CN110563535A - method for synthesizing 1, 2-disubstituted olefin compound by alkyne alkylation - Google Patents
method for synthesizing 1, 2-disubstituted olefin compound by alkyne alkylation Download PDFInfo
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Abstract
The invention discloses a method for synthesizing a 1, 2-disubstituted olefin compound by high-selectivity alkylation of alkyne, which comprises the following steps: adding a photosensitizer, an alkyne compound shown in a formula I and hans ester into a Schlenk reaction tube, dissolving aldehyde and secondary amine shown in a formula II into an organic solvent or a mixed solvent of 1, 4-dioxane and water under the atmosphere of protective gas to obtain a mixed solution, adding the mixed solution into the Schlenk reaction tube under the condition of protective gas, stirring and reacting for 6-14 hours (preferably 12 hours) at 25 ℃ under the irradiation of a light source to obtain a reaction solution, and carrying out post-treatment on the reaction solution to obtain the 1, 2-disubstituted alkene compound shown in a formula III. The method can synthesize the polysubstituted olefin which is difficult to prepare by the existing method, and has high reaction stereoselectivity; the catalyst is cheap and easy to obtain, and has low toxicity; the reaction condition is mild, and the energy consumption is saved; high yield, strong substrate universality, simple and convenient operation and the like.
Description
(I) technical field
The invention relates to a synthetic method of an organic compound, in particular to a synthetic method of a 1, 2-disubstituted olefin compound.
(II) background of the invention
Olefins are one of the most important and basic organic compounds, and olefin modules are commonly found in various biological common medicines and natural products and are also widely applied to the field of materials. In addition, olefins are the most commonly used intermediates in organic synthesis, and are capable of undergoing a series of reactions, such as polymerization, olefin metathesis, epoxidation, hydroformylation, and hydroamination. Therefore, the research and development of the related synthesis technology of the olefin compound have wide application prospect. Although chemists at home and abroad have developed various methods for synthesizing olefins with high efficiency and universality since the last century, the classic methods include witting reaction, Peterson reaction, Takai olefination reaction, olefin metathesis reaction, cross-coupling reaction and the like. The above methods still suffer from the disadvantages of low atom economy, too reactive or toxic alkenylation reagents required, the need to use excess bases, the lack of suitability for highly sterically hindered substrates, the need for expensive metal catalysts, etc. (see chem. rev.2013,113, 1313.).
The selective functionalization of inexpensive and readily available alkynes remains one of the simplest direct routes to complex alkenes. In recent years, with the rapid development of photo-redox reactions, alkylation reaction of photocatalytic unsaturated bonds becomes a research hotspot, but compared with alkylation reaction of photocatalytic olefins, the method for synthesizing multi-substituted olefins by alkylation of photocatalytic alkynes is still very limited due to stereoselectivity (see j.am. chem. soc.2017,139, 13579). Currently developed alkylating agents are: alkyl halide reagents, carboxylic acids and their derivatives, alkyl boron reagents, alkyl silicon reagents, Katritzky salts, ethers or tertiary amines. Although these alkylating agents have some advantages, they also have the disadvantages of toxicity, complicated preparation methods, low atom economy or poor substrate universality, poor stereoselectivity of the reaction, etc. From the perspective of green chemistry, aldehyde has the advantages of being cheap and easy to obtain, non-toxic, environment-friendly and the like, and is an alkylating reagent with good prospects, but related reports are few. In 2019, a Jiangzhi Yougong subject group of the university of Henan university establishes a DPZ and chiral phosphonic acid synergistic asymmetric catalytic system, utilizes aldehyde as a hydroxymethyl radical precursor, and realizes the construction of a chiral center at the alpha position of azaarene through the hydrogen bond interaction of chiral phosphonic acid and the basic nitrogen atom of azaarene to obtain a series of chiral pyridine derivatives (see J.Am.chem.Soc.2019,141, 5437.). In addition, the Gaunt group of cambridge university realizes three-component reaction of dialkylamine, aldehyde, and olefin to obtain a series of tertiary amine compounds (see Nature,2018,56,522). In both cases, the addition of aldehyde as alkylating agent to olefin and the retention of hydroxyl or amine moiety, while the addition of aldehyde as alkylating agent to alkyne is not reported. Therefore, the method for exploring the method for obtaining a series of functionalized olefins by using aldehyde as an alkylating reagent and realizing addition to alkyne with high stereoselectivity has important academic value and application prospect. More importantly, in the above-mentioned alkyne functionalization reactions, the double bonds of the resulting product remain in the original triple bond position, and it is very rare to simultaneously achieve the migration of the double bonds during the functionalization.
In view of the above background, it is necessary to develop a synthetic route for synthesizing a 1, 2-disubstituted alkene compound, which has the advantages of simple and easily available raw materials, cheap and easily available copper-based photosensitizer as a catalyst, aldehyde as an alkylating reagent, realization of product double bond migration, simple operation, high stereoselectivity and mild reaction.
Disclosure of the invention
Aiming at the defects in the prior art, the invention aims to provide a method for preparing a 1, 2-disubstituted olefin compound.
A method for synthesizing a 1, 2-disubstituted olefin compound by high-selectivity alkylation of alkyne specifically comprises the following steps:
Adding a photosensitizer, an alkyne compound shown in a formula I and hans ester into a Schlenk reaction tube, dissolving aldehyde and secondary amine shown in a formula II into an organic solvent or a mixed solvent of 1, 4-dioxane and water under the atmosphere of protective gas to obtain a mixed solution, adding the mixed solution into the Schlenk reaction tube under the condition of protective gas, stirring and reacting for 6-14 hours (preferably 12 hours) at 25 ℃ under the irradiation of a light source to obtain a reaction solution, and carrying out post-treatment on the reaction solution to obtain a 1, 2-disubstituted alkene compound shown in a formula III; the quantity ratio of the photosensitizer, the alkyne shown in the formula I, the hans ester, the aldehyde shown in the formula II and the secondary amine is 0.025-0.1:1:0.5-1.5:2-5: 2-5;
The photosensitizer has one of the following structures:
Formula I or formula III:
R1Is composed of One of (1);
R2Is one of H, Ph or 4-bromopinenyl;
R3Is H, Me, Et, n-Pr, n-Bu, n-pentanyl,Bn、i-Pr、One kind of (1).
Further, the secondary amine of the present invention is one of the following structures:
Still further, the secondary amine of the present invention is most preferably di-n-propylamine.
further, the photosensitizer is most preferably
Further, the organic solvent is one of acetonitrile, tetrahydrofuran, 1, 2-dichloroethane, N-dimethylformamide, 1, 4-dioxane, dimethyl sulfoxide, dichloromethane, cyclopentyl methyl ether, benzotrifluoride and ethyl acetate.
Further, the organic solvent of the present invention is preferably a mixed solvent of 1, 4-dioxane and water in a volume ratio of 20: 1.
Further, the total amount of the organic solvent added is 20mL/mmol based on the amount of the alkyne compound shown in the formula I.
Further, the light source is one of a 15W blue LED, a 30W blue LED, a 60W CFL and a 20W white LED.
Further, the light source is preferably a 30W blue LED.
Further, the protective gas is one of nitrogen or argon.
Further, the post-treatment method of the reaction solution comprises the following steps: and after the reaction is finished, adding 100-200 meshes of column chromatography silica gel into the obtained reaction liquid, carrying out reduced pressure distillation to remove the solvent, carrying out silica gel column chromatography separation on the obtained crude product, eluting by using petroleum ether as an eluent, tracking the elution process by TLC, collecting the eluent containing the target product, combining the eluents, and distilling off the solvent to obtain the 1, 2-disubstituted olefin compound shown in the formula III.
The starting alkynes for use in the present invention can be prepared by those skilled in the art on their own in accordance with the methods disclosed in the prior art.
compared with the prior art, the invention has the beneficial effects that:
The method can synthesize the polysubstituted olefin which is difficult to prepare by the existing method, and has high reaction stereoselectivity; the catalyst is cheap and easy to obtain, and has low toxicity; the reaction condition is mild, and the energy consumption is saved; high yield, strong substrate universality, simple and convenient operation and the like.
(IV) detailed description of the preferred embodiment
The invention will be further illustrated by the following examples, without limiting the scope of the invention:
The raw material alkyne is obtained by Sonogashira coupling, taking 4-phenyl phenylacetylene as an example, the typical steps are as follows:
Pd (PPh)3)2Cl2(0.04mmol,18mg), CuI (0.08mmol,15.2mg), 4-iodobiphenyl (2mmol,560mg) were added to the Schlenk reaction tube. Triethylamine (6mmol,833uL), freshly distilled acetonitrile (4mL), and trimethylethynyl silicon (2.4mmol) were added to the reaction tube under nitrogen, and the reaction was stirred at room temperature for 24 hours. After the reaction is finished, adding 100-200 meshes of column chromatography silica gel into the obtained reaction liquid, decompressing and distilling to remove the solvent, carrying out silica gel column chromatography separation on the obtained crude product, eluting by using petroleum ether as an eluent, tracking the elution process by TLC, collecting the eluent containing the target product, combining the eluents, and distilling to remove the solvent to obtain the pure product. The material was a white solid in 86% yield.
Example 1
Photosensitizer PS3(0.01mmol,11.5mg), 4-phenylphenylacetylene (0.2mmol,35.6mg), hans' ester (0.24mmol,60.8mg) were added to a dry Schlenk reaction tube, nitrogen was charged three times, a solution of butyraldehyde (1.0mmol,72.1mg) and diethylamine (1.0mmol,73.1mg) in acetonitrile (4mL) was added under nitrogen protection, and the reaction tube was stirred for 12 hours under 15W blue LED illumination. After the reaction is finished, adding 100-200 meshes of column chromatography silica gel into the obtained reaction liquid, decompressing and distilling to remove the solvent, carrying out silica gel column chromatography separation on the obtained crude product, eluting by using petroleum ether as an eluent, tracking the elution process by TLC, collecting the eluent containing the target product, combining the eluents, and distilling to remove the solvent to obtain the pure product. The material was a colorless liquid, 15% yield, and the product E/Z was 10/1.
