CN108774129A - The method that visible light catalytic organic boronic prepares esters of alpha, beta, unsaturated carboxylic acids derivative - Google Patents
The method that visible light catalytic organic boronic prepares esters of alpha, beta, unsaturated carboxylic acids derivative Download PDFInfo
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- CN108774129A CN108774129A CN201810783544.8A CN201810783544A CN108774129A CN 108774129 A CN108774129 A CN 108774129A CN 201810783544 A CN201810783544 A CN 201810783544A CN 108774129 A CN108774129 A CN 108774129A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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Abstract
The invention discloses a kind of visible light catalytic organic boronics to prepare α, the method of beta-unsaturated carboxylic acid ester derivant, Baylis Hillman derivatives, organic boronic, Lewis alkali and photochemical catalyst are added in organic solvent, 12-36 h are stirred under nitrogen atmosphere, visible light illumination, normal temperature and pressure conditions, reaction solution is post-treated later, obtain α, beta-unsaturated carboxylic acid ester derivant.The present invention prepares α, and beta-unsaturated carboxylic acid ester derivant, reaction condition is mild, easy to operate, and high selectivity, yield is good, and substituent group expansion is high;And visible light catalytic is used, have the characteristics that pollution-free, environmental-friendly, is a kind of very promising method.
Description
Technical field
The invention belongs to technical field of organic chemistry, and α is prepared using visible light catalytic organic boronic more particularly to a kind of,
The method of beta-unsaturated carboxylic acid ester derivant.The reaction condition of this method has simple and convenient, easy to operation, conversion zone selection
Property it is good, substituent group convenient for regulation and control the advantages that.
Background technology
α, beta-unsaturated carboxylic acid ester derivant are a kind of important organic synthesis intermediates, are had in organic synthesis important
Meaning can synthesize many important compounds by chemical transformation.For example alpha, beta-unsaturated carboxylic acid is to prepare pharmacological actives
The important intermediate of matter such as calcium antagonist or insecticide can also prepare the acid with optically active by asymmetric hydrogenation.In addition
Alpha, beta-unsaturated carboxylic acid hydroxy alkyl ester and the monomer of vinyl, which carry out copolyreaction, can obtain the change with excellent antistatic capability
Fiber is learned, is suitable for the coating of electronics, automobile, nonferrous materials, the adhesive with specific function can also be made;This kind of production
Product and acrylic ester monomer polymerize to obtain synthetic rubber with good heat-resisting and oil resistivity;The latex of the product can be used in paper
In the processing of product, the water resistance and intensity of paper products are improved;Also the additive of lubricating oil and the high score of specific function be can be used as
The synthon of sub- material.In recent years, a variety of synthesis α of organic chemists' new development, beta-unsaturated carboxylic acid ester derivant
Method.Such as Thomas (Chem.Eur.J.2009,15,4710-4715) et al. is reported and is produced by Baylis-Hillman additions
Object sets out, the back flow reaction under the catalytic action of rhodium with aryl boric acid or three potassium fluoborate of aryl, has the choosing of good region
Selecting property is poor, but target product almost only has Z formula structures, can not but obtain the product of Z formula structures well.M.L.N.Rao
(Tetrahedron, 2010,66,3623-3632) et al. by the Baylis-Hillman addition compound products of palladium chtalyst halogenation with
Substitution reaction occurs for triaryl bismuth, has synthesized a series of α, beta-unsaturated carboxylic acid ester derivant, but raw material is confined to triaryl
Bismuth, not only use condition is harsh, but also can not use heterocycle or aliphatic compound, while having the life of by-product biphenyl
At.Be recently reported organic three potassium fluoborate of photoactivation prepare esters of alpha, beta, unsaturated carboxylic acids (Tetrahedron Letters,
2018,59,2046-2049), this method mild condition is easy to operate, but is only limitted to three potassium fluoborate salt of benzyl and secondary carbon base.Together
Tri- potassium fluoborates of Shi Youji are also required to be prepared from organic boronic, and relative to organic boronic, atom utilization is low.More than being based on
Analysis, research and development go out it is a kind of more efficiently convenient greenization prepare α, the method for beta-unsaturated carboxylic acid ester derivant is that have
Significance.
Invention content
The object of the present invention is to provide a kind of esters of alpha, beta, unsaturated carboxylic acids derivative is prepared using visible light catalytic organic boronic
The method of object.
