CN116332900A - Olefin compound and synthesis method thereof - Google Patents

Olefin compound and synthesis method thereof Download PDF

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CN116332900A
CN116332900A CN202111589902.XA CN202111589902A CN116332900A CN 116332900 A CN116332900 A CN 116332900A CN 202111589902 A CN202111589902 A CN 202111589902A CN 116332900 A CN116332900 A CN 116332900A
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vinyl
sulfone
alcohol
phosphine
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吴雪松
郭红梅
何斌卿
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Huazhong University of Science and Technology
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Huazhong University of Science and Technology
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    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
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    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
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    • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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Abstract

The invention discloses an olefin compound and a synthesis method thereof. The method comprises the following steps: under the protection of inert gas, dissolving alcohol and alkali in a first organic solvent, adding carbon disulfide at the temperature of 0-26 ℃ to enable the alcohol and the carbon disulfide to generate xanthate in situ, and then removing the organic solvent in vacuum; wherein the alcohol does not include a group having an active hydrogen at the a-position; adding a sulfone compound, a trivalent phosphine compound, a second organic solvent and a drying agent into the xanthate serving as an alkyl radical precursor under the protection of inert gas; under the condition of the temperature of 26-60 ℃, under the irradiation of visible light, the alkyl radical precursor and the sulfone compound are subjected to radical coupling reaction to obtain an olefin compound; the sulfone compound is alkenyl sulfone or allyl sulfone. Under the condition of no photocatalyst, the invention directly excites xanthate anions generated in situ by alcohol and carbon disulfide through visible light, and realizes the synthesis of olefin compounds under the action of trivalent phosphine.

Description

Olefin compound and synthesis method thereof
Technical Field
The invention belongs to the technical field of synthesis of olefin compounds, and in particular relates to an olefin compound and a synthesis method thereof.
Background
Alkyl radicals are one of the most important intermediates in organic synthesis. In the last decade, visible light driven photochemical strategies have become powerful tools for obtaining alkyl radicals, allowing various chemical transformations to be achieved under mild conditions. Unlike photoredox catalysis and methods involving electron donor-acceptor (EDA) complex formation, the direct excitation of the alkyl source by visible light is the most direct way to provide alkyl radicals. However, most organic molecules are not absorbed in the visible region, and therefore this strategy has not been developed until recently the advent of directly visible-excitable reducing alkyl radical precursors. Melchiorre discloses that 4-alkyl-1, 4-dihydropyridines can be directly excited under irradiation with visible light to provide alkyl radicals. Ohmiya and its co-workers disclose visible light excitation of alkyl borates based on tridentate ligands. The excited states of these precursors exhibit very strong reducing power and thus the conversion of the two intermediates subsequently produced can take place by Single Electron Transfer (SET) while activating another reaction substrate and generating alkyl radicals. In addition to the strong reduction potential, the independence of photoexcitation makes the SET pathway of such reactant direct excitation methods more flexible than the EDA pathway, providing a simple no-photocatalyst strategy for the conversion of alkyl radicals involved. Nevertheless, the presently disclosed methods still have limitations: (1) 4-alkyl-1, 4-dihydropyridines are not suitable for generating unstable primary alkyl radicals; (2) Alkyl borates based on tridentate ligands exhibit limited functional group tolerance to alkyl structures or require cumbersome preparation. Thus, developing a new class of readily available, visible light-excitable precursors with strong reducing power, suitable for generating structurally diverse alkyl radicals from abundant and readily available raw materials, remains an urgent and challenging task.
