethyl diazoacetate, fragrant boric acid compound, Phen, CuI and K3PO4Mixing, then under atmosphere of inert gases in 90-110 DEG C confined reaction 1.2-3 hour, reaction end it is post-treated to obtain the final product.The present invention have the characteristics that catalyst system is simple, raw material is cheap and easy to get, superior functional group compatibility, high region and chemo-selective, wide application range of substrates it is general, be suitable for synthesize it is various (E)‑βAryl-β,γBeta-unsaturated esters compound.
Description
Technical field
The invention belongs to technical field of organic synthetic chemistry, and in particular to a kind of copper catalysis alkynes and ethyl diazoacetate and
Fragrant acid reaction, one-step synthesis (E)-βAryl-β,γThe method of beta-unsaturated esters compound.
Background technique
β,γBeta-unsaturated esters compound is widely present in the active natural products of important biomolecule, meanwhile, in organic conjunction
Organic synthesis intermediate ((a) Millar, J. G. is also important in; Oehlschlager, A. C.; Wong, J.
W. J. Org. Chem.1983, 48, 4404. (b) Oehlschlager, A. C.; Wong, J. W.;
Verigin, V. G.; Pierced, H. D. J. Org. Chem.1983, 48, 5009. (c) Liang, J. L.;
Javed, U.; Lee, S. H.; Park, J. G.; Jahng, Y. Arch. Pharm. Res. 2014, 37,
862. (d) Eissler, S.; Nahrwold, M.; Neumann, B.; Stammler, H. G.; Sewald, N.Org. Lett. 2007, 9, 817.), therefore, the synthetic method for preparing such compound causes the extensive of organic chemist
Concern.
Currently, method reported in the literature specifically includes that the carbonylation of (1) allyl substrate and CO containing leaving group
React ((a) Tsuji, J.; Sato, K.; Okumoto, H.J. Org. Chem. 1984, 49, 1341. (b)
Murahashi, S.; Imada, Y.; Taniguchi, Y.; Higashiura, S. J. Org. Chem.1993,58, 1538. (c) Liu, Q.; Wu, L.; Jiao, H.; Fang, X.; Jackstell, R.; Beller, M.Angew. Chem., Int. Ed. 2013, 52, 8064.)；(2) alkenyl trifluoroborate and 2- ethyl chloroacetate intersect
Coupling reaction ((a) Molander, G. A.; Barcellos, T.; Traister, K. M.Org. Lett. 2013,15, 3342. (b) Brown, H. C.; Cho, B. T.; Park, W. S. J. Org. Chem. 1986, 51,
3398.)；(3) α, decarboxylation alkyl carboxylation reaction (Gao, the B. of beta-unsaturated acid; Xie, Y.; Shen, Z.; Yang,
L.; Huang, H. Org. Lett.2015, 17, 4968.).Such compound is synthesized in spite of more method, but
There is also some disadvantages, for example, using gas raw material is not easy to operate, need expensive metallic catalyst, and atom utilization is low, stands
Body selectivity difficulty or ease control etc..Importantly, for synthesis (E)-βAryl-β,γBeta-unsaturated esters compound still lacks row
Effective method.Therefore, develop cheap catalyst system, realize (E)-βAryl-β,γBeta-unsaturated esters compound it is green
Color, efficiently synthesize it is of crucial importance.
Summary of the invention
Present invention aims to overcome that prior art defect, provide it is a kind of (E)-βAryl-β,γBeta-unsaturated esters compound
Synthetic method, be to be reacted by cuprous iodide catalysis alkynes and ethyl diazoacetate and virtue boric acid one-step synthesis and obtained, the party
Method has the characteristics that reaction step is simple, raw material is cheap and easy to get, wide application range of substrates is general, stereoselectivity is high.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of (E)-βAryl-β,γThe synthetic method of beta-unsaturated esters compound, specifically includes the following steps:
By alkynes compound, solvent, ethyl diazoacetate, fragrant boric acid compound, Phen (Phen), CuI and K3PO4
Mixing, then under atmosphere of inert gases in 90-110 DEG C confined reaction 1.2-3 hour, reaction end it is post-treated to obtain the final product.