Characterization data:1H NMR(500MHz,CDCl3)δ7.61-7.59(m,2H),7.54(d,J=8.2Hz,2H),7.44(t,J=7.7Hz,2H),7.36-7.33(m,1H),7.28(d,J=8.0Hz,2H),5.65-5.54(m,2H),3.39(d,J=6.1Hz,2H),2.04(dd,J1=14.0Hz,J2=7.1Hz,2H),1.43(m,2H),0.93(t,J=7.4Hz,3H);13C NMR(125M,CDCl3)δ141.2,140.3,138.9,132.1,128.9,128.8,128.7,127.1,127.04,127.02,38.7,34.7,22.6,13.7.
The olefin obtained above can be subjected to epoxidation reaction to obtain an epoxy compound (see J.Am.chem.Soc.2013,135,10930.)
4- (2-hexen-1-yl) -1, 1' -biphenyl (0.3mmol,70.9mg) was dissolved in CH at 0 deg.C2Cl2To (3mL) was added m-chloroperoxybenzoic acid (75% pure, 0.45mmol,103.5mg) slowly and the reaction was continued at 0 ℃ with stirring until completion of the olefinic reaction by TLC. After the reaction is finished, adding NaHSO3Quenching excess meta-chloroperoxybenzoic acid in aqueous solution, filtering, and adding NaHCO3Washing the organic phase with water solution, adding 100-200 mesh column chromatography silica gel into the organic phase after washing, distilling under reduced pressure to remove solvent, separating the crude product by silica gel column chromatography, eluting with petroleum ether/ethyl acetate (100/1) as eluent, tracking the elution process by TLC, collecting the eluent containing the target product, mixing the eluents, and evaporating to remove solvent to obtain the pure product with a yield of 81%.
Example 2
Photosensitizer PS4(0.01mmol,10.5mg), phenylacetylene (0.2mmol,20.4mg), hans' ester (0.24mmol,60.8mg) were added to a dry Schlenk reaction tube, nitrogen was charged three times, butyraldehyde (1.0mmol,72.1mg) and diethylamine (1.0mmol,73.1mg) in acetonitrile (4mL) were added under nitrogen protection, and the reaction tube was stirred under 15W blue LED illumination for 12 hours. After the reaction is finished, adding 100-200 meshes of column chromatography silica gel into the obtained reaction liquid, decompressing and distilling to remove the solvent, carrying out silica gel column chromatography separation on the obtained crude product, eluting by using petroleum ether as an eluent, tracking the elution process by TLC, collecting the eluent containing the target product, combining the eluents, and distilling to remove the solvent to obtain the pure product. The material was a colorless liquid, 14% yield, and the product E/Z was 10/1.
Characterization data:1H NMR(500M,CDCl3)δ7.32-7.29(m,2H),7.22-7.19(m,3H),5.62-5.50(m,2H),3.35(d,J=6.3Hz,2H),2.20(q,7.2Hz,2H),1.46-1.38(m,2H),0.92(t,J=7.4Hz,3H);13C NMR(125MHz,CDCl3)δ141.2,131.9,128.9,128.5,128.3,125.9,39.1,34.6,22.6,13.7.
Example 3
Photosensitizer PS5(0.01mmol,12.0mg), 4-bromophenylacetylene (0.2mmol,36.2mg), hans' ester (0.24mmol,60.8mg) were added to a dry Schlenk reaction tube, nitrogen was charged three times, a solution of butyraldehyde (1.0mmol,72.1mg) and diethylamine (1.0mmol,73.1mg) in acetonitrile (4mL) was added under nitrogen protection, and the reaction tube was stirred for 12 hours under 15W blue LED illumination. After the reaction is finished, adding 100-200 meshes of column chromatography silica gel into the obtained reaction liquid, decompressing and distilling to remove the solvent, carrying out silica gel column chromatography separation on the obtained crude product, eluting by using petroleum ether as an eluent, tracking the elution process by TLC, collecting the eluent containing the target product, combining the eluents, and distilling to remove the solvent to obtain the pure product. The material was a colorless liquid, 27% yield, and the product E/Z11/1.
Characterization data:1H NMR(500M,CDCl3)δ7.42(d,J=8.4Hz,2H),7.08(d,J=8.4Hz,2H),5.58-5.49(m,2H),3.30(d,J=4.9Hz,2H),2.05-2.01(m,2H),1.46-1.38(m,2H),0.92(t,J=7.4Hz,3H);13C NMR(125MHz,CDCl3)δ140.1,132.5,131.4,130.3,128.3,119.6,38.4,34.6,22.6,13.7.
The olefin obtained above can be subjected to epoxidation reaction to obtain an epoxy compound (see J.Am.chem.Soc.2013,135,10930.)
4-bromo- (2-hexen-1-yl) benzene (0.3mmol,71.7mg) was dissolved in CH at 0 deg.C2Cl2To (3mL) was added m-chloroperoxybenzoic acid (75% pure, 0.45mmol,103.5mg) slowly and the reaction was continued at 0 ℃ with stirring until completion of the olefinic reaction by TLC. After the reaction is finished, adding NaHSO3quenching excess meta-chloroperoxybenzoic acid in aqueous solution, filtering, and adding NaHCO3Washing the organic phase with water solution, adding 100-200 mesh column chromatography silica gel into the organic phase after washing, distilling under reduced pressure to remove solvent, separating the crude product by silica gel column chromatography, eluting with petroleum ether/ethyl acetate (100/1) as eluent, tracking the elution process by TLC, collecting the eluent containing the target product, mixing the eluents, and evaporating to remove solvent to obtain the pure product with 79% yield.
Example 4
Photosensitizer PS6(0.01mmol,11.1mg), 4-chlorophenylacetylene (0.2mmol,27.3mg), hans' ester (0.24mmol,60.8mg) were added to a dried Schlenk reaction tube, nitrogen was charged three times, butyraldehyde (1.0mmol,72.1mg) and diethylamine (1.0mmol,73.1mg) in acetonitrile (4mL) were added under nitrogen protection, and the reaction tube was stirred for 12 hours under 15W blue LED illumination. After the reaction is finished, adding 100-200 meshes of column chromatography silica gel into the obtained reaction liquid, decompressing and distilling to remove the solvent, carrying out silica gel column chromatography separation on the obtained crude product, eluting by using petroleum ether as an eluent, tracking the elution process by TLC, collecting the eluent containing the target product, combining the eluents, and distilling to remove the solvent to obtain the pure product. The material was a colorless liquid, 20% yield, and the product E/Z13/1.
Characterization data:1H NMR(500M,CDCl3)δ7.27(d,J=8.4Hz,2H),7.13(d,J=8.4Hz,2H),5.58-5.49(m,2H),3.31(d,J=5.0Hz,2H),2.05-2.01(m,2H),1.45-1.38(m,2H),0.92(t,J=7.4Hz,3H);13C NMR(125MHz,CDCl3)δ139.6,132.4,131.6,129.8,128.41,128.39,38.4,34.6,22.6,13.7.
The olefin obtained above can be subjected to epoxidation reaction to obtain an epoxy compound (see J.Am.chem.Soc.2013,135,10930.)
1-chloro- (2-hexen-1-yl) benzene (0.3mmol,58.4mg) was dissolved in CH at 0 deg.C2Cl2To (3mL) was added m-chloroperoxybenzoic acid (75% pure, 0.45mmol,103.5mg) slowly and the reaction was continued at 0 ℃ with stirring until completion of the olefinic reaction by TLC. After the reaction is finished, adding NaHSO3Quenching excess meta-chloroperoxybenzoic acid in aqueous solution, filtering, and adding NaHCO3Washing the organic phase with water solution, adding 100-200 mesh column chromatography silica gel into the organic phase after washing, distilling under reduced pressure to remove solvent, separating the crude product by silica gel column chromatography, eluting with petroleum ether/ethyl acetate (100/1) as eluent, tracking the elution process by TLC, collecting the eluent containing the target product, mixing the eluents, and evaporating to remove solvent to obtain the pure product with a yield of 75%.
example 5
The photosensitizers PS7(0.01mmol,6.5mg), 4-cyanobenzene acetylene (0.2mmol,25.4mg), hans' ester (0.24mmol,60.8mg) were added to a dry Schlenk reaction tube, nitrogen was charged three times, a solution of butyraldehyde (1.0mmol,72.1mg) and diethylamine (1.0mmol,73.1mg) in acetonitrile (4mL) was added under nitrogen protection, and the tube was stirred for 12 hours under 15W blue LED illumination. After the reaction is finished, adding 100-200 meshes of column chromatography silica gel into the obtained reaction liquid, distilling under reduced pressure to remove the solvent, carrying out silica gel column chromatography separation on the obtained crude product, eluting by using petroleum ether/ethyl acetate 20/1 as an eluent, tracking the elution process by TLC, collecting eluent containing the target product, combining the eluents, and distilling off the solvent to obtain the pure product. The material was a colorless liquid, 6% yield, and the product E/Z was 10/1.
Characterization data:1H NMR(500M,CDCl3)δ7.57(d,J=8.3Hz,2H),7.29(d,J=8.4Hz,2H),5.58-5.49(m,2H),3.39(d,J=5.0Hz,2H),2.05-2.01(m,2H),1.45-1.38(m,2H),0.91(t,J=7.4Hz,3H);13C NMR(125MHz,CDCl3)δ146.8,133.4,132.1,129.2,127.1,119.1,109.8,39.1,34.5,22.4,13.6.
Example 6
Photosensitizer PS8(0.01mmol,9.1mg), methyl 4-acetylenylbenzoate (0.2mmol,32mg), hans' ester (0.24mmol,60.8mg) were added to a dry Schlenk reaction tube, nitrogen was charged three times, butyraldehyde (1.0mmol,72.1mg) and diethylamine (1.0mmol,73.1mg) in acetonitrile (4mL) were added under nitrogen protection, and the reaction tube was stirred under 15W blue LED illumination for 12 hours. After the reaction is finished, adding 100-200 meshes of column chromatography silica gel into the obtained reaction liquid, distilling under reduced pressure to remove the solvent, carrying out silica gel column chromatography separation on the obtained crude product, eluting by using petroleum ether/ethyl acetate 20/1 as an eluent, tracking the elution process by TLC, collecting eluent containing the target product, combining the eluents, and distilling off the solvent to obtain the pure product. The material was a colorless liquid, 13% yield, and the product E/Z was 10/1.
characterization data:1H NMR(500M,CDCl3)δ7.97(d,J=8.2Hz,2H),7.26(d,J=8.3Hz,2H),5.60-5.50(m,2H),3.92(s,3H),3.39(d,J=5.0Hz,2H),2.05-2.01(m,2H),1.45-1.38(m,2H),0.91(t,J=7.4Hz,3H);13C NMR(125MHz,CDCl3)δ167.2,146.7,132.8,129.7,128.5,127.92,127.91,52.0,39.1,34.6,22.5,13.7.