Alcohol compounds constitute an attractive target for exploring the source of alkyl radicals due to their abundance. Although under the catalysis of photo-redox, C (sp) of alcohol is realized through oxidation-reduction prosthetic group activation or phosphine-mediated deoxidization reaction 3 ) O bond homolysis has been widely developed, but these catalytic systems are generally not suitable for generating unstable primary alkyl radicals. To address this long-standing challenge, macMillan recently disclosed a method of activating alcohols with benzoxazole salts. Meanwhile, the subject group of the present inventors discloses a one-pot strategy using xanthates as alcohol activating groups to provide alkyl radicals for Giese reactions under photo-redox catalysis. Both of these processes provide an efficient method for obtaining alkyl radicals from a wide range of primary, secondary and tertiary alcohols; however, the use of expensive iridium catalysts in these strategies has prompted us to develop a cost-effective and practical alcohol activation strategy that is devoid of a catalyst.
Disclosure of Invention
Aiming at the defects or improvement demands of the prior art, the invention provides an olefin compound and a synthesis method thereof, which aim to directly excite xanthate anions generated in situ by alcohol and carbon disulfide through visible light under the condition of not using a photocatalyst, and realize the synthesis of the olefin compound under the action of trivalent phosphine. Thus solving the technical problem that an expensive catalyst is necessary to be adopted in the current synthesis method.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for promoting synthesis of an olefin compound from an alcohol by visible light, the method comprising the steps of:
(1) Under the protection of inert gas, dissolving alcohol and alkali in a first organic solvent, adding carbon disulfide at the temperature of 0-26 ℃ to enable the alcohol and the carbon disulfide to generate xanthate in situ, and then removing the organic solvent in vacuum; wherein the alcohol does not include a group having an active hydrogen at the a-position;
(2) Adding a sulfone compound, a trivalent phosphine compound, a second organic solvent and a drying agent into the xanthate serving as an alkyl radical precursor under the protection of inert gas;
(3) Under the condition of the temperature of 26-60 ℃, under the irradiation of visible light, the alkyl radical precursor and the sulfone compound are subjected to radical coupling reaction to obtain an olefin compound; wherein the sulfone compound is alkenyl sulfone or allyl sulfone.
Here, the visible light may be, for example, blue light having a wavelength of 400 to 480 nm.
Preferably, the first organic solvent in the step (1) is one of tetrahydrofuran, petroleum ether, isopropyl ether, diethyl ether, dichloromethane, n-pentane, n-hexane, cyclohexane and 1, 4-dioxane.
Preferably, the base is one of cesium carbonate, cesium fluoride, sodium hydroxide, sodium carbonate, sodium acetate, sodium bicarbonate, sodium hydride, potassium phosphate, potassium hydroxide, potassium carbonate, potassium tert-butoxide, sodium tert-butoxide, lithium tert-butoxide, triethylamine, diisopropylethylamine, and potassium bis (trimethylsilyl) amide, and preferably, the base is one of potassium tert-butoxide, sodium tert-butoxide, lithium tert-butoxide, triethylamine, diisopropylethylamine, and potassium bis (trimethylsilyl) amide.
Preferably, the second organic solvent in the step (2) is at least one of methanol, trifluoroethanol, N-hexane, acetonitrile, dimethyl sulfoxide, diethyl ether, N-dimethylformamide, N-dimethylacetamide, ethylene glycol dimethyl ether, tetrahydrofuran, benzotrifluoride, dichloromethane, trichloromethane, and 1, 4-dioxane; preferably, the second organic solvent in the step (2) is at least two of methanol, n-hexane, acetonitrile, ethylene glycol dimethyl ether and 1, 4-dioxane.
Preferably, the phosphine compound is a trialkylphosphine, triarylphosphine, phosphite or phosphoramidite; preferably, the phosphine compound is one of tricyclohexylphosphine, tributylphosphine, triisopropylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, tris (4-methoxyphenyl) phosphine, tris (2-methoxyphenyl) phosphine, triethyl phosphite, triphenyl phosphite, tris (pentafluorophenyl) phosphine, and hexaethylphosphorous triamine, and preferably, the phosphine compound is one of tricyclohexylphosphine, tributylphosphine, diphenylcyclohexylphosphine, tris (4-methylphenyl) phosphine, tris (4-methoxyphenyl) phosphine, and triethyl phosphite.