To achieve the above object, the present invention adopts the following technical scheme that:Visible light catalytic organic boronic prepares α, β-insatiable hunger
With the method for carboxylic ester derivative, it is characterised in that:
Organic boronic, Lewis alkali and light shown in Baylis-Hillman derivatives, formula (II) shown in formula (I) are urged
Agent is added in organic solvent, stirs 12-36h under nitrogen atmosphere, visible light illumination, normal temperature and pressure conditions, later reaction solution
It is post-treated, obtain α shown in formula (III), beta-unsaturated carboxylic acid ester derivant;
Wherein, the photochemical catalyst is selected from following compounds:
Eosin Y、Ir(ppy)3、[Ir(ppy)2(dtbpy)]PF6、[Ir(dF-CF3-ppy)2(dtbpy)]PF6;
Wherein, in formula (I), (II), (III), Boc is tertbutyloxycarbonyl, R1For the alkyl of C1~C6, aryl, substitution virtue
Base or heterocyclic aryl, R2For the alkyl, aryl or substituted aryl of C1~C6;It is mono-substituted on the aromatic ring of the substituted aryl or more
Substitution, substituent group are each independently selected from alkyl, fluorine, chlorine, bromine or the methoxyl group of C1~C5.
In method of the present invention, since reaction substrate Baylis-Hillman derivatives are not soluble in water, it is soluble in two
The organic solvents such as chloromethanes, acetonitrile, acetone, ether, therefore reaction dissolvent uses organic solvent;
Further, recommend the volumetric usage of organic solvent with the object of raw material Baylis-Hillman derivatives shown in formula (I)
The quality of matter is calculated as 5~10mL/mmol.
Further, the organic solvent is preferably acetonitrile, dichloromethane, N-Methyl pyrrolidone, ether;
Further, the organic solvent is most preferably N-Methyl pyrrolidone.
Further, recommend the throwing of Baylis-Hillman derivatives shown in the formula (I) and organic boronic shown in formula (II)
The ratio between amount of material matter is 1:1.5.
Further, the Lewis alkali is preferably 4-dimethylaminopyridine, Isosorbide-5-Nitrae-diazabicylo [2.2.2] octane, 1-
Azabicyclic [2.2.2] octane.
Further, the Lewis alkali is most preferably Isosorbide-5-Nitrae-diazabicylo [2.2.2] octane.
Further, recommend the substance that feeds intake of Baylis-Hillman derivatives shown in the formula (I) and Lewis alkali amount it
Than being 1:0.2.
Further, the molar ratio of Baylis-Hillman derivatives and photochemical catalyst shown in the formula (I) is recommended to be
1000~50:1, preferably 100:1.
Further, the photochemical catalyst is preferably Ir (ppy)3、[Ir(dF-CF3-ppy)2(dtbpy)]PF6、[Ir
(ppy)2(dtbpy)]PF6;
Further, the photochemical catalyst is most preferably [Ir (dF-CF3-ppy)2(dtbpy)]PF6。
Further, the reaction time is preferably 20-24h.
Further, the light source is preferably one of following:25~45W white lights energy-saving lamp, 7~14W blue LED lamps.
Further, the light source is preferably:45W white light energy-saving lamps.
The post-processing approach of reaction solution of the present invention is:After reaction, gained reaction solution is dilute with 0.1mol/L
Salt acid elution, ether extract three times, merge organic phase, organic layer three times with saturated common salt water washing, dry by anhydrous sodium sulfate.Rotation
It is detached by silica gel column chromatography after dry solvent, with petrol ether/ethyl acetate (20/1) for eluant, eluent, collects washing containing target product
α shown in the de- isolated formula of liquid (III), beta-unsaturated carboxylic acid ester derivant.
Photochemical catalyst used in preparation method of the present invention, the introductions such as physicochemical property, synthetic method can be found in following
Document:
[1]Inorg.Synth.1990,338;
[2]Inorg.Chem.1991,30,1685;
[3]J.Am.Chem.Soc.2004,126,2763;
[4]Chem.Mater.2005,17,5712;
[5]Org.Synth.2018,95,29-45。
Compared with prior art, the beneficial effects of the present invention are:
The present invention prepares α, and beta-unsaturated carboxylic acid ester derivant, reaction condition is mild, easy to operate, high selectivity, receives
Rate is good, and substituent group expansion is high;And use visible light catalytic, have the characteristics that it is pollution-free, environmental-friendly, be one kind have very much
The method of foreground.