Specifically, the alkynes compound is preferably phenylacetylene, 4- methyl phenylacetylene, 4- Liquid Crystal Compounds Intermediate p-Ethyl-phenylacetylene, 4- propyl
Phenylacetylene, 4- butyl phenylacetylene, 4- tert-butyl benzene acetylene, 4- fluorobenzene acetylene, 4- chlorobenzene acetylene, 4- bromobenzene acetylene, 3- fluorophenethyl
Alkynes, 3- chlorobenzene acetylene, 2- fluorobenzene acetylene, 2- chlorobenzene acetylene, methyl propargyl ether, glycidyl propargyl ether or cyclopropyl second
Alkynes etc..
Specifically, the virtue boric acid compound is preferably phenyl boric acid, 4- methylphenylboronic acid, 4- ethyl phenyl boric acid, 4- different
Propyl phenyl boric acid, 4- tert-butylbenzeneboronic acid, 4- vinylphenylboronic acid, 4- chlorophenylboronic acid, 4- bromobenzeneboronic acid, 3- methylphenylboronic acid,
3- methoxyphenylboronic acid, 3- fluorobenzoic boric acid, 3- chlorophenylboronic acid or 3- bromobenzeneboronic acid etc..
Further, above-mentioned (E)-βAryl-β,γIn the synthetic method of beta-unsaturated esters compound, the alkynes class
The molar ratio for closing object, ethyl diazoacetate and fragrant boric acid compound is preferably 1.2-1.5:1:2-3.
Further, above-mentioned (E)-βAryl-β,γIn the synthetic method of beta-unsaturated esters compound, the ligand is adjacent luxuriant and rich with fragrance
The molar ratio of sieve quinoline and ethyl diazoacetate is preferred 5-15:100.
Further, above-mentioned (E)-βAryl-β,γIn the synthetic method of beta-unsaturated esters compound, the catalyst CuI
Molar ratio with ethyl diazoacetate is preferably 5-15:100.
Further, above-mentioned (E)-βAryl-β,γIn the synthetic method of beta-unsaturated esters compound, the alkali K3PO4With
The molar ratio of ethyl diazoacetate is preferably 1.5-2.5:1.
Further, above-mentioned (E)-βAryl-β,γIn the synthetic method of beta-unsaturated esters compound, the solvent is preferred
For Isosorbide-5-Nitrae-dioxane, every 0.3mmol ethyl diazoacetate addition 1-2ml Isosorbide-5-Nitrae-dioxane is advisable；The inert gas is
Nitrogen or argon gas.
It is ligand, K by catalyst, Phen of CuI in the present invention3PO4It is anti-in 1,4- dioxane solvent for alkali
It answers, reacts stereoselectivity together with bifunctional dough through alkynes with ethyl diazoacetate and fragrant boronic acid compounds by alkynes
One step obtain (E)-βAryl-β,γBeta-unsaturated esters compound.Compound 1 is the phenylacetylene that aromatic ring has various substituent groups in figure
Class compound, alkyl propargyl ether compound etc..Compound 2 is ethyl diazoacetate, and compound 3 is that aromatic ring has various substitutions
Phenylboronic acid compound of base etc..Chemical equation is as follows:
。
In the present invention, the reaction of the bifunctional dough of alkynes due to can efficiently, a step of Atom economy synthesize take more
For alkene, rapidly developed in recent years.Currently, the bifunctional dough repercussion study of alkynes is concentrated mainly on two new bases
Group is introduced between on two carbon atoms of alkynes, i.e. 1, the 2- difunctionality dough reaction of alkynes, however, the bis- officials of 1,1- of alkynes
Energy dough (together with bifunctional dough) is reacted, i.e., two new groups is introduced on the same carbon atom of alkynes, is but seldom ground
Study carefully.Therefore, present invention research and develop cheap transition metal-catalyzed alkynes reacted together with bifunctional dough be effectively synthesized (E)-βAryl-β,γBeta-unsaturated esters compound has important theoretical significance and application value.Compared to the prior art, originally
The novelty of invention is:
Synthetic method reaction of the present invention raw material used is easily obtained from industrial products, and reagent is cheap, and catalyst system is simple, substrate
Range is wide in range, and operation is simple, and yield is higher, be high region and chemo-selective synthesis (E)-βAryl-β,γInsatiable hunger
Provide simple and practical method with ester compounds, be suitable for synthesize it is various (E)-βAryl-β,γBeta-unsaturated esters compound.