Example 7
photosensitizer PS5(0.005mmol,6.0mg), 4-methylsulfonylphenylacetylene (0.2mmol,32mg), hans' ester (0.24mmol,60.8mg) were added to a dry Schlenk reaction tube, nitrogen was charged three times, a solution of butyraldehyde (1.0mmol,72.1mg) and diethylamine (1.0mmol,73.1mg) in acetonitrile (4mL) was added under nitrogen protection, and the reaction tube was stirred for 12 hours under 15W blue LED illumination. After the reaction is finished, adding 100-200 meshes of column chromatography silica gel into the obtained reaction liquid, distilling under reduced pressure to remove the solvent, carrying out silica gel column chromatography separation on the obtained crude product, eluting by using petroleum ether/ethyl acetate 5/1 as an eluent, tracking the elution process by TLC, collecting eluent containing the target product, combining the eluents, and distilling off the solvent to obtain the pure product. The material was a colorless liquid, 13% yield, and the product E/Z was 10/1.
characterization data:1H NMR(500M,CDCl3)δ7.86(d,J=8.3Hz,2H),7.39(d,J=8.4Hz,2H),5.59-5.51(m,2H),3.42(d,J=4.9Hz,2H),3.05(s,3H),2.05-2.01(m,2H),1.45-1.37(m,2H),0.91(t,J=7.4Hz,3H);13C NMR(125MHz,CDCl3)δ147.8,138.2,133.4,129.4,127.5,127.2,44.6,38.9,34.5,22.5,13.6.
The olefin obtained above can be subjected to epoxidation reaction to obtain an epoxy compound (see J.Am.chem.Soc.2013,135,10930.)
1- (2-hexen-1-yl) -4-methylsulfonylbenzene (0.3mmol,71.5mg) was dissolved in CH at 0 deg.C2Cl2To (3mL) was added m-chloroperoxybenzoic acid (75% pure, 0.45mmol,103.5mg) slowly and the reaction was continued at 0 ℃ with stirring until completion of the olefinic reaction by TLC. After the reaction is finished, adding NaHSO3Quenching excess meta-chloroperoxybenzoic acid in aqueous solution, filtering, and adding NaHCO3Washing the organic phase with water solution, adding 100-200 mesh column chromatography silica gel into the organic phase after washing, distilling under reduced pressure to remove solvent, separating the crude product by silica gel column chromatography, eluting with petroleum ether/ethyl acetate 5/1 as eluent, tracking the elution process by TLC, collecting the eluent containing the target product, mixing the eluents, and evaporating to remove solvent to obtain the pure product with a yield of 80%.
Example 8
Photosensitizer PS5(0.015mmol,18mg), 4-methylphenylacetylene (0.2mmol,23.2mg), hans' ester (0.24mmol,60.8mg) were added to a dried Schlenk reaction tube, nitrogen was charged three times, butyraldehyde (1.0mmol,72.1mg) and diethylamine (1.0mmol,73.1mg) in acetonitrile (4mL) were added under nitrogen protection, and the reaction tube was stirred under 15W blue LED illumination for 12 hours. After the reaction is finished, adding 100-200 meshes of column chromatography silica gel into the obtained reaction liquid, decompressing and distilling to remove the solvent, carrying out silica gel column chromatography separation on the obtained crude product, eluting by using petroleum ether as an eluent, tracking the elution process by TLC, collecting the eluent containing the target product, combining the eluents, and distilling to remove the solvent to obtain the pure product. The material was a colorless liquid, 34% yield, and the product E/Z was 10/1.
Characterization data:1H NMR(500M,CDCl3)δ7.12-7.08(m,4H),5.60-5.48(m,2H),3.31(d,J=6.3Hz,2H),2.34(s,3H),2.04-1.99(m,2H),1.45-1.37(m,2H),0.91(t,J=7.4Hz,3H);13C NMR(125MHz,CDCl3)δ138.1,135.3,131.6,129.2,129.0,128.4,38.7,34.6,22.6,21.0,13.7.
Example 9
photosensitizer PS5(0.02mmol,24mg), 4-methoxyphenylacetylene (0.2mmol,26.4mg), hans' ester (0.24mmol,60.8mg) were added to a dried Schlenk reaction tube, nitrogen was charged three times, butyraldehyde (1.0mmol,72.1mg) and diethylamine (1.0mmol,73.1mg) in acetonitrile (4mL) were added under nitrogen protection, and the reaction tube was stirred under 15W blue LED illumination for 12 hours. After the reaction is finished, adding 100-200 meshes of column chromatography silica gel into the obtained reaction liquid, decompressing and distilling to remove the solvent, carrying out silica gel column chromatography separation on the obtained crude product, eluting by using petroleum ether as an eluent, tracking the elution process by TLC, collecting the eluent containing the target product, combining the eluents, and distilling to remove the solvent to obtain the pure product. The material was a colorless liquid, 30% yield, and the product E/Z was 7/1.
Characterization data:1H NMR(500M,CDCl3)δ7.12(d,J=8.6Hz,2H),6.85(d,J=8.6Hz,2H),5.60-5.47(m,2H),3.81(s,3H),3.29(d,J=6.3Hz,2H),2.04-2.00(m,2H),1.45-1.38(m,2H),0.92(t,J=7.4Hz,3H);13C NMR(125MHz,CDCl3)δ157.9,133.2,131.6,129.37,129.35,113.8,55.3,38.2,34.6,22.7,13.7.
The olefin obtained above can be subjected to epoxidation reaction to obtain an epoxy compound (see J.Am.chem.Soc.2013,135,10930.)
1- (2-hexen-1-yl) -4-methoxybenzene (0.3mmol,57.1mg) was dissolved in CH at 0 deg.C2Cl2To (3mL) was added m-chloroperoxybenzoic acid (75% pure, 0.45mmol,103.5mg) slowly and the reaction was continued at 0 ℃ with stirring until completion of the olefinic reaction by TLC. After the reaction is finished, adding NaHSO3Quenching excess meta-chloroperoxybenzoic acid in aqueous solution, filtering, and adding NaHCO3Washing the organic phase with water solution, adding 100-200 mesh column chromatography silica gel into the organic phase after washing, distilling under reduced pressure to remove solvent, separating the crude product by silica gel column chromatography, eluting with petroleum ether/ethyl acetate 50/1 as eluent, tracking the elution process by TLC, collecting the eluent containing the target product, mixing the eluents, and evaporating to remove solvent to obtain the pure product with 82% yield.
Example 10
Photosensitizer PS5(0.015mmol,18mg), benzoic acid (4-ethynylphenyl) ester (0.2mmol,44.4mg), hanster (0.24mmol,60.8mg) were added to a dry Schlenk reaction tube, nitrogen was charged three times, butyraldehyde (1.0mmol,72.1mg) and diethylamine (1.0mmol,73.1mg) in ethyl acetate (4mL) were added under nitrogen, and the reaction tube was stirred for 12 hours under 15W blue LED illumination. After the reaction is finished, adding 100-200 meshes of column chromatography silica gel into the obtained reaction liquid, distilling under reduced pressure to remove the solvent, carrying out silica gel column chromatography separation on the obtained crude product, eluting with petroleum ether/ethyl acetate (40/1), collecting eluent containing the target product, combining the eluents, and distilling off the solvent to obtain a pure product. The material was a colorless liquid, 37% yield, and the product E/Z11/1.
Characterization data:1H NMR(500M,CDCl3)δ8.23(d,J=7.4Hz,2H),7.66(t,J=7.4Hz,1H),7.53(t,J=7.7Hz,2H),7.27(d,J=8.4Hz,2H),7.16(d,J=8.3Hz,2H),5.64-5.53(m,2H),3.38(d,J=5.9Hz,2H),2.05(dd,J1=13.6Hz,J2=6.8Hz,2H),1.48-1.41(m,2H),0.94(t,J=7.4Hz,3H);13C NMR(126MHz,CDCl3)δ165.3,149.1,138.8,133.5,132.2,130.2,129.7,129.2,128.7,128.5,121.5,38.5,34.6,22.6,13.7.
the olefin obtained above can be subjected to epoxidation reaction to obtain an epoxy compound (see J.Am.chem.Soc.2013,135,10930.)
Benzoic acid [4- (2-hexen-1-yl) phenyl ] at 0 ℃]The ester (0.3mmol,84.1mg) was dissolved in CH2Cl2To (3mL) was added m-chloroperoxybenzoic acid (75% pure, 0.45mmol,103.5mg) slowly and the reaction was continued at 0 ℃ with stirring until completion of the olefinic reaction by TLC. After the reaction is finished, adding NaHSO3quenching excess meta-chloroperoxybenzoic acid in aqueous solution, filtering, and adding NaHCO3Washing the organic phase with an aqueous solution, and obtaining the organic phase after the washing is finishedAdding 100-200 mesh column chromatography silica gel into the phase, distilling under reduced pressure to remove the solvent, separating the obtained crude product by silica gel column chromatography, eluting with petroleum ether/ethyl acetate 20/1 as eluent, tracking the elution process by TLC, collecting the eluent containing the target product, combining the eluents, and distilling off the solvent to obtain the pure product with the yield of 67%.
Example 11
photosensitizer PS5(0.015mmol,18mg), N- (4 ethynylphenyl) benzamide (0.2mmol,44.2mg), hanster (0.24mmol,60.8mg) were added to a dry Schlenk reaction tube, nitrogen was charged three times, a solution of butyraldehyde (1.0mmol,72.1mg) and diethylamine (1.0mmol,73.1mg) in tetrahydrofuran (4mL) was added under nitrogen, and the reaction tube was stirred for 12 hours under 15W blue LED illumination. After the reaction is finished, adding 100-200 meshes of column chromatography silica gel into the obtained reaction liquid, distilling under reduced pressure to remove the solvent, carrying out silica gel column chromatography separation on the obtained crude product, tracking the elution process by petroleum ether/ethyl acetate 5/1, collecting eluent containing the target product, combining the eluents, and distilling off the solvent to obtain the pure product. The material was a white solid in 25% yield and the product E/Z was 10/1.