Preferably, the alkenyl sulfone is (2- (arylsulfonyl) vinyl) benzene, (2- (alkylsulfonyl) vinyl) benzene or (2- (alkylsulfonyl) vinyl) arene; the allyl sulfone is one of (3- (arylsulfonyl) -2-aryl-1-propene, 2- ((alkylsulfonyl) methyl) acrylate, 2- ((arylsulfonyl) methyl) acrylate or 2- ((arylsulfonyl) methyl) acrylonitrile, preferably the alkenyl sulfone is (2- (phenylsulfonyl) vinyl) benzene, 1-methyl-4- (2- (phenylsulfonyl) vinyl) benzene, 1-fluoro-4- (2- (phenylsulfonyl) vinyl) benzene, 1-chloro-4- (2- (phenylsulfonyl) vinyl) benzene, 1-methoxy-4- (2- (phenylsulfonyl) vinyl) benzene, 1- (tert-butyl) -4- (2- (phenylsulfonyl) vinyl) benzene, 2- (2- (phenylsulfonyl) vinyl) naphthalene, (2- (methylsulfonyl) vinyl) benzene, (2- (propylsulfonyl) vinyl) benzene, and the allyl sulfone is (3- (methylsulfonyl) -2-phenyl-propene, 2- ((methylsulfonyl) methyl) acrylate or 2- ((benzenesulfonyl) methyl) acrylonitrile.
Preferably, the desiccant is
Figure BDA0003429500230000042
Molecular sieves, & gt>
Figure BDA0003429500230000043
Molecular sieves, & gt>
Figure BDA0003429500230000044
One of molecular sieve, sodium sulfate and magnesium sulfate; the wavelength of the visible light is 400-500nm.
Preferably, the mol ratio of the alcohol, the alkali, the carbon disulfide, the sulfone compound to the phosphinous compound is 1 (1.0-1.1): 1.0-5.0): 1.0-3.5): 1.0-3.0.
According to another aspect of the present invention, there is provided an olefinic compound.
Preferably, the compound is represented by the following formula I:
Figure BDA0003429500230000041
wherein R is 1 Is an alkyl, benzyl or allyl group containing no active hydrogen in the a position;
R 2 is aryl, naphthyl or heteroaryl;
R 3 is hydrogen, methyl, ester, cyano, aryl or alkyl.
In general, the above technical solutions conceived by the present invention can achieve at least the following advantageous effects compared to the prior art.
(1) In the invention, xanthate generated in situ by alcohol and carbon disulfide is firstly provided as an alkyl radical precursor and is directly used for activating a C-O bond, and under the condition of no use of a photocatalyst, xanthate anions are directly excited by visible light, and the synthesis of olefin compounds is realized under the action of trivalent phosphine.
Specifically, the reaction mechanism in the invention is as follows: the method comprises the steps of directly exciting xanthate anions generated in situ under the action of alkali by alcohol and carbon disulfide to reach an excited state under the irradiation of visible light, then carrying out single electron transfer with alkenyl sulfone or allyl sulfone to generate free radical species with sulfur as a center, then combining with trivalent phosphorus, removing a phosphine sulfide compound to generate alkoxythiocarbonyl free radicals, losing one molecule of carbonyl sulfide to obtain alkyl free radicals, carrying out conjugate addition on the alkyl free radicals and vinyl sulfone or allyl sulfone, and then eliminating sulfinyl free radicals to obtain the olefin compound.
Solves the technical problems that the substrate structure is generally limited, the method is not suitable for generating primary alkyl free radicals and expensive photocatalyst is necessary to be used in the reaction in the prior art.
(2) In the invention, preferably one of potassium tert-butoxide, sodium tert-butoxide, lithium tert-butoxide, triethylamine, diisopropylethylamine and bis (trimethylsilyl) aminopotassium is used as a base, and the solubility of the base in a nonpolar organic solvent is good, and under the same condition, the reaction yield can be higher than 70%.