Description of the drawings
Fig. 1 is product 2- (cyclohexyl methyl) -3- phenylacrylic acid methyl esters1H NMR spectras.
Fig. 2 is product 2- (cyclohexyl methyl) -3- phenylacrylic acid methyl esters13C NMR spectras.
Specific implementation mode
The technical solution further illustrated the present invention below by specific embodiment, but protection scope of the present invention is not
It is only limitted to this.
Baylis-Hillman derivant structures formula and reaction equation used in following embodiment is as follows:
Ir [dF (CF used in following embodiment3)ppy]2(dtbbpy)PF6The structural formula of catalyst is as follows:
Embodiment 1
In Schlenk pipes, 2- ((tert-butoxycarbonyl oxygroup) (phenyl) methyl) methyl acrylate is sequentially added
(146.2mg, 0.5mmol), hexamethylene ylboronic acid (96.0mg, 0.75mmol), Isosorbide-5-Nitrae-diazabicylo [2.2.2] octane
(11.2mg, 0.1mmol), Ir [dF (CF3)ppy]2(dtbbpy)PF6(5.6mg, 0.005mmol) and N-Methyl pyrrolidone
(3mL), connects nitrogen atmosphere, is stirred at room temperature for 24 hours under 45W energy-saving lamp white lights.After completion of the reaction, gained reaction solution is used
The dilute hydrochloric acid of 0.1mol/L washs, and ether extracts three times, and three times with saturated common salt water washing, anhydrous sodium sulfate is dry for merging organic layer
It is dry.It is detached by silica gel column chromatography after being spin-dried for solvent, with PE/EA (20/1) for eluant, eluent, collects the eluent containing target product
Isolated faint yellow target product 2- (cyclohexyl methyl) -3- phenylacrylic acid methyl esters, yield 81.33%.Characterization of The Products number
According to as follows:1H NMR(500MHz,CDCl3)δ7.70(s,1H),7.42–7.37(m,4.4H),7.34–7.30(m,4.4H),
7.28–7.27(m,1H),7.25–7.23(m,3.7H),6.60(s,1.7H),3.83(s,3H),3.66(s,5.1H),2.50
(d, J=7.1Hz, 2H), 2.32 (d, J=6.9Hz, 3.4H), 1.82-1.79 (m, 3.4H), 1.72-1.66 (m, 6.7H),
1.55–1.44(m,3.4H),1.28–1.11(m,10.2H),0.98–0.87(m,6H)。
Embodiment 2
In Schlenk pipes, 2- ((tert-butoxycarbonyl oxygroup) (phenyl) methyl) methyl acrylate is sequentially added
(146.2mg, 0.5mmol), hexamethylene ylboronic acid (96.0mg, 0.75mmol), Isosorbide-5-Nitrae-diazabicylo [2.2.2] octane
(11.2mg, 0.1mmol), Ir [dF (CF3)ppy]2(dtbbpy)PF6(5.6mg, 0.005mmol) and ether (3mL), connects nitrogen
Atmosphere is stirred at room temperature for 24 hours under 45W energy-saving lamp white lights.After completion of the reaction, the dilute hydrochloric acid of gained reaction solution 0.1mol/L
Washing, ether extract three times, and merging organic layer three times with saturated common salt water washing, dry by anhydrous sodium sulfate.Lead to after being spin-dried for solvent
Silica gel column chromatography separation is crossed, with PE/EA (20/1) for eluant, eluent, collects isolated yellowish Semu of eluent containing target product
Mark product 2- (cyclohexyl methyl) -3- phenylacrylic acid methyl esters, yield 78.26%.