Detailed description of the invention
Fig. 1 be 1 product of embodiment (E)-βAryl-β,γBeta-unsaturated esters 4a's1H NMR spectra；
Fig. 2 be 1 product of embodiment (E)-βAryl-β,γBeta-unsaturated esters 4a's13C NMR spectra；
Fig. 3 be 2 product of embodiment (E)-βAryl-β,γBeta-unsaturated esters 4b's1H NMR spectra；
Fig. 4 be 2 product of embodiment (E)-βAryl-β,γBeta-unsaturated esters 4b's13C NMR spectra；
Fig. 5 be 4 product of embodiment (E)-βAryl-β,γBeta-unsaturated esters 4d's1H NMR spectra；
Fig. 6 be 4 product of embodiment (E)-βAryl-β,γBeta-unsaturated esters 4d's13C NMR spectra；
Fig. 7 be 5 product of embodiment (E)-βAryl-β,γBeta-unsaturated esters 4e's1H NMR spectra；
Fig. 8 be 5 product of embodiment (E)-βAryl-β,γBeta-unsaturated esters 4e's13C NMR spectra.
Specific embodiment
Technical solution of the present invention is further discussed in detail with reference to embodiments, but protection scope of the present invention
It is not limited thereto.
Embodiment 1
Firstly, being put into stirrer in the seal pipe of 35 mL, and 33 μ L ethyl diazoacetates (0.3 mmol), 1 are added according to this,
To methylphenylboronic acid (0.9 mmol), mixing is equal by 4- dioxane (1 mL), 41 μ L phenylacetylenes (0.36 mmol), 124.9 mg
It is even.Then, 5.4 mg Phen (0.03 mmol), 5.7 mg CuI are sequentially added into above-mentioned uniformly mixed solution
(0.03 mmol) and 130.0 mg K3PO4(0.6 mmol).After all drugs add, about 3 points of nitrogen are passed through into seal pipe
Clock, the air excluded in seal pipe are stirred to react 1.5 hours with cock sealing orifice under the conditions of 100 DEG C.After reaction,
System is cooled to room temperature, 3 mL distilled water are added into reaction system, are extracted with ethyl acetate, merges organic phase, decompression is steamed
Organic phase solvent is removed in distillation, through silica gel column chromatography (VPetroleum ether: VEthyl acetate=50:1) obtain 71.0 mg colorless liquid product 4a, yield
85%.Reaction sees below formula:
Spectrum elucidation data
1H NMR (400 MHz, CDCl3): δ= 1.17 (t, J = 7.2 Hz, 3H), 2.36 (s, 3H), 3.69
(s, 2H), 4.11 (q, J = 7.2 Hz, 2H), 7.00 (s, 1H), 7.18 (d, J = 7.6 Hz, 2H),
7.28-7.41 (m, 7H); 13C NMR (100 MHz, CDCl3): δ= 14.1, 21.1, 36.6, 60.8, 126.1,
127.1, 128.4, 128.8, 129.2, 130.4, 134.5, 137.4, 137.6, 138.8, 171.6. HRMS
(ESI-TOF).Calcd for C19H21O2, [M+H]+ m/z 281.1542, Found 281.1537。
Above-mentioned 4a compound can be used for synthesizing known substance 3- aryl naphthols:
84 mg 4a (0.3 mmol) are dissolved in the dense H of 300 mg2SO4In, it is stirred at room temperature 2 hours.After reaction, careful to add
Enter 2 mL cold water, be extracted with ethyl acetate (3 x, 5 mL), merges organic phase, vacuum distillation removes the solvent of organic phase, through silicon
Plastic column chromatography (VPetroleum ether: VEthyl acetate=10:1) 52.0 mg white solid product 5a are obtained, yield 74%, reaction equation is as follows:
。
Embodiment 2
Firstly, being put into stirrer in the seal pipe of 35 mL, and 33 μ L ethyl diazoacetates (0.3 mmol), 1 are added according to this,
4- dioxane (1 mL), 47 μ L to methyl phenylacetylene (0.36 mmol), 124.9 mg to methylphenylboronic acid (0.9 mmol),
It is uniformly mixed.Then, 5.4 mg Phen (0.03 mmol), 5.7 mg are sequentially added into above-mentioned uniformly mixed solution
CuI (0.03 mmol) and 130.0 mg K3PO4(0. 6 mmol).After all drugs add, nitrogen is passed through into seal pipe
About 3 minutes, the air excluded in seal pipe was stirred 1.5 hours under the conditions of 100 DEG C with cock sealing orifice.Reaction terminates