(3) In the present invention, one of tricyclohexylphosphine, tributylphosphine, diphenylcyclohexylphosphine, tris (4-methylphenyl) phosphine, tris (4-methoxyphenyl) phosphine, triethyl phosphite is preferably used as the phosphine compound, since these phosphine compounds can give a reaction yield of more than 70% as a preferable sulfur capturing agent. In the invention, the mixed organic solvent is preferably 1,4-dioxane, ethylene glycol dimethyl ether and acetonitrile, so that xanthate can be better dissolved, and the reaction yield can be higher than 70%.
(4) The molar ratio of alcohol, base, carbon disulphide to alkenyl sulphone or allyl sulphone, trivalent phosphorus compound is defined in the present invention. If the amount of the base is too small, the hydrogen of the alcohol cannot be completely extracted, resulting in a decrease in the amount of xanthate to be produced, thereby decreasing the reaction yield. If the alkali is too much, the excess alkali reacts with carbon disulphide to reduce the reaction yield.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
The synthetic procedure of the present invention is represented by the following formula:
Figure BDA0003429500230000061
the specific reaction paths of the present invention are shown below, which include two possible paths:
Figure BDA0003429500230000062
in the present invention, the alcohol does not include a group having an active hydrogen at the a-position. For example, the group such as carbonyl group, sulfonyl group, cyano group, or ester group is a group having an active hydrogen at the a-position, and the alcohol in the present invention is, for example, an alcohol containing no carbonyl group, sulfonyl group, or the like. The reason is that: under alkaline conditions, alcohols containing active hydrogen groups at the a-position tend to pull off hydrogen protons at the a-position, thereby causing side reactions.
The olefin compounds prepared by the invention include, but are not limited to, the following compounds having structures shown in any one of the formulas I-1 to II-3:
Figure BDA0003429500230000071
the technical scheme of the invention is further described by a specific example:
example 1
The starting cyclohexanol (30 mg,0.30 mmol), potassium tert-butoxide (35 mg,0.32 mmol) and dried tetrahydrofuran (3.0 mL) were added sequentially under nitrogen in an oven-dried 12mL glass vial equipped with a magnetic stirrer. The reaction mixture was stirred at room temperature for 30 minutes, then CS was added via microinjection at 0 ℃ 2 (68 mg, 54. Mu.L, 0.90 mmol) and stirring at 0℃was continued for 3 hours and then the solvent was removed in vacuo. The reaction system was purged with nitrogen, and (2- (methylsulfonyl) vinyl) benzene (136 mg,0.75 mmol), tris (4-methoxyphenyl) phosphine (159 mg,0.45 mmol),
Figure BDA0003429500230000081
Molecular sieves (45 mg) and 1, 4-dioxane/ethylene glycol dimethyl ether/acetonitrile (2.0 mL/1.0mL/0.5 mL). The reaction mixture was irradiated with a 30W blue LED lamp and kept at 40 ℃ and stirred for 24 hours. Separating by column chromatography with petroleum ether/ethyl acetate (200:1),the chromatographic liquid is removed under reduced pressure to obtain the disubstituted alkene compound with the structure shown in the formula I-1, colorless liquid is obtained, and the yield is 89%.
The following is a nuclear magnetic resonance and high resolution mass spectrometry test of the product, and the results are as follows:
1 H NMR(400MHz,CDCl 3 )δ7.37(d,J＝7.3Hz,2H),7.31(t,J＝7.6Hz,2H),7.20(t,J＝7.2Hz,1H),6.37(d,J＝16.0Hz,1H),6.25–6.15(m,1H),2.20–2.09(m,1H),1.87–1.67(m,5H),1.38–1.14(m,5H). 13 C NMR(101MHz,CDCl 3 )δ138.2,137.0,128.6,127.4,126.9,126.1,41.3,33.1,26.3,26.2.HRMS(EI):m/z[M] + calcd for C 14 H 18 :186.1409,found:186.1405.
example 2
This example was conducted in the same manner as in example 1 except that the synthesis of an olefin compound was conducted in the same manner as in example 1,
the starting alcohol added was methanol (9.6 mg,0.30 mmol) and the alkenyl sulfone added was methyl 4- (2- (methylsulfonyl) vinyl) benzoate (180 mg,0.75 mmol). The disubstituted alkene compound with the structure of formula I-2 is obtained as colorless liquid with the yield of 60%.