Embodiment 3
In Schlenk pipes, 2- ((tert-butoxycarbonyl oxygroup) (phenyl) methyl) methyl acrylate is sequentially added
(146.2mg, 0.5mmol), hexamethylene ylboronic acid (96.0mg, 0.75mmol), Isosorbide-5-Nitrae-diazabicylo [2.2.2] octane
(11.2mg, 0.1mmol), Ir [dF (CF3)ppy]2(dtbbpy)PF6(5.6mg, 0.005mmol) and dichloromethane (3mL), connects
Nitrogen atmosphere is stirred at room temperature for 24 hours under 45W energy-saving lamp white lights.After completion of the reaction, gained reaction solution is dilute with 0.1mol/L
Salt acid elution, ether extract three times, and merging organic layer three times with saturated common salt water washing, dry by anhydrous sodium sulfate.It is spin-dried for solvent
It is detached afterwards by silica gel column chromatography, with PE/EA (20/1) for eluant, eluent, it is isolated yellowish to collect the eluent containing target product
Color target product 2- (cyclohexyl methyl) -3- phenylacrylic acid methyl esters, yield 56.72%.
Embodiment 4
In Schlenk pipes, 2- ((tert-butoxycarbonyl oxygroup) (phenyl) methyl) methyl acrylate is sequentially added
(146.2mg, 0.5mmol), hexamethylene ylboronic acid (96.0mg, 0.75mmol), Isosorbide-5-Nitrae-diazabicylo [2.2.2] octane
(11.2mg, 0.1mmol), Ir [dF (CF3)ppy]2(dtbbpy)PF6(5.6mg, 0.005mmol) and 1,2- dichloroethanes
(3mL), connects nitrogen atmosphere, is stirred at room temperature for 24 hours under 45W energy-saving lamp white lights.After completion of the reaction, gained reaction solution is used
The dilute hydrochloric acid of 0.1mol/L washs, and ether extracts three times, and three times with saturated common salt water washing, anhydrous sodium sulfate is dry for merging organic layer
It is dry.It is detached by silica gel column chromatography after being spin-dried for solvent, with PE/EA (20/1) for eluant, eluent, collects the eluent containing target product
Isolated faint yellow target product 2- (cyclohexyl methyl) -3- phenylacrylic acid methyl esters, yield 61.23%.
Embodiment 5
In Schlenk pipes, 2- ((tert-butoxycarbonyl oxygroup) (phenyl) methyl) methyl acrylate is sequentially added
(146.2mg, 0.5mmol), hexamethylene ylboronic acid (96.0mg, 0.75mmol), Isosorbide-5-Nitrae-diazabicylo [2.2.2] octane
(11.2mg, 0.1mmol), Ir [dF (CF3)ppy]2(dtbbpy)PF6(5.6mg, 0.005mmol) and dimethyl sulfoxide (DMSO) (3mL),
Nitrogen atmosphere is connect, is stirred at room temperature for 24 hours under 45W energy-saving lamp white lights.After completion of the reaction, gained reaction solution is with 0.1mol/L's
Dilute hydrochloric acid washs, and ether extracts three times, and merging organic layer three times with saturated common salt water washing, dry by anhydrous sodium sulfate.It is spin-dried for molten
It is detached by silica gel column chromatography after agent, with PE/EA (20/1) for eluant, eluent, it is isolated light to collect the eluent containing target product
Yellow target product 2- (cyclohexyl methyl) -3- phenylacrylic acid methyl esters, yield 59.56%.
Embodiment 6
In Schlenk pipes, 2- ((tert-butoxycarbonyl oxygroup) (phenyl) methyl) methyl acrylate is sequentially added
(146.2mg, 0.5mmol), hexamethylene ylboronic acid (96.0mg, 0.75mmol), Isosorbide-5-Nitrae-diazabicylo [2.2.2] octane
(11.2mg, 0.1mmol), Ir [dF (CF3)ppy]2(dtbbpy)PF6(5.6mg, 0.005mmol) and n,N dimethylformamide
(3mL), connects nitrogen atmosphere, is stirred at room temperature for 24 hours under 45W energy-saving lamp white lights.After completion of the reaction, gained reaction solution is used
The dilute hydrochloric acid of 0.1mol/L washs, and ether extracts three times, and three times with saturated common salt water washing, anhydrous sodium sulfate is dry for merging organic layer
It is dry.It is detached by silica gel column chromatography after being spin-dried for solvent, with PE/EA (20/1) for eluant, eluent, collects the eluent containing target product
Isolated faint yellow target product 2- (cyclohexyl methyl) -3- phenylacrylic acid methyl esters, yield 48.85%.