Afterwards, system is cooled to room temperature, 3 mL distilled water is added into reaction system, are extracted with ethyl acetate, merge organic phase, decompression
The solvent of organic phase is distilled off, through silica gel column chromatography (VPetroleum ether: VEthyl acetate=50:1) obtain 72.0 mg colorless liquid product 4b
(its No. CAS is 130240-35-6), yield 82%.Reaction sees below formula:
Spectrum elucidation data
Colorless oil. 1H NMR (400 MHz, CDCl3): δ= 1.19 (t, J = 7.2 Hz, 3H), 2.37
(s, 3H), 2.38 (s, 3H), 3.71 (s, 2H), 4.12 (q, J = 7.2 Hz, 2H), 6.99 (s, 1H),
7.18 (d, J = 5.2 Hz, 2H), 7.20 (d, J = 5.2 Hz, 2H), 7.29 (d, J = 8.0 Hz, 2H),
7.41 (d, J = 8.0 Hz, 2H); 13C NMR (100 MHz, CDCl3): δ= 14.1, 21.1, 21.2, 36.6,
60.7, 126.0, 128.6, 129.1, 129.1, 130.4, 133.8, 134.6, 136.8, 137.2, 138.9,
171.7. HRMS(ESI-TOF).Calcd for C20H23O2, [M+H]+ m/z 295.1698, Found 295.1688。
Embodiment 3:
Firstly, being put into stirrer in the seal pipe of 35 mL, and 33 μ L ethyl diazoacetates (0.3 mmol), 1 are added according to this,
4- dioxane (1 mL), 42 μ L to methylphenylboronic acid (0.9 mmol), mix fluorobenzene acetylene (0.36 mmol), 124.9 mg
It closes uniform.Then, 5.4 mg Phen (0.03 mmol), 5.7 mg CuI are sequentially added into above-mentioned uniformly mixed solution
(0.03 mmol) and 130.0 mg K3PO4(0. 6 mmol).After all drugs add, about 3 points of nitrogen are passed through into seal pipe
Clock, the air excluded in seal pipe are stirred 1.5 hours under the conditions of 100 DEG C with cock sealing orifice.After reaction, by body
System is cooled to room temperature, and 3 mL distilled water are added into reaction system, are extracted with ethyl acetate, and merges organic phase, and vacuum distillation removes
The solvent for going organic phase, through silica gel column chromatography (VPetroleum ether: VEthyl acetate=50:1) obtain 63.0 mg colorless liquid product 4c, yield
70%.Reaction sees below formula:
Spectrum elucidation data
Colorless oil. 1H NMR (400 MHz, CDCl3): δ= 1.18 (t, J = 7.2 Hz, 3H), 2.37
(s, 3H), 3.65 (s, 2H), 4.11 (q, J = 7.2 Hz, 2H), 6.95 (s, 1H), 7.06 (t, J =
7.2 Hz, 2H), 7.18 (d, J = 8.0 Hz, 2H), 7.34-7.40 (m, 4H); 13C NMR (100 MHz,
CDCl3): δ= 14.1, 21.1, 36.5, 60.8, 115.3 (d, J = 21.0 Hz), 126.0, 129.2,
129.3, 130.4 (d, J = 8.0 Hz), 133.6 (d, J = 4.0 Hz), 134.6, 137.5, 138.5,
161.9 (d, J = 245.0 Hz), 171.5. HRMS(ESI-TOF).Calcd for C19H20FO2, [M+H]+ m/z
299.1447, Found 299.1438。
Embodiment 4
Firstly, being put into stirrer in the seal pipe of 35 mL, and 33 μ L ethyl diazoacetates (0.3 mmol), 1 are added according to this,
Chlorophenylboronic acid (0.9 mmol) between 4- dioxane (2 mL), 41 μ L phenylacetylenes (0.36 mmol), 145.0 mg, mixing are equal
It is even.Then, 5.4 mg Phen (0.03 mmol), 5.7 mg CuI are sequentially added into above-mentioned uniformly mixed solution
(0.03 mmol) and 130.0 mg K3PO4(0. 6 mmol).After all drugs add, about 3 points of nitrogen are passed through into seal pipe
Clock, the air excluded in seal pipe are stirred 1.5 hours under the conditions of 100 DEG C with cock sealing orifice.After reaction, by body
System is cooled to room temperature, and 3 mL distilled water are added into reaction system, are extracted with ethyl acetate, and merges organic phase, and vacuum distillation removes
The solvent for going organic phase, through silica gel column chromatography (VPetroleum ether: VEthyl acetate=50:1) obtain 65.0 mg colorless liquid product 4d, yield
72%.Reaction sees below formula:
Spectrum elucidation data
Colorless oil. 1H NMR (400 MHz, CDCl3): δ= 1.18 (t, J = 7.2 Hz, 3H), 3.68