The following is a nuclear magnetic resonance and high resolution mass spectrometry test of the product, and the results are as follows:
1 H NMR(400MHz,CDCl 3 )δ7.96(d,J＝8.3Hz,2H),7.33(d,J＝8.3Hz,2H),6.97(d,J＝15.5Hz,1H),6.29(d,J＝15.4Hz,1H),3.90(s,3H),2.41(s,3H). 13 C NMR(101MHz,CDCl 3 )δ167.0,141.6,130.2,129.7,129.5,128.5,128.0,125.2,124.3,123.3,52.2,14.8.HRMS(EI):m/z[M+H]+calcd for C 11 H 13 O 2 :177.0910,found:177.0905.
example 3
This example was conducted in the same manner as in example 1 except that the synthesis of an olefin compound was conducted in the same manner as in example 1,
the starting alcohol added was cyclohexylmethanol (34 mg,0.30 mmol) and the alkenyl sulfone added was methyl 4- (2- (methylsulfonyl) vinyl) benzoate (180 mg,0.75 mmol). The disubstituted alkene compound I-3 with the structure shown in the formula I-3 is obtained as colorless liquid, and the yield is 91%.
The following is a nuclear magnetic resonance and high resolution mass spectrometry test of the product, and the results are as follows:
1 H NMR(400MHz,CDCl 3 )δ7.95(d,J＝8.4Hz,2H),7.38(d,J＝8.3Hz,2H),6.42–6.30(m,2H),3.90(s,3H),2.12(t,J＝6.1Hz,2H),1.81–1.61(m,5H),1.46–1.34(m,1H),1.30–1.09(m,3H),1.00–0.90(m,2H). 13 C NMR(101MHz,CDCl 3 )δ167.1,142.5,133.0,130.1,130.0,128.3,125.8,52.1,41.3,38.2,33.3,26.6,26.4.HRMS(EI):m/z[M+Na] + calcd for C 17 H 22 O 2 Na:281.1512,found:281.1518.
example 4
This example was conducted in the same manner as in example 1 except that the synthesis of an olefin compound was conducted in the same manner as in example 1,
the starting alcohol was 2, 2-dimethyl-1-propanol (24 mg,0.30 mmol) and the alkenyl sulfone was methyl 4- (2- (methylsulfonyl) vinyl) benzoate (180 mg,0.75 mmol) to give a disubstituted alkene compound of formula I-4 as a colorless liquid in 60% yield.
The following is a nuclear magnetic resonance and high resolution mass spectrometry test of the product, and the results are as follows:
1 H NMR(400MHz,CDCl 3 )δ7.96(d,J＝8.5Hz,2H),7.40(d,J＝8.4Hz,2H),6.39(d,J＝3.4Hz,2H),3.90(s,3H),2.17–2.05(m,2H),0.95(s,9H). 13 C NMR(101MHz,CDCl3)δ167.1,142.5,131.5,131.2,130.0,128.4,126.0,52.1,47.8,31.7,29.6.HRMS(EI):m/z[M+H] + calcd for C 15 H 21 O 2 :233.1536,found:233.1532.
example 5
This example was conducted in the same manner as in example 1 except that the synthesis of an olefin compound was conducted in the same manner as in example 1,
the added raw material alcohol is tetrahydrofurfuryl alcohol (31 mg,0.30 mmol), the added alkenyl sulfone is 4- (2- (methylsulfonyl) vinyl) methyl benzoate (180 mg,0.75 mmol), the column chromatography separation is carried out by petroleum ether/ethyl acetate (30:1), and the chromatographic liquid is removed under reduced pressure, thus obtaining the disubstituted alkene compound with the structure shown in formula I-5, which is a white solid with the yield of 60%.