Characterization data:1H NMR(500M,CDCl3)δ8.01(s,1H),7.87-7.85(m,2H),7.57(d,J=8.4Hz,2H),7.53(t,J=7.4Hz,1H),7.45(t,J=7.6Hz,2H),7.18(d,J=8.4Hz,2H),5.61-5.50(m,2H),3.33(d,J=6.1Hz,2H),2.04(dd,J1=13.9Hz,J2=7.1Hz,2H),1.46-1.39(m,2H),0.93(t,J=7.4Hz,2H);13C NMR(125MHz,CDCl3)δ165.8,137.5,135.8,135.1,131.9,131.7,129.0,128.9,128.7,127.0,120.5,38.5,34.6,22.6,13.7.
The olefin obtained above can be subjected to epoxidation reaction to obtain an epoxy compound (see J.Am.chem.Soc.2013,135,10930.)
At 0 deg.CThen, N- [4- (2-hexen-1-yl) phenyl]benzamide (0.3mmol,83.8mg) was dissolved in CH2Cl2to (3mL) was added m-chloroperoxybenzoic acid (75% pure, 0.45mmol,103.5mg) slowly and the reaction was continued at 0 ℃ with stirring until completion of the olefinic reaction by TLC. After the reaction is finished, adding NaHSO3Quenching excess meta-chloroperoxybenzoic acid in aqueous solution, filtering, and adding NaHCO3washing the organic phase with water solution, adding 100-200 mesh column chromatography silica gel into the organic phase after washing, distilling under reduced pressure to remove solvent, separating the crude product by silica gel column chromatography, eluting with petroleum ether/ethyl acetate 5/1 as eluent, tracking the elution process by TLC, collecting the eluent containing the target product, mixing the eluents, and evaporating to remove solvent to obtain the pure product with yield of 60%.
Example 12
Photosensitizer PS5(0.015mmol,18mg), 3-bromophenylacetylene (0.2mmol,36.2mg), hans' ester (0.24mmol,60.8mg) were added to a dry Schlenk reaction tube, nitrogen was charged three times, butyraldehyde (1.0mmol,72.1mg) and diethylamine (1.0mmol,73.1mg) in 1, 2-dichloroethane (4mL) were added under nitrogen protection, and the reaction tube was stirred for 12 hours under 15W blue LED illumination. After the reaction is finished, adding 100-200 meshes of column chromatography silica gel into the obtained reaction liquid, decompressing and distilling to remove the solvent, carrying out silica gel column chromatography separation on the obtained crude product, eluting by using petroleum ether as an eluent, tracking the elution process by TLC, collecting the eluent containing the target product, combining the eluents, and distilling to remove the solvent to obtain the pure product. The material was a colorless liquid, 17% yield, and the product had an E/Z of 12/1.
characterization data:1H NMR(500M,CDCl3)δ7.36-7.34(m,2H),7.17(t,J=7.6Hz,1H),7.13(d,J=7.7Hz,1H),5.59-5.51(m,2H),3.32(d,J=3.5Hz,2H),2.06-2.02(m,2H),1.47-1.40(m,2H),0.93(t,J=7.4Hz,3H);13C NMR(125MHz,CDCl3)δ143.5,132.7,131.5,129.9,129.0,128.0,127.1,122.4,38.7,34.6,22.6,13.7.
The olefin obtained above can be subjected to epoxidation reaction to obtain an epoxy compound (see J.Am.chem.Soc.2013,135,10930.)
3-bromo- (2-hexen-1-yl) benzene (0.3mmol,71.7mg) was dissolved in CH at 0 deg.C2Cl2To (3mL) was added m-chloroperoxybenzoic acid (75% pure, 0.45mmol,103.5mg) slowly and the reaction was continued at 0 ℃ with stirring until completion of the olefinic reaction by TLC. After the reaction is finished, adding NaHSO3Quenching excess meta-chloroperoxybenzoic acid in aqueous solution, filtering, and adding NaHCO3Washing the organic phase with water solution, adding 100-200 mesh column chromatography silica gel into the organic phase after washing, distilling under reduced pressure to remove solvent, separating the crude product by silica gel column chromatography, eluting with petroleum ether/ethyl acetate (100/1) as eluent, tracking the elution process by TLC, collecting the eluent containing the target product, mixing the eluents, and evaporating to remove solvent to obtain the pure product with a yield of 75%.
Example 13
Photosensitizer PS5(0.015mmol,18mg), 2-bromophenylacetylene (0.2mmol,36.2mg), hans' ester (0.24mmol,60.8mg) were added to a dry Schlenk reaction tube, nitrogen was charged three times, butyraldehyde (1.0mmol,72.1mg) and diethylamine (1.0mmol,73.1mg) in N, N-dimethylformamide (4mL) were added under nitrogen protection, and the reaction tube was stirred for 12 hours under 15W blue LED illumination. After the reaction is finished, adding 100-200 meshes of column chromatography silica gel into the obtained reaction liquid, decompressing and distilling to remove the solvent, carrying out silica gel column chromatography separation on the obtained crude product, eluting by using petroleum ether as an eluent, tracking the elution process by TLC, collecting the eluent containing the target product, combining the eluents, and distilling to remove the solvent to obtain the pure product. The material was a colorless liquid in 21% yield, the product having an E/Z of 10/1
Characterization data:1H NMR(500M,CDCl3)δ7.56(d,J=7.6Hz,1H),7.29-7.25(m,2H),7.10-7.07(m,1H),5.62-5.51(m,2H),3.48(d,J=5.9Hz,2H),2.04(dd,J1=13.4Hz,J2=7.2Hz,2H),1.47-1.39(m,2H),0.93(t,J=7.4Hz,3H);13C NMR(125MHz,CDCl3)δ140.5,132.8,132.7,130.3,127.6,127.4,127.0,124.6,39.1,34.7,22.6,13.7.
Example 14
Photosensitizer PS5(0.015mmol,18mg), 2-ethynyl-6-fluorobenzonitrile (0.2mmol,29.2mg), hanster (0.24mmol,60.8mg) were added to a dry Schlenk reaction tube, nitrogen was charged three times, butyraldehyde (1.0mmol,72.1mg) and diethylamine (1.0mmol,73.1mg) in 1, 4-dioxane (4mL) were added under nitrogen, and the reaction tube was stirred under 15W blue LED illumination for 12 hours. After the reaction is finished, adding 100-200 meshes of column chromatography silica gel into the obtained reaction liquid, distilling under reduced pressure to remove the solvent, carrying out silica gel column chromatography separation on the obtained crude product, eluting by using petroleum ether/ethyl acetate 40/1 as an eluent, tracking the elution process by TLC, collecting eluent containing the target product, combining the eluents, and distilling off the solvent to obtain the pure product. The material was a colorless liquid in 40% yield, and the product characterized by E/Z13/1:1H NMR(500M,CDCl3)δ7.51(td,J1=8.1Hz,J2=5.9Hz,1H),7.14(d,J=7.8Hz,1H),7.05(t,J=8.5Hz,1H),5.64-5.58(m,1H),5.55-5.50(m,1H),3.55(d,J=6.4Hz,2H),2.05-2.00(m,2H),0.90(t,J=7.4Hz,3H);13C NMR(125MHz,CDCl3)δ163.6(d,J=258.4Hz),147.3,134.3,134.2,125.7,125.0(d,J=3.3Hz),113.6(d,J=19.6Hz),113.1,101.7(d,J=15.0Hz),37.4(d,J=1.8Hz),34.5,22.4,13.6.
The olefin obtained above can be subjected to epoxidation reaction to obtain an epoxy compound (see J.Am.chem.Soc.2013,135,10930.)
2-fluoro-6- (2-hexen-1-yl) -benzonitrile (0.3mmol,60.9mg) was dissolved in CH at 0 deg.C2Cl2To (3mL) was added m-chloroperoxybenzoic acid (75% pure, 0.45mmol,103.5mg) slowly and the reaction was continued at 0 ℃ with stirring until completion of the olefinic reaction by TLC. After the reaction is finished, adding NaHSO3Quenching excess meta-chloroperoxybenzoic acid in aqueous solution, filtering, and adding NaHCO3Washing the organic phase with water solution, adding 100-200 mesh column chromatography silica gel into the organic phase after washing, distilling under reduced pressure to remove solvent, separating the crude product by silica gel column chromatography, eluting with petroleum ether/ethyl acetate 50/1 as eluent, tracking the elution process by TLC, collecting the eluent containing the target product, mixing the eluents, and evaporating to remove solvent to obtain the pure product with a yield of 71%.
Example 15
photosensitizer PS5(0.015mmol,18mg), 2-naphthylacetylene (0.2mmol,30.4mg), hanster (0.24mmol,60.8mg) were added to a dried Schlenk reaction tube, nitrogen was charged three times, butyraldehyde (1.0mmol,72.1mg) and diethylamine (1.0mmol,73.1mg) in dimethyl sulfoxide (4mL) were added under nitrogen protection, and the reaction tube was stirred under 15W blue LED illumination for 12 hours. After the reaction is finished, adding 100-200 meshes of column chromatography silica gel into the obtained reaction liquid, decompressing and distilling to remove the solvent, carrying out silica gel column chromatography separation on the obtained crude product, eluting by using petroleum ether as an eluent, tracking the elution process by TLC, collecting the eluent containing the target product, combining the eluents, and distilling to remove the solvent to obtain the pure product. The material was a colorless liquid, 12% yield, and the product E/Z was 10/1.
Characterization data:1H NMR(500M,CDCl3)δ7.86-7.82(m,3H),7.67(s,1H),7.55-7.44(m,2H),7.39(dd,J1=8.4Hz,J2=1.3Hz,1H),5.74-5.68(m,1H),5.65-5.59(m,1H),3.55(d,J=6.5Hz,2H),2.10(q,J=7.0Hz,2H),1.50-1.44(m,2H),0.98(t,J=7.4Hz,3H);13C NMR(125MHz,CDCl3)δ138.7,133.7,132.2,132.1,128.8,127.9,127.6,127.49,127.45,126.4,125.9,125.2,39.2,34.7,22.6,13.7.
The olefin obtained above can be subjected to epoxidation reaction to obtain an epoxy compound (see J.Am.chem.Soc.2013,135,10930.)