Embodiment 7
In Schlenk pipes, 2- ((tert-butoxycarbonyl oxygroup) (phenyl) methyl) methyl acrylate is sequentially added
(146.2mg, 0.5mmol), hexamethylene ylboronic acid (96.0mg, 0.75mmol), 4-dimethylaminopyridine (12.2mg, 0.1mmol),
Ir[dF(CF3)ppy]2(dtbbpy)PF6(5.6mg, 0.005mmol) and N-Methyl pyrrolidone (3mL), connects nitrogen atmosphere,
It is stirred at room temperature for 24 hours under 45W energy-saving lamp white lights.After completion of the reaction, gained reaction solution is washed with the dilute hydrochloric acid of 0.1mol/L, second
Ether extracts three times, and merging organic layer three times with saturated common salt water washing, dry by anhydrous sodium sulfate.Pass through silicagel column after being spin-dried for solvent
Chromatography collects the isolated faint yellow target product 2- of eluent containing target product with PE/EA (20/1) for eluant, eluent
(cyclohexyl methyl) -3- phenylacrylic acid methyl esters, yield 68.91%.
Embodiment 8
In Schlenk pipes, 2- ((tert-butoxycarbonyl oxygroup) (phenyl) methyl) methyl acrylate is sequentially added
(146.2mg, 0.5mmol), hexamethylene ylboronic acid (96.0mg, 0.75mmol), 1- azabicyclics [2.2.2] octane (11.1mg,
0.1mmol)、Ir[dF(CF3)ppy]2(dtbbpy)PF6(5.6mg, 0.005mmol) and N-Methyl pyrrolidone (3mL), connects nitrogen
Gas atmosphere is stirred at room temperature for 24 hours under 45W energy-saving lamp white lights.After completion of the reaction, gained reaction solution dilute salt of 0.1mol/L
Acid elution, ether extract three times, and merging organic layer three times with saturated common salt water washing, dry by anhydrous sodium sulfate.After being spin-dried for solvent
It is detached by silica gel column chromatography, with PE/EA (20/1) for eluant, eluent, it is isolated faint yellow to collect the eluent containing target product
Target product 2- (cyclohexyl methyl) -3- phenylacrylic acid methyl esters, yield 75.63%.
Embodiment 9
In Schlenk pipes, 2- ((tert-butoxycarbonyl oxygroup) (phenyl) methyl) methyl acrylate is sequentially added
(142.2mg, 0.5mmol), benzyl boric acid (102.0mg, 0.75mmol), 1- azabicyclics [2.2.2] octane (11.1mg,
0.1mmol)、Ir[dF(CF3)ppy]2(dtbbpy)PF6(5.6mg, 0.005mmol) and N-Methyl pyrrolidone (3mL), connects nitrogen
Gas atmosphere is stirred at room temperature for 24 hours under 45W energy-saving lamp white lights.After completion of the reaction, gained reaction solution dilute salt of 0.1mol/L
Acid elution, ether extract three times, and merging organic layer three times with saturated common salt water washing, dry by anhydrous sodium sulfate.After being spin-dried for solvent
It is detached by silica gel column chromatography, with PE/EA (20/1) for eluant, eluent, it is isolated faint yellow to collect the eluent containing target product
Target product 2- benzals -4-phenylbutyrate methyl esters, yield 77.55%.
Embodiment 10
In Schlenk pipes, 2- ((tert-butoxycarbonyl oxygroup) (4- chlorphenyls) methyl) methyl acrylate is sequentially added
(172.6mg, 0.5mmol), benzyl boric acid (102.0mg, 0.75mmol), 1- azabicyclics [2.2.2] octane (11.1mg,
0.1mmol)、Ir[dF(CF3)ppy]2(dtbbpy)PF6(5.6mg, 0.005mmol) and N-Methyl pyrrolidone (3mL), connects nitrogen
Gas atmosphere is stirred at room temperature for 24 hours under 45W energy-saving lamp white lights.After completion of the reaction, gained reaction solution dilute salt of 0.1mol/L
Acid elution, ether extract three times, and merging organic layer three times with saturated common salt water washing, dry by anhydrous sodium sulfate.After being spin-dried for solvent
It is detached by silica gel column chromatography, with PE/EA (20/1) for eluant, eluent, it is isolated faint yellow to collect the eluent containing target product
Target product 2- (4- chlorine benzal) -4-phenylbutyrate methyl esters, yield 72.63%.