(s, 2H), 4.12 (q, J = 7.2 Hz, 2H), 7.02 (s, 1H), 7.26-7.39 (m, 8H), 7.50 (s,
1H); 13C NMR (100 MHz, CDCl3): δ= 14.1, 36.6, 60.9, 124.5, 126.5, 127.5,
127.6, 128.5, 128.7, 129.6, 132.3, 133.6, 134.4, 137.0, 143.7, 171.1. HRMS
(ESI-TOF).Calcd for C18H18ClO2, [M+H]+ m/z 301.0995, Found 301.0992。
Embodiment 5
Firstly, being put into stirrer in the seal pipe of 35 mL, and 33 μ L ethyl diazoacetates (0.3 mmol), 1 are added according to this,
4- dioxane (1 mL), 31 μ L methylpropynyl ethers (0.36 mmol), 124.9 mg to methylphenylboronic acid (0.9 mmol),
It is uniformly mixed.Then, 5.4 mg Phen (0.03 mmol), 5.7 mg are sequentially added into above-mentioned uniformly mixed solution
CuI (0.03 mmol) and 130.0 mg K3PO4(0. 6 mmol).After all drugs add, nitrogen is passed through into seal pipe
About 3 minutes, the air excluded in seal pipe was stirred 1.5 hours under the conditions of 100 DEG C with cock sealing orifice.Reaction terminates
Afterwards, system is cooled to room temperature, 3 mL distilled water is added into reaction system, are extracted with ethyl acetate, merge organic phase, decompression
The solvent of organic phase is distilled off, through silica gel column chromatography (VPetroleum ether: VEthyl acetate=70:1) 68.5 mg colorless liquid product 4e are obtained,
Yield 92%.Reaction sees below formula:
Spectrum elucidation data
Colorless oil. 1H NMR (400 MHz, CDCl3): δ= 1.19 (t, J = 7.2 Hz, 3H), 2.34
(s, 3H), 3.39 (s, 3H), 3.53 (s, 2H), 4.10-4.17 (m, 4H), 6.07 (t, J = 6.4 Hz,
1H), 7.13 (d, J = 7.6 Hz, 2H), 7.31 (d, J = 8.0 Hz, 2H); 13C NMR (100 MHz,
CDCl3): δ= 14.1, 21.0, 36.4, 58.2, 60.8, 69.4, 125.9, 127.5, 129.0, 135.4,
137.2, 138.5, 170.9. HRMS(ESI-TOF).Calcd for C15H20NaO3, [M+Na]+ m/z 271.1310,
Found 271.1303。
Embodiment 6
Firstly, being put into stirrer in the seal pipe of 35 mL, and 33 μ L ethyl diazoacetates (0.3 mmol), 1 are added according to this,
4- dioxane (1 mL), 31 μ L cyclopropyl acethlenes (0.36 mmol), 124.9 mg mix methylphenylboronic acid (0.9 mmol)
It closes uniform.Then, 5.4 mg Phen (0.03 mmol), 5.7 mg CuI are sequentially added into above-mentioned uniformly mixed solution
(0.03 mmol) and 130.0 mg K3PO4(0. 6 mmol).After all drugs add, about 3 points of nitrogen are passed through into seal pipe
Clock, the air excluded in seal pipe are stirred 1.5 hours under the conditions of 100 DEG C with cock sealing orifice.After reaction, by body
System is cooled to room temperature, and 3 mL distilled water are added into reaction system, are extracted with ethyl acetate, and merges organic phase, and vacuum distillation removes
The solvent for going organic phase, through silica gel column chromatography (VPetroleum ether: VEthyl acetate=70:1) obtain 66.0 mg colorless liquid product 4f, yield
90%.Reaction sees below formula:
Spectrum elucidation data
Colorless oil. 1H NMR (400 MHz, CDCl3): δ= 0.47-0.51 (m, 2H), 0.85-0.88
(m, 2H), 1.20 (t, J = 7.2 Hz, 3H), 1.58-1.66 (m, 1H), 2.31 (s, 3H), 3.61 (s,
2H), 4.12 (q, J = 7.2 Hz, 2H), 5.31 (d, J = 9.2 Hz, 1H), 7.09 (d, J = 8.0 Hz,
2H), 7.24 (d, J = 8.4 Hz, 2H); 13C NMR (100 MHz, CDCl3): δ= 7.5, 11.3, 14.1,
21.0, 36.4, 60.6, 125.4, 128.9, 130.8, 135.7, 136.2, 139.2, 171.7. HRMS(ESI-
TOF).Calcd for C16H21O2, [M+H]+ m/z 245.1542, Found 245.1538。
Claims (8)
1. a kind of (E)-βAryl-β,γThe synthetic method of beta-unsaturated esters compound, which comprises the following steps:
By alkynes compound, solvent, ethyl diazoacetate, fragrant boric acid compound, Phen, CuI and K3PO4Mixing, so
Afterwards under atmosphere of inert gases in 90-110 DEG C confined reaction 1.2-3 hours, reaction terminate it is post-treated to obtain the final product.