The following is a nuclear magnetic resonance and high resolution mass spectrometry test of the product, and the results are as follows:
1 H NMR(400MHz,CDCl 3 )δ7.96(d,J＝8.5Hz,2H),7.40(d,J＝8.4Hz,2H),6.49(d,J＝16.0Hz,1H),6.42–6.35(m,1H),4.01–3.93(m,1H),3.90(s,4H),3.78–3.71(m,1H),2.55–2.37(m,2H),2.05–1.98(m,1H),1.96–1.82(m,2H),1.63–1.48(m,1H). 13 C NMR(101MHz,CDCl 3 )δ167.1,142.2,131.2,130.1,130.0,128.6,126.1,78.7,68.1,52.1,39.4,31.1,25.8.HRMS(EI):m/z[M+Na] + calcd for C 15 H 18 O 3 Na:269.1148,found:269.1145.
example 6
This example was conducted in the same manner as in example 1 except that the synthesis of an olefin compound was conducted in the same manner as in example 1,
the added raw material alcohol is N-Boc-4-piperidinemethanol (65 mg,0.30 mmol), the added alkenyl sulfone is methyl 4- (2- (methylsulfonyl) vinyl) benzoate (180 mg,0.75 mmol) and is separated by column chromatography with petroleum ether/ethyl acetate (30:1), and the chromatographic liquid is removed under reduced pressure to obtain the disubstituted alkene compound with the structure shown in the formula I-6, which is a white solid with the yield of 77%.
The following is a nuclear magnetic resonance and high resolution mass spectrometry test of the product, and the results are as follows:
1 H NMR(400MHz,CDCl 3 )δ7.95(d,J＝8.2Hz,2H),7.37(d,J＝8.3Hz,2H),6.40(d,J＝15.9Hz,1H),6.30(m,J＝15.8,7.0Hz,1H),4.07(s,2H),3.89(s,3H),2.67(t,J＝12.7Hz,2H),2.17(t,J＝6.9Hz,2H),1.69(d,J＝13.1Hz,2H),1.62–1.50(m,1H),1.44(s,9H),1.21–1.07(m,2H). 13 C NMR(101MHz,CDCl 3 )δ167.0,155.0,142.1,131.5,130.9,130.0,128.5,125.9,79.4,52.1,43.9,40.2,36.4,32.1,28.6.HRMS(EI):m/z[M+Na] + calcd for C 21 H 29 NO 4 Na:382.1989,found:382.1987.
example 7
This example was conducted in the same manner as in example 1 except that the synthesis of an olefin compound was conducted in the same manner as in example 1,
the added raw material alcohol is 3-methoxy-1-propanol (27 mg,0.30 mmol), the added alkenyl sulfone is 4- (2- (methylsulfonyl) vinyl) methyl benzoate (180 mg,0.75 mmol), column chromatography separation is carried out by petroleum ether/ethyl acetate (30:1), and the chromatographic liquid is removed under reduced pressure to obtain the disubstituted alkene compound with the structure shown in formula I-7, which is a white solid with the yield of 75%.
The following is a nuclear magnetic resonance and high resolution mass spectrometry test of the product, and the results are as follows:
1 H NMR(400MHz,CDCl 3 )δ7.96(d,J＝8.5Hz,2H),7.39(d,J＝8.3Hz,2H),6.44(d,J＝15.9Hz,1H),6.39–6.32(m,1H),3.90(s,3H),3.42(t,J＝6.4Hz,2H),3.35(s,3H),2.36–2.25(m,2H),1.80–1.73(m,2H). 13 C NMR(101MHz,CDCl 3 )δ167.0,142.3,133.3,130.0,129.6,128.4,125.9,72.1,58.7,52.1,29.8,29.2.HRMS(EI):m/z[M+H] + calcd for C 14 H 19 O 3 :235.1329,found:235.1329.