Embodiment 11
In Schlenk pipes, 2- ((tert-butoxycarbonyl oxygroup) (phenyl) methyl) methyl acrylate is sequentially added
(142.2mg, 0.5mmol), isopropyl ylboronic acid (65.9mg, 0.75mmol), 1- azabicyclics [2.2.2] octane (11.1mg,
0.1mmol)、Ir[dF(CF3)ppy]2(dtbbpy)PF6(5.6mg, 0.005mmol) and N-Methyl pyrrolidone (3mL), connects nitrogen
Gas atmosphere is stirred at room temperature for 24 hours under 45W energy-saving lamp white lights.After completion of the reaction, gained reaction solution dilute salt of 0.1mol/L
Acid elution, ether extract three times, and merging organic layer three times with saturated common salt water washing, dry by anhydrous sodium sulfate.After being spin-dried for solvent
It is detached by silica gel column chromatography, with PE/EA (20/1) for eluant, eluent, it is isolated faint yellow to collect the eluent containing target product
Target product 2- benzal -4- methylvaleric acid methyl esters, yield 68.98%.
Embodiment 12
In Schlenk pipes, 2- ((tert-butoxycarbonyl oxygroup) (phenyl) methyl) methyl acrylate is sequentially added
(142.2mg, 0.5mmol), cyclopenta boric acid (68.5mg, 0.75mmol), 1- azabicyclics [2.2.2] octane (11.1mg,
0.1mmol)、Ir[dF(CF3)ppy]2(dtbbpy)PF6(5.6mg, 0.005mmol) and N-Methyl pyrrolidone (3mL), connects nitrogen
Gas atmosphere is stirred at room temperature for 24 hours under 45W energy-saving lamp white lights.After completion of the reaction, gained reaction solution dilute salt of 0.1mol/L
Acid elution, ether extract three times, and merging organic layer three times with saturated common salt water washing, dry by anhydrous sodium sulfate.After being spin-dried for solvent
It is detached by silica gel column chromatography, with PE/EA (20/1) for eluant, eluent, it is isolated faint yellow to collect the eluent containing target product
Target product 2- (cyclopentyl-methyl) -3- phenylacrylic acid methyl esters, yield 74.12%.
Embodiment 13
In Schlenk pipes, 2- ((tert-butoxycarbonyl oxygroup) (2- thiophene) methyl) methyl acrylate is sequentially added
(149.2mg, 0.5mmol), benzyl boric acid (102.0mg, 0.75mmol), 1- azabicyclics [2.2.2] octane (11.1mg,
0.1mmol)、Ir[dF(CF3)ppy]2(dtbbpy)PF6(5.6mg, 0.005mmol) and N-Methyl pyrrolidone (3mL), connects nitrogen
Gas atmosphere is stirred at room temperature for 24 hours under 45W energy-saving lamp white lights.After completion of the reaction, gained reaction solution dilute salt of 0.1mol/L
Acid elution, ether extract three times, and merging organic layer three times with saturated common salt water washing, dry by anhydrous sodium sulfate.After being spin-dried for solvent
It is detached by silica gel column chromatography, with PE/EA (20/1) for eluant, eluent, it is isolated faint yellow to collect the eluent containing target product
Target product 4- phenyl -2- (thiophene -2- methylenes) methyl butyrate, yield 58.31%.
Embodiment 14
In Schlenk pipes, 2- ((tert-butoxycarbonyl oxygroup) (2- pyridines) methyl) methyl acrylate is sequentially added
(146.2mg, 0.5mmol), benzyl boric acid (102.0mg, 0.75mmol), 1- azabicyclics [2.2.2] octane (11.1mg,
0.1mmol)、Ir[dF(CF3)ppy]2(dtbbpy)PF6(5.6mg, 0.005mmol) and N-Methyl pyrrolidone (3mL), connects nitrogen
Gas atmosphere is stirred at room temperature for 24 hours under 45W energy-saving lamp white lights.After completion of the reaction, gained reaction solution dilute salt of 0.1mol/L
Acid elution, ether extract three times, and merging organic layer three times with saturated common salt water washing, dry by anhydrous sodium sulfate.After being spin-dried for solvent
It is detached by silica gel column chromatography, with PE/EA (20/1) for eluant, eluent, it is isolated faint yellow to collect the eluent containing target product
Target product 4- phenyl -2- (pyridine -2- methylenes) methyl butyrate, yield 55.19%.