2- (2-hexen-1-yl) -naphthalene (0.3mmol,63.0mg) was dissolved in CH at 0 deg.C2Cl2to (3mL) was added m-chloroperoxybenzoic acid (75% pure, 0.45mmol,103.5mg) slowly and the reaction was continued at 0 ℃ with stirring until completion of the olefinic reaction by TLC. After the reaction is finished, adding NaHSO3Quenching excess meta-chloroperoxybenzoic acid in aqueous solution, filtering, and adding NaHCO3Washing the organic phase with water solution, adding 100-200 mesh column chromatography silica gel into the organic phase after washing, distilling under reduced pressure to remove the solvent, separating the crude product by silica gel column chromatography, eluting with petroleum ether/ethyl acetate (100/1) as eluent, tracking the elution process by TLC, collecting the eluent containing the target product, combining the eluents, and evaporating to remove the solvent to obtain the pure product with the yield of 87%.
Example 16
photosensitizer PS5(0.015mmol,18mg),2- (4-ethynylphenyl) thiophene (0.2mmol,36.8mg), hanster (0.24mmol,60.8mg) were added to a dry Schlenk reaction tube, nitrogen was charged three times, butyraldehyde (1.0mmol,72.1mg) and diethylamine (1.0mmol,73.1mg) in cyclopentyl methyl ether (4mL) were added under nitrogen, and the reaction tube was stirred for 12 hours under 15W blue LED illumination. After the reaction is finished, adding 100-200 meshes of column chromatography silica gel into the obtained reaction liquid, decompressing and distilling to remove the solvent, carrying out silica gel column chromatography separation on the obtained crude product, eluting by using petroleum ether as an eluent, tracking the elution process by TLC, collecting the eluent containing the target product, combining the eluents, and distilling to remove the solvent to obtain the pure product. The material was a colorless liquid in 41% yield, the product having an E/Z of 12/1
Characterization data:1H NMR(500M,CDCl3)δ7.58(d,J=8.2Hz,2H),7.32(dd,J1=3.6Hz,J2=1.1Hz,1H),7.29(dd,J1=5.1Hz,J2=1.1Hz,1H),7.24(d,J=8.3Hz,2H),7.11(dd,J1=5.1Hz,J2=3.6Hz,1H),5.66-5.55(m,2H),3.39(d,J=5.9Hz,2H),2.07(dd,J1=13.3Hz,J2=7.2Hz,2H),0.97(t,J=7.4Hz,3H);13C NMR(125MHz,CDCl3)δ144.6,140.6,132.18,132.15,129.0,128.7,127.9,126.0,124.3,122.7,38.7,34.6,22.6,13.7.
The olefin obtained above can be subjected to epoxidation reaction to obtain an epoxy compound (see J.Am.chem.Soc.2013,135,10930.)
At 0 deg.C, 2- [4- (2-hexen-1-yl) phenyl]-thiophene (0.3mmol,72.7mg) dissolved in CH2Cl2To (3mL) was added m-chloroperoxybenzoic acid (75% pure, 0.45mmol,103.5mg) slowly and the reaction was continued at 0 ℃ with stirring until completion of the olefinic reaction by TLC. After the reaction is finished, adding NaHSO3Quenching excess meta-chloroperoxybenzoic acid in aqueous solution, filtering, and adding NaHCO3Washing the organic phase with water solution, adding 100-200 mesh column chromatography silica gel into the organic phase after washing, distilling under reduced pressure to remove solvent, separating the crude product by silica gel column chromatography, eluting with petroleum ether/ethyl acetate (100/1) as eluent, tracking the elution process by TLC, collecting the eluent containing the target product, mixing the eluents, and evaporating to remove solvent to obtain the pure product with a yield of 68%.
Example 17
Photosensitizer PS5(0.015mmol,18mg),4- (ethynylphenyl) pyridine (0.2mmol,35.8mg), hanster (0.24mmol,60.8mg) were added to a dry Schlenk reaction tube, nitrogen was charged three times, butyraldehyde (1.0mmol,72.1mg) and dibutyraldehyde were added under nitrogen protectionEthylamine (1.0mmol,73.1mg) in trifluorotoluene (4mL) was added to the reaction tube and the tube was stirred for 12 hours under 15W blue LED illumination. After the reaction is finished, adding 100-200 meshes of column chromatography silica gel into the obtained reaction liquid, distilling under reduced pressure to remove the solvent, carrying out silica gel column chromatography separation on the obtained crude product, eluting by using petroleum ether/ethyl acetate (10/1) as an eluent, tracking the elution process by TLC (thin layer chromatography), collecting eluent containing a target product, combining the eluent, and distilling off the solvent to obtain a pure product. The material was a colorless liquid in 17% yield, and the product characterized by E/Z9/1:1H NMR(500M,CDCl3)δ8.65(d,J=6.0Hz,2H),7.58(d,J=8.1Hz,2H),7.50(d,J=6.1Hz,2H),7.32(d,J=8.1Hz,2H),5.63-5.54(m,2H),3.40(d,J=5.3Hz,2H),2.06-2.02(m,2H),1.47-1.39(m,2H),0.93(t,J=7.4Hz,3H);13C NMR(125MHz,CDCl3)δ150.2,148.2,142.4,135.7,132.4,129.2,128.3,126.9,121.4,38.7,34.6,22.6,13.7.
the olefin obtained above can be subjected to epoxidation reaction to obtain an epoxy compound (see J.Am.chem.Soc.2013,135,10930.)
4- [4- (2-hexen-1-yl) phenyl at 0 ℃]-pyridine (0.3mmol,71.2mg) dissolved in CH2Cl2To (3mL) was added m-chloroperoxybenzoic acid (75% pure, 0.45mmol,103.5mg) slowly and the reaction was continued at 0 ℃ with stirring until completion of the olefinic reaction by TLC. After the reaction is finished, adding NaHSO3Quenching excess meta-chloroperoxybenzoic acid in aqueous solution, filtering, and adding NaHCO3Washing the organic phase with water solution, adding 100-200 mesh column chromatography silica gel into the organic phase after washing, distilling under reduced pressure to remove solvent, separating the crude product by silica gel column chromatography, eluting with petroleum ether/ethyl acetate (100/1) as eluent, tracking the elution process by TLC, collecting the eluent containing the target product, mixing the eluents, and evaporating to remove solvent to obtain the pure product with a yield of 72%.
example 18
Photosensitizer PS5(0.015mmol,18mg), 5-ethynylbenzothiophene (0.2mmol,31.6mg), hanster (0.24mmol,60.8mg) were added to a dry Schlenk reaction tube, nitrogen was charged three times, butyraldehyde (1.0mmol,72.1mg) and diethylamine (1.0mmol,73.1mg) in a solution of 1, 4-dioxane/water of 4/0.2mL (4mL) were added under nitrogen, and the reaction tube was stirred for 12 hours under 15W blue LED illumination. After the reaction is finished, adding 100-200 meshes of column chromatography silica gel into the obtained reaction liquid, decompressing and distilling to remove the solvent, carrying out silica gel column chromatography separation on the obtained crude product, eluting by using petroleum ether as an eluent, tracking the elution process by TLC, collecting the eluent containing the target product, combining the eluents, and distilling to remove the solvent to obtain the pure product. The material was a colorless liquid in 45% yield, the product having an E/Z of 10/1
Characterization data:1H NMR(500M,CDCl3)δ7.83(d,J=8.3Hz,1H),7.67(d,J=0.8Hz,1H),7.45(d,J=5.5Hz,1H),7.32(dd,J1=5.4Hz,J2=0.6Hz,1H),7.24(dd,J1=8.3Hz,J2=1.5Hz,1H),5.70-5.64(m,1H),5.62-5.56(m,1H),3.50(d,J=6.5Hz,2H),2.10-2.05(m,2H),1.50-1.43(m,2H),0.96(t,J=7.4Hz,3H);13C NMR(125MHz,CDCl3)δ140.0,137.4,137.3,131.9,129.2,126.4,125.5,123.7,123.1,122.2,39.0,34.6,22.6,13.7.
The olefin obtained above can be subjected to epoxidation reaction to obtain an epoxy compound (see J.Am.chem.Soc.2013,135,10930.)
5- (2-hexen-1-yl) benzothiophene (0.3mmol,64.9mg) was dissolved in CH at 0 deg.C2Cl2to (3mL) was added m-chloroperoxybenzoic acid (75% pure, 0.45mmol,103.5mg) slowly and the reaction was continued at 0 ℃ with stirring until completion of the olefinic reaction by TLC. After the reaction is finished, adding NaHSO3Quenching excess meta-chloroperoxybenzoic acid in aqueous solution, filtering, and adding NaHCO3Washing the organic phase with the aqueous solutionAnd finally, adding 100-200 meshes of column chromatography silica gel into the obtained organic phase, distilling under reduced pressure to remove the solvent, carrying out silica gel column chromatography separation on the obtained crude product, eluting by using petroleum ether/ethyl acetate (100/1) as an eluent, tracking the elution process by TLC (thin layer chromatography), collecting eluent containing the target product, combining the eluents, and evaporating to remove the solvent to obtain a pure product with the yield of 76%.
example 19
photosensitizer PS5(0.015mmol,18mg), 3-ethynylbenzothiophene (0.2mmol,31.6mg), hanster (0.24mmol,60.8mg) were added to a dry Schlenk reaction tube, charged with nitrogen three times, butyraldehyde (1.0mmol,72.1mg) and dimethylamine (2M in THF,0.5mL) in 4, 4-dioxane/water (4mL) were added under nitrogen protection, and the reaction tube was stirred under 15W blue LED illumination for 12 hours. After the reaction is finished, adding 100-200 meshes of column chromatography silica gel into the obtained reaction liquid, decompressing and distilling to remove the solvent, carrying out silica gel column chromatography separation on the obtained crude product, eluting by using petroleum ether as an eluent, tracking the elution process by TLC, collecting the eluent containing the target product, combining the eluents, and distilling to remove the solvent to obtain the pure product. The material was a colorless liquid in 5% yield, and the product characterized by E/Z9/1:1H NMR(500M,CDCl3)δ7.88(d,J=7.3Hz,1H),7.79(d,J=7.5Hz,1H),7.42-7.35(m,2H),7.13(s,1H),5.73-5.61(m,2H),3.57(d,J=6.2Hz,2H),2.08-2.04(m,2H),1.48-1.40(m,2H),0.94(t,J=7.4Hz,3H);13C NMR(125MHz,CDCl3)δ140.6,138.9,135.7,132.7,127.0,124.1,123.8,122.8,121.9,121.7,34.6,32.0,22.6,13.7
The olefin obtained above can be subjected to epoxidation reaction to obtain an epoxy compound (see J.Am.chem.Soc.2013,135,10930.)