2. as described in claim 1 (E)-βAryl-β,γThe synthetic method of beta-unsaturated esters compound, which is characterized in that described
Alkynes compound is phenylacetylene, 4- methyl phenylacetylene, 4- Liquid Crystal Compounds Intermediate p-Ethyl-phenylacetylene, 4- propyl phenylacetylene, 4- butyl phenylacetylene, uncle 4-
Butyl phenylacetylene, 4- fluorobenzene acetylene, 4- chlorobenzene acetylene, 4- bromobenzene acetylene, 3- fluorobenzene acetylene, 3- chlorobenzene acetylene, 2- fluorobenzene acetylene,
2- chlorobenzene acetylene, methyl propargyl ether, glycidyl propargyl ether or cyclopropyl acethlene.
3. as described in claim 1 (E)-βAryl-β,γThe synthetic method of beta-unsaturated esters compound, which is characterized in that described
Fragrant boric acid compound is phenyl boric acid, 4- methylphenylboronic acid, 4- ethyl phenyl boric acid, 4- isopropyl benzene boronic acid, 4- tert-butyl benzene boron
Acid, 4- vinylphenylboronic acid, 4- chlorophenylboronic acid, 4- bromobenzeneboronic acid, 3- methylphenylboronic acid, 3- methoxyphenylboronic acid, 3- fluorobenzene boron
Acid, 3- chlorophenylboronic acid or 3- bromobenzeneboronic acid.
4. as described in Claims 2 or 3 (E)-βAryl-β,γThe synthetic method of beta-unsaturated esters compound, which is characterized in that
The molar ratio of the alkynes compound, ethyl diazoacetate and fragrant boric acid compound is 1.2-1.5:1:2-3.
5. as claimed in claim 4 (E)-βAryl-β,γThe synthetic method of beta-unsaturated esters compound, which is characterized in that described
The molar ratio of Phen and ethyl diazoacetate is 5-15:100.
6. as claimed in claim 4 (E)-βAryl-β,γThe synthetic method of beta-unsaturated esters compound, which is characterized in that described
The molar ratio of CuI and ethyl diazoacetate is 5-15:100.
7. as claimed in claim 4 (E)-βAryl-β,γThe synthetic method of beta-unsaturated esters compound, which is characterized in that described
K3PO4Molar ratio with ethyl diazoacetate is 1.5-2.5:1.
8. as claimed in claim 4 (E)-βAryl-β,γThe synthetic method of beta-unsaturated esters compound, which is characterized in that described
Solvent is 1,4- dioxane；The inert gas is nitrogen or argon gas.
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Non-Patent Citations (4)
| Title |
|---|
| NAN-NAN WANG等: "Synergistic Rhodium/Copper Catalysis: Synthesis of 1,3-Enynes and N‑Aryl Enaminones", 《ORGANIC LETTERS》 * |
| QI SUN等: "Copper-catalyzed 1,1-difunctionalization of terminal alkynes: a three-component reaction for the construction of vinyl sulfones", 《SCIENCE CHINA CHEMISTRY》 * |
| YUNHE LV等: "Copper-catalyzed 1,1-arylalkylation of terminal alkynes with diazo esters and organoboronic acids", 《CHEMICAL COMMUNICATIONS》 * |
| YUNHE LV等: "Copper-Catalyzed Regio- and Stereoselective 1,1-Dicarbofunctionalization of Terminal Alkynes", 《ORGANIC LETTERS》 * |
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