example 8
This example was conducted in the same manner as in example 1 except that the synthesis of an olefin compound was conducted in the same manner as in example 1,
the added raw material alcohol is 3-methylthiopropanol (32 mg,0.30 mmol), the added alkenyl sulfone is 4- (2- (methylsulfonyl) vinyl) methyl benzoate (180 mg,0.75 mmol) and is separated by column chromatography with petroleum ether/ethyl acetate (30:1), and the chromatographic liquid is removed under reduced pressure to obtain the disubstituted alkene compound with the structure shown in formula I-8, which is a white solid with the yield of 70%.
The following is a nuclear magnetic resonance and high resolution mass spectrometry test of the product, and the results are as follows:
1 H NMR(400MHz,CDCl 3 )δ7.96(d,J＝8.1Hz,2H),7.39(d,J＝8.1Hz,2H),6.45(d,J＝15.9Hz,1H),6.37–6.30(m,1H),3.90(s,3H),2.55(t,J＝7.3Hz,2H),2.35(q,J＝7.1Hz,2H),2.11(s,3H),1.84–1.73(m,2H). 13 C NMR(101MHz,CDCl 3 )δ167.1,142.2,132.8,130.0,130.0,128.5,125.9,52.1,33.8,32.2,28.6,15.6.HRMS(EI):m/z[M+H] + calcd for C 14 H 19 O 2 S:251.1100,found:251.1103.
example 9
This example was conducted in the same manner as in example 1 except that the synthesis of an olefin compound was conducted in the same manner as in example 1,
the added raw material alcohol is 2- (trimethylsilyl) ethanol (35 mg,0.30 mmol), the added alkenyl sulfone is 4- (2- (methylsulfonyl) vinyl) methyl benzoate (180 mg,0.75 mmol) and is separated by column chromatography by petroleum ether/ethyl acetate (30:1), and the chromatographic liquid is removed under reduced pressure to obtain the disubstituted alkene compound with the structure shown in formula I-9, wherein the colorless liquid has the yield of 70%.
The following is a nuclear magnetic resonance and high resolution mass spectrometry test of the product, and the results are as follows:
1 H NMR(400MHz,CDCl 3 )δ7.97(d,J＝8.3Hz,2H),7.39(d,J＝8.3Hz,2H),6.41(d,J＝2.5Hz,2H),3.91(s,3H),2.31–2.19(m,2H),0.75–0.64(m,2H),0.04(s,9H). 13 C NMR(101MHz,CDCl 3 )δ167.1,142.7,136.9,130.0,128.3,127.7,125.8,52.1,27.6,16.2,-1.5.HRMS(EI):m/z[M+H] + calcd for C 15 H 23 O 2 Si:263.1462,found:263.1457.
example 10
This example was conducted in the same manner as in example 1 except that the synthesis of an olefin compound was conducted in the same manner as in example 1,
the starting alcohol added was 4, 4-trifluoro-1-butanol (38 mg,0.30 mmol) and the alkenyl sulfone added was methyl 4- (2- (methylsulfonyl) vinyl) benzoate (180 mg,0.75 mmol) to give the disubstituted alkene compound of formula I-10 as a colorless liquid in 83% yield.
The following is a nuclear magnetic resonance and high resolution mass spectrometry test of the product, and the results are as follows:
1 H NMR(400MHz,CDCl 3 )δ7.97(d,J＝8.1Hz,2H),7.39(d,J＝8.2Hz,2H),6.45(d,J＝15.9Hz,1H),6.33–6.25(m,1H),3.90(s,3H),2.32(q,J＝7.2Hz,2H),2.20–2.04(m,2H),1.83–1.70(m,2H). 13 C NMR(101MHz,CDCl 3 )δ167.0,141.9,131.8,130.6,130.0,128.8,127.3(q,J＝277.8Hz),126.0,52.1,33.2(q,J＝28.5Hz),32.0,21.5(q,J＝2.8Hz). 19 F NMR(376MHz,CDCl 3 )δ-66.23(t,J＝10.9Hz).HRMS(EI):m/z[M+H] + calcd for C 14 H 16 F 3 O 2 :273.1097,found:273.1099.