3- (2-hexen-1-yl) benzothiophene (0.3mmol,64.9mg) was dissolved at 0 deg.CIn CH2Cl2To (3mL) was added m-chloroperoxybenzoic acid (75% pure, 0.45mmol,103.5mg) slowly and the reaction was continued at 0 ℃ with stirring until completion of the olefinic reaction by TLC. After the reaction is finished, adding NaHSO3Quenching excess meta-chloroperoxybenzoic acid in aqueous solution, filtering, and adding NaHCO3Washing the organic phase with water solution, adding 100-200 mesh column chromatography silica gel into the organic phase after washing, distilling under reduced pressure to remove the solvent, separating the crude product by silica gel column chromatography, eluting with petroleum ether/ethyl acetate (100/1) as eluent, tracking the elution process by TLC, collecting the eluent containing the target product, combining the eluents, and evaporating to remove the solvent to obtain the pure product with the yield of 57%.
example 20
Photosensitizer PS5(0.015mmol,18mg), 4-phenylphenylacetylene (0.2mmol,35.6mg), hans' ester (0.24mmol,60.8mg) were added to a dry Schlenk reaction tube, nitrogen was charged three times, a solution of valeraldehyde (1.0mmol,86.1mg) and di-n-propylamine (1.0mmol,101.2mL) in 1, 4-dioxane/water (4/0.2 mL) was added under nitrogen protection, and the reaction tube was stirred under 15W blue LED illumination for 12 hours. After the reaction is finished, adding 100-200 meshes of column chromatography silica gel into the obtained reaction liquid, decompressing and distilling to remove the solvent, carrying out silica gel column chromatography separation on the obtained crude product, eluting by using petroleum ether as an eluent, tracking the elution process by TLC, collecting the eluent containing the target product, combining the eluents, and distilling to remove the solvent to obtain the pure product. The material was a colorless liquid, 68% yield, and the product E/Z was 10/1.
Characterization data:1H NMR(500MHz,CDCl3)δ7.61(dd,J1=8.3Hz,J2=1.2Hz,2H),7.55(d,J=8.2Hz,2H),7.45(t,J=7.7Hz,2H),7.37-7.33(m,1H),7.30-7.28(m,2H),5.65-5.54(m,2H),3.40(d,J=5.9Hz,2H),2.07(dd,J1=13.2Hz,J2=6.8Hz,2H),1.43-1.31(m,4H),0.95-0.91(m,3H);13C NMR(125MHz,CDCl3)δ141.2,140.3,138.9,132.3,128.9,128.7,128.6,127.1,127.04,127.02,38.7,32.2,31.7,22.3,14.0.
The olefin obtained above can be subjected to epoxidation reaction to obtain an epoxy compound (see J.Am.chem.Soc.2013,135,10930.)
4- (2-hepten-1-yl) -1, 1' -biphenyl (0.3mmol,75.0mg) was dissolved in CH at 0 deg.C2Cl2To (3mL) was added m-chloroperoxybenzoic acid (75% pure, 0.45mmol,103.5mg) slowly and the reaction was continued at 0 ℃ with stirring until completion of the olefinic reaction by TLC. After the reaction is finished, adding NaHSO3Quenching excess meta-chloroperoxybenzoic acid in aqueous solution, filtering, and adding NaHCO3Washing the organic phase with water solution, adding 100-200 mesh column chromatography silica gel into the organic phase after washing, distilling under reduced pressure to remove solvent, separating the crude product by silica gel column chromatography, eluting with petroleum ether/ethyl acetate (100/1) as eluent, tracking the elution process by TLC, collecting the eluent containing the target product, mixing the eluents, and evaporating to remove solvent to obtain the pure product with 83% yield.
Example 21
Photosensitizer PS5(0.015mmol,18mg), 4-phenylphenylacetylene (0.2mmol,35.6mg), hans' ester (0.24mmol,60.8mg) were added to a dry Schlenk reaction tube, nitrogen was charged three times, hexanal (1.0mmol,100.2mg) and tetrahydropyrrole (1.0mmol,71.1mg) in 4, 4-dioxane/water (4/0.2 mL) were added under nitrogen, the reaction tube was stirred under 15W blue LED illumination for 12 hours. After the reaction is finished, adding 100-200 meshes of column chromatography silica gel into the obtained reaction liquid, distilling under reduced pressure to remove the solvent, carrying out silica gel column chromatography separation on the obtained crude product, eluting by using petroleum ether as an eluent, tracking the elution process by TLC, collecting the eluent containing the target product, combining the eluents, and distilling off the solvent to obtain the pure product. The material was a colorless liquid, 14% yield, and the product E/Z was 10/1. Characterization data:1H NMR(500MHz,CDCl3)δ7.65(dd,J1=8.2Hz,2H),7.59(d,J=8.2Hz,2H),7.49(t,J=7.7Hz,2H),7.42-7.36(m,1H),7.33(d,J=8.2Hz,2H),5.70-5.60(m,2H),3.44(d,J=5.8Hz,2H),2.11(dd,J1=13.4Hz,J2=7.1Hz,2H),1.49-1.35(m,6H),0.97(t,J=6.9Hz,3H);13C NMR(125MHz,CDCl3)δ141.2,140.3,138.9,132.4,128.9,128.7,128.6,127.1,127.03,127.01,38.7,32.5,31.5,29.2,22.6,14.1.
The olefin obtained above can be subjected to epoxidation reaction to obtain an epoxy compound (see J.Am.chem.Soc.2013,135,10930.)
4- (2-octen-1-yl) -1, 1' -biphenyl (0.3mmol,79.3mg) was dissolved in CH at 0 deg.C2Cl2to (3mL) was added m-chloroperoxybenzoic acid (75% pure, 0.45mmol,103.5mg) slowly and the reaction was continued at 0 ℃ with stirring until completion of the olefinic reaction by TLC. After the reaction is finished, adding NaHSO3quenching excess meta-chloroperoxybenzoic acid in aqueous solution, filtering, and adding NaHCO3washing the organic phase with water solution, adding 100-200 mesh column chromatography silica gel into the organic phase after washing, distilling under reduced pressure to remove solvent, separating the crude product by silica gel column chromatography, eluting with petroleum ether/ethyl acetate (100/1) as eluent, tracking the elution process by TLC, collecting the eluent containing the target product, mixing the eluents, and evaporating to remove solvent to obtain the pure product with the yield of 80%.
Example 22
The photosensitizers PS5(0.015mmol,18mg), 4-phenylphenylacetylene (0.2mmol,35.6mg), hanster (0.24mmol,60.8mg) were added to a dry Schlenk reaction tube, nitrogen was charged three times, and 5-chloropentanal (1.0mmol,120.5mg) and piperidine (1.0mmol,85.2mg) in 1, 4-bis (N-bis) were added under nitrogen protectionThe reaction tube was stirred under 15W blue LED irradiation for 12 hours at 4/0.2mL solution (4mL) of oxahexacyclic/water. After the reaction is finished, adding 100-200 meshes of column chromatography silica gel into the obtained reaction liquid, decompressing and distilling to remove the solvent, carrying out silica gel column chromatography separation on the obtained crude product, eluting by using petroleum ether as an eluent, tracking the elution process by TLC, collecting the eluent containing the target product, combining the eluents, and distilling to remove the solvent to obtain the pure product. The material was a colorless liquid, 23% yield, and the product E/Z was 10/1. Characterization data:1H NMR(500MHz,CDCl3)δ7.63(dd,J1=8.2Hz,J2=1.2Hz,2H),7.58(d,J=8.2Hz,2H),7.47(t,J=7.7Hz,2H),7.39-7.36(m,1H),7.30(d,J=8.2Hz,2H),5.70-5.65(m,1H),5.60-5.55(m,1H),3.59(t,J=6.7Hz,2H),3.42(d,J=6.6Hz,2H),2.13(q,J=6.9Hz,2H),1.87-1.81(m,2H),1.62-1.56(m,2H);13C NMR(125MHz,CDCl3)δ141.1,134.0,138.9,131.3,129.4,128.9,128.7,127.1,127.03,127.01,45.0,38.7,32.1,31.7,26.7.
The olefin obtained above can be subjected to epoxidation reaction to obtain an epoxy compound (see J.Am.chem.Soc.2013,135,10930.)
4- (7-chloro-2-hepten-1-yl) -1, 1' -biphenyl (0.3mmol,85.5mg) was dissolved in CH at 0 deg.C2Cl2to (3mL) was added m-chloroperoxybenzoic acid (75% pure, 0.45mmol,103.5mg) slowly and the reaction was continued at 0 ℃ with stirring until completion of the olefinic reaction by TLC. After the reaction is finished, adding NaHSO3quenching excess meta-chloroperoxybenzoic acid in aqueous solution, filtering, and adding NaHCO3Washing the organic phase with water solution, adding 100-200 mesh column chromatography silica gel into the organic phase after washing, distilling under reduced pressure to remove solvent, separating the crude product by silica gel column chromatography, eluting with petroleum ether/ethyl acetate (100/1) as eluent, tracking the elution process by TLC, collecting the eluent containing the target product, mixing the eluents, and evaporating to remove solvent to obtain the pure product with yield of 78%.
example 23
Photosensitizer PS5(0.015mmol,18mg), 4-phenylphenylacetylene (0.2mmol,35.6mg), hans' ester (0.24mmol,60.8mg) were added to a dry Schlenk reaction tube, nitrogen was charged three times, a solution of phenylacetaldehyde (1.0mmol,120.2mg) and di-n-propylamine (1.0mmol,101.2mL) in 1, 4-dioxane/water (4/0.2 mL) was added under nitrogen protection, and the reaction tube was stirred for 12 hours under 30W blue LED illumination. After the reaction is finished, adding 100-200 meshes of column chromatography silica gel into the obtained reaction liquid, decompressing and distilling to remove the solvent, carrying out silica gel column chromatography separation on the obtained crude product, eluting by using petroleum ether as an eluent, tracking the elution process by TLC, collecting the eluent containing the target product, combining the eluents, and distilling to remove the solvent to obtain the pure product. The material was a colorless liquid in 49% yield, and the product characterized by E/Z10/1:1H NMR(500MHz,CDCl3)δ7.61(dd,J1=8.2Hz,J2=1.1Hz,2H),7.55(d,J=8.2Hz,2H),7.45(t,J=7.7Hz,2H),7.37-7.29(m,5H),7.24-7.21(m,3H),5.79-5.70(m,2H),3.44(d,J=4.4Hz,2H),3.42(d,J=4.4Hz,2H);13C NMR(125MHz,CDCl3)δ141.1,140.7,139.9,139.0,130.6,130.3,128.9,128.7,128.5,128.4,127.2,127.05,127.04,126.0,39.0,38.6.
the olefin obtained above can be subjected to epoxidation reaction to obtain an epoxy compound (see J.Am.chem.Soc.2013,135,10930.)