Embodiment 15
In Schlenk pipes, 2- ((tert-butoxycarbonyl oxygroup) (1- naphthalenes) methyl) methyl acrylate is sequentially added
(171.2mg, 0.5mmol), benzyl boric acid (102.0mg, 0.75mmol), 1- azabicyclics [2.2.2] octane (11.1mg,
0.1mmol)、Ir[dF(CF3)ppy]2(dtbbpy)PF6(5.6mg, 0.005mmol) and N-Methyl pyrrolidone (3mL), connects nitrogen
Gas atmosphere is stirred at room temperature for 24 hours under 45W energy-saving lamp white lights.After completion of the reaction, gained reaction solution dilute salt of 0.1mol/L
Acid elution, ether extract three times, and merging organic layer three times with saturated common salt water washing, dry by anhydrous sodium sulfate.After being spin-dried for solvent
It is detached by silica gel column chromatography, with PE/EA (20/1) for eluant, eluent, it is isolated faint yellow to collect the eluent containing target product
Target product 4- phenyl -2- (naphthalene -2- methylenes) methyl butyrate, yield 65.28%.
Embodiment 16
In Schlenk pipes, 2- ((tert-butoxycarbonyl oxygroup) (phenyl) methyl) ethyl acrylate is sequentially added
(153.2mg, 0.5mmol), benzyl boric acid (102.0mg, 0.75mmol), 1- azabicyclics [2.2.2] octane (11.1mg,
0.1mmol)、Ir[dF(CF3)ppy]2(dtbbpy)PF6(5.6mg, 0.005mmol) and N-Methyl pyrrolidone (3mL), connects nitrogen
Gas atmosphere is stirred at room temperature for 24 hours under 45W energy-saving lamp white lights.After completion of the reaction, gained reaction solution dilute salt of 0.1mol/L
Acid elution, ether extract three times, and merging organic layer three times with saturated common salt water washing, dry by anhydrous sodium sulfate.After being spin-dried for solvent
It is detached by silica gel column chromatography, with PE/EA (20/1) for eluant, eluent, it is isolated faint yellow to collect the eluent containing target product
Target product 2- benzals -4-phenylbutyrate ethyl ester, yield 75.15%.
Embodiment 17
In Schlenk pipes, 2- ((tert-butoxycarbonyl oxygroup) (phenyl) methyl) tert-butyl acrylate is sequentially added
(167.2mg, 05mmol), benzyl boric acid (102.0mg, 0.75mmol), 1- azabicyclics [2.2.2] octane (11.1mg,
0.1mmol)、Ir[dF(CF3)ppy]2(dtbbpy)PF6(5.6mg, 0.005mmol) and N-Methyl pyrrolidone (3mL), connects nitrogen
Gas atmosphere is stirred at room temperature for 24 hours under 45W energy-saving lamp white lights.After completion of the reaction, gained reaction solution dilute salt of 0.1mol/L
Acid elution, ether extract three times, and merging organic layer three times with saturated common salt water washing, dry by anhydrous sodium sulfate.After being spin-dried for solvent
It is detached by silica gel column chromatography, with PE/EA (20/1) for eluant, eluent, it is isolated faint yellow to collect the eluent containing target product
The target product 2- benzals -4-phenylbutyrate tert-butyl ester, yield 72.52%.
Embodiment 18 (comparative example)
In Schlenk pipes, 2- ((tert-butoxycarbonyl oxygroup) (phenyl) methyl) methyl acrylate is sequentially added
(146.2mg, 0.5mmol), hexamethylene ylboronic acid (96.0mg, 0.75mmol), Ir [dF (CF3)ppy]2(dtbbpy)PF6
(5.6mg, 0.005mmol) and N-Methyl pyrrolidone (3mL), connects nitrogen atmosphere, and room temperature is stirred under 45W energy-saving lamp white lights
It mixes for 24 hours.After completion of the reaction, the generation of product is can't detect with TLC.