4- (4-phenyl-2-buten-1-yl) -1, 1' -biphenyl (0.3mmol,85.3mg) was dissolved in CH at 0 deg.C2Cl2To (3mL) was added m-chloroperoxybenzoic acid (75% pure, 0.45mmol,103.5mg) slowly and the reaction was continued at 0 ℃ with stirring until completion of the olefinic reaction by TLC. After the reaction is finished, adding NaHSO3quenching excess meta-chloroperoxybenzoic acid in aqueous solution, filtering, and adding NaHCO3Washing the organic phase with an aqueous solution, and obtaining the organic phase after the washing is finishedAdding 100-200 mesh column chromatography silica gel into the phase, distilling under reduced pressure to remove the solvent, separating the obtained crude product by silica gel column chromatography, eluting with petroleum ether/ethyl acetate (100/1) as eluent, tracking the elution process by TLC, collecting the eluent containing the target product, mixing the eluents, and distilling off the solvent to obtain the pure product with the yield of 78%.
Example 24
Photosensitizer PS5(0.015mmol,18mg), 4-phenylphenylacetylene (0.2mmol,35.6mg), hanster (0.24mmol,60.8mg) were added to a dry Schlenk reaction tube, nitrogen was charged three times, a solution of citronellal (1.0mmol,154.2mg) and di-n-propylamine (1.0mmol,101.2mL) in 1, 4-dioxane/water (4mL) was added under nitrogen protection, and the reaction tube was stirred under 60W CFL for 12 hours. After the reaction is finished, adding 100-200 meshes of column chromatography silica gel into the obtained reaction liquid, decompressing and distilling to remove the solvent, carrying out silica gel column chromatography separation on the obtained crude product, eluting by using petroleum ether as an eluent, tracking the elution process by TLC, collecting the eluent containing the target product, combining the eluents, and distilling to remove the solvent to obtain the pure product. The material was a colorless liquid, 60% yield, and the product E/Z was 10/1.
Characterization data:1H NMR(500MHz,CDCl3)δ7.62(d,J=7.7Hz,2H),7.56(d,J=8.1Hz,2H),7.46(t,J=7.7Hz,2H),7.36(t,J=7.4Hz,1H),7.30(d,J=8.1Hz,2H),5.66-5.54(m,2H),5.15(t,J=7.1Hz,1H),3.43(d,J=6.3Hz,2H),2.14-1.91(m,4H),1.73(s,3H),1.65(s3H),1.59-1.52(m,1H),1.45-1.38(m,1H),1.24-1.17(m,1H),0.94(d,J=6.7Hz,3H);13C NMR(125MHz,CDCl3)δ141.2,140.3,138.9,131.1,130.7,129.9,128.9,128.7,127.1,127.03,127.02,124.9,40.0,38.8,36.7,32.8,25.8,25.6,19.5,17.7.
The olefin obtained above can be subjected to epoxidation reaction to obtain an epoxy compound (see J.Am.chem.Soc.2013,135,10930.)
4- (5, 9-dimethyl-2, 8-maladien-1-yl) -1, 1' -biphenyl (0.3mmol,95.5mg) was dissolved in CH at 0 deg.C2Cl2To (3mL) was added m-chloroperoxybenzoic acid (75% pure, 0.6mmol,207mg) slowly and the reaction was continued at 0 ℃ with stirring until completion of the olefinic reaction by TLC. After the reaction is finished, adding NaHSO3Quenching excess meta-chloroperoxybenzoic acid in aqueous solution, filtering, and adding NaHCO3Washing the organic phase with water solution, adding 100-200 mesh column chromatography silica gel into the organic phase after washing, distilling under reduced pressure to remove solvent, separating the crude product by silica gel column chromatography, eluting with petroleum ether/ethyl acetate (100/1) as eluent, tracking the elution process by TLC, collecting the eluent containing the target product, mixing the eluents, and evaporating to remove solvent to obtain the pure product with a yield of 49%.
Example 25
Photosensitizer PS5(0.015mmol,18mg), 4-phenylphenylacetylene (0.2mmol,35.6mg), hans' ester (0.24mmol,60.8mg) were added to a dry Schlenk reaction tube, nitrogen was charged three times, a solution of tert-butyl 3-formylpiperidine-1-carboxylate (1.0mmol,215mg) and di-n-propylamine (1.0mmol,101.2mL) in 1, 4-dioxane/water (4/0.2 mL) was added under nitrogen protection, and the reaction tube was stirred under 20W white LED illumination for 12 hours. After the reaction is finished, adding 100-200 meshes of column chromatography silica gel into the obtained reaction liquid, distilling under reduced pressure to remove the solvent, carrying out silica gel column chromatography separation on the obtained crude product, eluting by using petroleum ether/ethyl acetate (10/1) as an eluent, tracking the elution process by TLC (thin layer chromatography), collecting eluent containing a target product, combining the eluent, and distilling off the solvent to obtain a pure product. The material was a colorless liquid, 65% yield, and the product E/Z was 10/1.
Characterization data:1H NMR(500MHz,CDCl3)δ7.61(d,J=7.2Hz,2H),7.54(d,J=8.1Hz,2H),7.45(t,J=7.7Hz,2H),7.35(t,J=7.4Hz,1H),7.27(d,J=8.5Hz,2H),5.73-5.67(m,1H),5.49-5.45(m,1H),3.98-3.96(m,2H),3.40(d,J=6.7Hz,2H),2.79-2.73(m,2H),2.24-2.13(m,1H),1.90-1.86(m,1H),1.70-1.67(m,2H),1.49(s,9H),1.34-1.27(m,1H).13C NMR(125MHz,CDCl3)δ154.9,141.1,139.7,139.0,133.5,129.0,128.9,128.7,127.1,127.04,127.02,79.3,38.9,38.7,30.9,28.5.
Example 26
photosensitizer PS5(0.015mmol,18mg), 4-phenylphenylacetylene (0.2mmol,35.6mg), hans' ester (0.1mmol,25.3mg) were added to a dry Schlenk reaction tube, nitrogen was charged three times, a solution of butyraldehyde (1.0mmol,72.1mg) and di-n-propylamine (1.0mmol,101.2mL) in 1, 4-dioxane/water (4/0.2 mL) was added under nitrogen protection (4mL), and the reaction tube was stirred under 30W blue LED illumination for 12 hours. After the reaction is finished, adding 100-200 meshes of column chromatography silica gel into the obtained reaction liquid, decompressing and distilling to remove the solvent, carrying out silica gel column chromatography separation on the obtained crude product, eluting by using petroleum ether as an eluent, tracking the elution process by TLC, collecting the eluent containing the target product, combining the eluents, and distilling to remove the solvent to obtain the pure product. The material was a colorless liquid, 64% yield, and the product E/Z was 10/1.
Example 27
Photosensitizer PS5(0.015mmol,18mg), 4-phenylphenylacetylene (0.2mmol,35.6mg), hans' ester (0.2mmol,50.6mg) were added to a dry Schlenk reaction tube, nitrogen was charged three times, a solution of butyraldehyde (1.0mmol,72.1mg) and di-n-propylamine (1.0mmol,101.2mL) in 1, 4-dioxane/water (4/0.2 mL) was added under nitrogen protection (4mL), and the reaction tube was stirred under 30W blue LED illumination for 12 hours. After the reaction is finished, adding 100-200 meshes of column chromatography silica gel into the obtained reaction liquid, decompressing and distilling to remove the solvent, carrying out silica gel column chromatography separation on the obtained crude product, eluting by using petroleum ether as an eluent, tracking the elution process by TLC, collecting the eluent containing the target product, combining the eluents, and distilling to remove the solvent to obtain the pure product. The material was a colorless liquid, 74% yield, and the product E/Z was 10/1.
Example 27
Photosensitizer PS5(0.015mmol,18mg), 4-phenylphenylacetylene (0.2mmol,35.6mg), hans' ester (0.3mmol,75.9mg) were added to a dry Schlenk reaction tube, nitrogen was charged three times, a solution of butyraldehyde (1.0mmol,72.1mg) and di-n-propylamine (1.0mmol,101.2mL) in 1, 4-dioxane/water (4/0.2 mL) was added under nitrogen protection (4mL), and the reaction tube was stirred under 30W blue LED illumination for 12 hours. After the reaction is finished, adding 100-200 meshes of column chromatography silica gel into the obtained reaction liquid, decompressing and distilling to remove the solvent, carrying out silica gel column chromatography separation on the obtained crude product, eluting by using petroleum ether as an eluent, tracking the elution process by TLC, collecting the eluent containing the target product, combining the eluents, and distilling to remove the solvent to obtain the pure product. The material was a colorless liquid, 74% yield, and the product E/Z was 10/1.
Example 28
Photosensitizer PS5(0.015mmol,18mg), 4-phenylphenylacetylene (0.2mmol,35.6mg), hans' ester (0.3mmol,75.9mg) were added to a dry Schlenk reaction tube, nitrogen was charged three times, a solution of butyraldehyde (1.0mmol,72.1mg) and di-n-propylamine (1.0mmol,101.2mL) in 1, 4-dioxane/water (4/0.2 mL) was added under nitrogen protection (4mL), and the reaction tube was stirred under 30W blue LED illumination for 12 hours. After the reaction is finished, adding 100-200 meshes of column chromatography silica gel into the obtained reaction liquid, decompressing and distilling to remove the solvent, carrying out silica gel column chromatography separation on the obtained crude product, eluting by using petroleum ether as an eluent, tracking the elution process by TLC, collecting the eluent containing the target product, combining the eluents, and distilling to remove the solvent to obtain the pure product. The material was a colorless liquid, 77% yield, and the product E/Z was 10/1.
Example 29
Photosensitizer PS5(0.015mmol,18mg), 4-phenylphenylacetylene (0.2mmol,35.6mg), hans' ester (0.24mmol,60.8mg) were added to a dry Schlenk reaction tube, nitrogen was charged three times, a solution of butyraldehyde (0.8mmol,57.7mg) and di-n-propylamine (0.8mmol,81.0mL) in 1, 4-dioxane/water (4/0.2 mL) was added under nitrogen protection (4mL), and the reaction tube was stirred under 30W blue LED illumination for 12 hours. After the reaction is finished, adding 100-200 meshes of column chromatography silica gel into the obtained reaction liquid, decompressing and distilling to remove the solvent, carrying out silica gel column chromatography separation on the obtained crude product, eluting by using petroleum ether as an eluent, tracking the elution process by TLC, collecting the eluent containing the target product, combining the eluents, and distilling to remove the solvent to obtain the pure product. The material was a colorless liquid, 78% yield, and the product E/Z was 10/1.
example 30
photosensitizer PS5(0.015mmol,18mg), 4-phenylphenylacetylene (0.2mmol,35.6mg), hans' ester (0.24mmol,60.8mg) were added to a dry Schlenk reaction tube, nitrogen was charged three times, a solution of butyraldehyde (0.6mmol,43.3mg) and di-n-propylamine (0.6mmol,60.7mL) in 1, 4-dioxane/water (4/0.2 mL) was added under nitrogen protection (4mL), and the reaction tube was stirred under 30W blue LED illumination for 12 hours. After the reaction is finished, adding 100-200 meshes of column chromatography silica gel into the obtained reaction liquid, decompressing and distilling to remove the solvent, carrying out silica gel column chromatography separation on the obtained crude product, eluting by using petroleum ether as an eluent, tracking the elution process by TLC, collecting the eluent containing the target product, combining the eluents, and distilling to remove the solvent to obtain the pure product. The material was a colorless liquid, 79% yield, and the product E/Z was 10/1.
Example 31
Photosensitizer PS5(0.015mmol,18mg), 4-phenylphenylacetylene (0.2mmol,35.6mg), hans' ester (0.24mmol,60.8mg) were added to a dry Schlenk reaction tube, nitrogen was charged three times, a solution of butyraldehyde (0.4mmol,28.8mg) and di-n-propylamine (0.4mmol,40.5mL) in 1, 4-dioxane/water (4/0.2 mL) was added under nitrogen protection (4mL), and the reaction tube was stirred under 30W blue LED illumination for 12 hours. After the reaction is finished, adding 100-200 meshes of column chromatography silica gel into the obtained reaction liquid, decompressing and distilling to remove the solvent, carrying out silica gel column chromatography separation on the obtained crude product, eluting by using petroleum ether as an eluent, tracking the elution process by TLC, collecting the eluent containing the target product, combining the eluents, and distilling to remove the solvent to obtain the pure product. The material was a colorless liquid, 58% yield, and the product E/Z was 10/1.
Example 32
Photosensitizer PS5(0.015mmol,18mg), 4-phenylphenylacetylene (0.2mmol,35.6mg), hans' ester (0.24mmol,60.8mg) were added to a dry Schlenk reaction tube, nitrogen was charged three times, a solution of butyraldehyde (0.6mmol,43.3mg) and di-n-propylamine (0.6mmol,60.7mL) in 1, 4-dioxane/water (4/0.2 mL) was added under nitrogen protection (4mL), and the reaction tube was stirred for 8 hours under 30W blue LED illumination. After the reaction is finished, adding 100-200 meshes of column chromatography silica gel into the obtained reaction liquid, decompressing and distilling to remove the solvent, carrying out silica gel column chromatography separation on the obtained crude product, eluting by using petroleum ether as an eluent, tracking the elution process by TLC, collecting the eluent containing the target product, combining the eluents, and distilling to remove the solvent to obtain the pure product. The material was a colorless liquid, 68% yield, and the product E/Z was 10/1.
Example 32
Photosensitizer PS5(0.015mmol,18mg), 4-phenylphenylacetylene (0.2mmol,35.6mg), hans' ester (0.24mmol,60.8mg) were added to a dry Schlenk reaction tube, nitrogen was charged three times, a solution of butyraldehyde (0.6mmol,43.3mg) and di-n-propylamine (0.6mmol,60.7mL) in 1, 4-dioxane/water (4/0.2 mL) was added under nitrogen protection (4mL), and the reaction tube was stirred for 14 hours under 30W blue LED illumination. After the reaction is finished, adding 100-200 meshes of column chromatography silica gel into the obtained reaction liquid, decompressing and distilling to remove the solvent, carrying out silica gel column chromatography separation on the obtained crude product, eluting by using petroleum ether as an eluent, tracking the elution process by TLC, collecting the eluent containing the target product, combining the eluents, and distilling to remove the solvent to obtain the pure product. The material was a colorless liquid, 71% yield, and the product E/Z was 10/1.
Claims (10)
1. A method for synthesizing a 1, 2-disubstituted olefin compound by high-selectivity alkylation of alkyne is characterized by comprising the following steps: the method comprises the following steps:
Adding a photosensitizer, an alkyne compound shown in a formula I and hans ester into a Schlenk reaction tube, dissolving aldehyde and secondary amine shown in a formula II into an organic solvent or a mixed solvent of 1, 4-dioxane and water under the atmosphere of protective gas to obtain a mixed solution, adding the mixed solution into the Schlenk reaction tube under the condition of protective gas, stirring and reacting for 6-14 hours (preferably 12 hours) at 25 ℃ under the irradiation of a light source to obtain a reaction solution, and carrying out post-treatment on the reaction solution to obtain a 1, 2-disubstituted alkene compound shown in a formula III; the quantity ratio of the photosensitizer, the alkyne shown in the formula I, the hans ester, the aldehyde shown in the formula II and the secondary amine is 0.025-0.1:1:0.5-1.5:2-5: 2-5;
The photosensitizer has one of the following structures:
formula I or formula III:
R1Is composed of One of (1);
R2Is one of H, Ph or 4-bromopinenyl;
R3Is H, Me, Et, n-Pr, n-Bu, n-pentanyl,Bn、i-Pr、One kind of (1).
2. The method of claim 1, wherein: the secondary amine is one of the following structures:
3. The method of claim 2, wherein: the secondary amine is di-n-propylamine.
4. The method of claim 1, wherein: the photosensitizer is
5. The method of claim 1, wherein: the organic solvent is one of acetonitrile, tetrahydrofuran, 1, 2-dichloroethane, N-dimethylformamide, 1, 4-dioxane, dimethyl sulfoxide, dichloromethane, cyclopentyl methyl ether, trifluorotoluene and ethyl acetate.
6. The method of claim 1, wherein: the organic solvent is a mixed solvent of 1, 4-dioxane and water in a volume ratio of 20: 1.
7. The method of claim 1, wherein: the total amount of the organic solvent added is 20mL/mmol based on the amount of the substance of the alkyne compound shown in the formula I.
8. The method of claim 1, wherein: the light source is one of a 15W blue LED, a 30W blue LED, a 60W CFL or a 20W white LED.
9. The method of claim 1, wherein: the protective gas is one of nitrogen or argon.
10. the method of claim 1, wherein: the post-treatment method of the reaction solution comprises the following steps: and after the reaction is finished, adding 100-200 meshes of column chromatography silica gel into the obtained reaction liquid, carrying out reduced pressure distillation to remove the solvent, carrying out silica gel column chromatography separation on the obtained crude product, eluting by using petroleum ether as an eluent, tracking the elution process by TLC, collecting the eluent containing the target product, combining the eluents, and distilling off the solvent to obtain the 1, 2-disubstituted olefin compound shown in the formula III.
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112441936A (en) * | 2019-08-27 | 2021-03-05 | 浙江工业大学 | Method for synthesizing enaminone compounds |
CN112441935A (en) * | 2019-08-27 | 2021-03-05 | 浙江工业大学 | Synthesis method of beta-aminoketone compound |
CN112441940A (en) * | 2019-08-27 | 2021-03-05 | 浙江工业大学 | Method for synthesizing trifluoroethoxy alkene iodine compound |
CN115536505A (en) * | 2022-07-01 | 2022-12-30 | 湖南大学 | Copper-catalyzed regioselective iodination of terminal alkynes to (E) -beta-iodo-alpha, beta-unsaturated aldehydes |
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104130238A (en) * | 2014-08-04 | 2014-11-05 | 河南省科学院化学研究所有限公司 | Preparation method of rotigotine |
WO2014181362A1 (en) * | 2013-05-09 | 2014-11-13 | Council Of Scientific & Industrial Research | A process for the preparation of 3-aryl-2-hydroxy propanoic acid compounds |
CN104230734A (en) * | 2013-06-20 | 2014-12-24 | 中国科学院理化技术研究所 | Synthesis method for alpha-alkylation by visible light catalysis of secondary amine |
CN108658717A (en) * | 2018-06-08 | 2018-10-16 | 滁州学院 | A kind of decarboxylic reaction prepares the synthetic method of three substituted olefines |
-
2019
- 2019-08-28 CN CN201910799627.0A patent/CN110563535B/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014181362A1 (en) * | 2013-05-09 | 2014-11-13 | Council Of Scientific & Industrial Research | A process for the preparation of 3-aryl-2-hydroxy propanoic acid compounds |
CN104230734A (en) * | 2013-06-20 | 2014-12-24 | 中国科学院理化技术研究所 | Synthesis method for alpha-alkylation by visible light catalysis of secondary amine |
CN104130238A (en) * | 2014-08-04 | 2014-11-05 | 河南省科学院化学研究所有限公司 | Preparation method of rotigotine |
CN108658717A (en) * | 2018-06-08 | 2018-10-16 | 滁州学院 | A kind of decarboxylic reaction prepares the synthetic method of three substituted olefines |
Non-Patent Citations (2)
Title |
---|
THOMAS P. NICHOLLS ET AL.: "Identifying the potential of pulsed LED irradiation in synthesis: copper-photocatalysed C–F functionalisation", 《CHEM. COMMUN》 * |
XUAN-HUI OUYANG ET AL.: "Metal-Free Oxidative Decarbonylative Hydroalkylation of Alkynes with Secondary and Tertiary Alkyl Aldehydes", 《ADV. SYNTH. CATAL》 * |
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