Embodiment 19 (comparative example)
In Schlenk pipes, 2- ((tert-butoxycarbonyl oxygroup) (phenyl) methyl) methyl acrylate is sequentially added
(146.2mg, 0.5mmol), hexamethylene ylboronic acid (96.0mg, 0.75mmol), Isosorbide-5-Nitrae-diazabicylo [2.2.2] octane
(11.2mg, 0.1mmol) and N-Methyl pyrrolidone (3mL), connects nitrogen atmosphere, and room temperature is stirred under 45W energy-saving lamp white lights
It mixes for 24 hours.After completion of the reaction, the generation of product is can't detect with TLC.
Embodiment 20 (comparative example)
In Schlenk pipes, 2- ((tert-butoxycarbonyl oxygroup) (phenyl) methyl) methyl acrylate is sequentially added
(146.2mg, 0.5mmol), hexamethylene ylboronic acid (96.0mg, 0.75mmol), Isosorbide-5-Nitrae-diazabicylo [2.2.2] octane
(11.2mg, 0.1mmol), Ir [dF (CF3)ppy]2(dtbbpy)PF6(5.6mg, 0.005mmol) and N-Methyl pyrrolidone
(3mL), connects nitrogen atmosphere, is stirred at room temperature for 24 hours under unglazed irradiation.After completion of the reaction, the generation of product is can't detect with TLC.
Claims (10)
1. visible light catalytic organic boronic prepares α, the method for beta-unsaturated carboxylic acid ester derivant, it is characterised in that:By formula (I) institute
Organic solvent is added in organic boronic, Lewis alkali and photochemical catalyst shown in the Baylis-Hillman derivatives that show, formula (II)
In, 12-36h is stirred under nitrogen atmosphere, visible light illumination, normal temperature and pressure conditions, reaction solution is post-treated later, obtains formula
(III) esters of alpha, beta, unsaturated carboxylic acids derivative shown in;
Wherein, the photochemical catalyst is selected from following compounds:
Eosin Y、Ir(ppy)3、[Ir(ppy)2(dtbpy)]PF6、[Ir(dF-CF3-ppy)2(dtbpy)]PF6;
Wherein, in formula (I), (II), (III), Boc is tertbutyloxycarbonyl, R1For the alkyl of C1~C6, aryl, substituted aryl or miscellaneous
Cyclophane base, R2For the alkyl, aryl or substituted aryl of C1~C6;It is mono-substituted on the aromatic ring of the substituted aryl or polysubstituted,
Substituent group is each independently selected from alkyl, fluorine, chlorine, bromine or the methoxyl group of C1~C5.
2. the method as described in claim 1, it is characterised in that:The volumetric usage of organic solvent is with raw material shown in formula (I)
The quality of the substance of Baylis-Hillman derivatives is calculated as 5~10mL/mmol.
3. the method as described in claim 1, it is characterised in that:The organic solvent is preferably N-Methyl pyrrolidone.
4. the method as described in claim 1, it is characterised in that:Baylis-Hillman derivatives and formula shown in the formula (I)
(II) the ratio between amount for the substance that feeds intake of organic boronic shown in is 1:1.5.
5. the method as described in claim 1, it is characterised in that:The Lewis alkali is preferably 1,4- diazabicylos
[2.2.2] octane.
6. the method as described in claim 1, it is characterised in that:Baylis-Hillman derivatives shown in the formula (I) with
The ratio between amount for the substance that feeds intake of Lewis alkali is 1:0.2.
7. the method as described in claim 1, it is characterised in that:Baylis-Hillman derivatives and light shown in the formula (I)
The molar ratio of catalyst is 100:1.
8. the method as described in claim 1, it is characterised in that:The photochemical catalyst is preferably [Ir (dF-CF3-ppy)2
(dtbpy)]PF6。
9. the method as described in claim 1, it is characterised in that:The reaction time is preferably 20-24h.
10. such as claim 1-9 any one of them methods, it is characterised in that:The post-processing approach of the reaction solution is:Instead
After answering, gained reaction solution is washed with the dilute hydrochloric acid of 0.1mol/L, and ether extracts three times, merges organic phase, and organic layer is used full
Three times with brine It, anhydrous sodium sulfate is dried;It is detached by silica gel column chromatography after being spin-dried for solvent, with the stone of volume ratio 20/1
Oily ether/ethyl acetate solution is eluant, eluent, collects α, β-insatiable hunger shown in the isolated formula of eluent (III) containing target product
And carboxylic ester derivative.
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