example 11
This example was conducted in the same manner as in example 1 except that the synthesis of an olefin compound was conducted in the same manner as in example 1,
the starting alcohol added was 4-penten-1-ol (26 mg,0.30 mmol) and the alkenyl sulfone added was methyl 4- (2- (methylsulfonyl) vinyl) benzoate (180 mg,0.75 mmol) to give a disubstituted alkene compound of formula I-11 as a colorless liquid in 70% yield.
The following is a nuclear magnetic resonance and high resolution mass spectrometry test of the product, and the results are as follows:
1 H NMR(400MHz,CDCl 3 )δ7.96(d,J＝8.1Hz,2H),7.39(d,J＝8.3Hz,2H),6.42(d,J＝16.0Hz,1H),6.38–6.31(m,1H),5.88–5.78(m,1H),5.08–4.93(m,2H),3.90(s,3H),2.25(q,J＝7.0Hz,2H),2.12(q,J＝7.1Hz,2H),1.66–1.55(m,2H). 13 C NMR(101MHz,CDCl 3 )δ167.1,142.5,138.6,133.8,130.0,129.5,128.4,125.9,114.9,52.1,33.4,32.6,28.5.HRMS(EI):m/z[M+H] + calcd for C 15 H 18 O 2 Na:253.1199,found:253.1197.
example 12
This example was conducted in the same manner as in example 1 except that the synthesis of an olefin compound was conducted in the same manner as in example 1,
the starting alcohol added was benzyl alcohol (32 mg,0.30 mmol) and the alkenyl sulfone added was methyl 4- (2- (methylsulfonyl) vinyl) benzoate (180 mg,0.75 mmol), giving a disubstituted alkene compound of formula I-12 as a colorless liquid in 89% yield.
The following is a nuclear magnetic resonance and high resolution mass spectrometry test of the product, and the results are as follows:
1 H NMR(400MHz,CDCl 3 )δ7.96(d,J＝8.1Hz,2H),7.39(d,J＝8.1Hz,2H),7.32(t,J＝7.5Hz,2H),7.24(d,J＝7.1Hz,3H),6.54–6.41(m,2H),3.89(s,3H),3.57(d,J＝4.6Hz,2H). 13 C NMR(101MHz,CDCl 3 )δ167.1,142.1,139.7,132.3,130.3,130.0,128.8,128.7,128.4,126.5,126.1,52.1,39.5.HRMS(EI):m/z[M+H] + calcd for C 17 H 17 O 2 :253.1123,found:253.1224.
example 13
This example was conducted in the same manner as in example 1 except that the synthesis of an olefin compound was conducted in the same manner as in example 1,
the starting alcohol added was 1-pyrenylmethanol (70 mg,0.30 mmol) and the alkenyl sulfone added was methyl 4- (2- (methylsulfonyl) vinyl) benzoate (180 mg,0.75 mmol) to give the disubstituted alkene compound of formula I-13 as a white solid in 42% yield.
The following is a nuclear magnetic resonance and high resolution mass spectrometry test of the product, and the results are as follows:
1 H NMR(400MHz,CDCl 3 )δ8.26(d,J＝9.2Hz,1H),8.20–8.07(m,4H),8.04(s,2H),7.99(t,J＝7.6Hz,1H),7.90(d,J＝8.0Hz,3H),7.33(d,J＝8.4Hz,2H),6.75–6.68(m,1H),6.42(d,J＝15.9Hz,1H),4.27(d,J＝5.9Hz,2H),3.87(s,3H). 13 C NMR(101MHz,CDCl 3 )δ167.1,142.0,133.4,132.3,131.5,131.0,130.5,130.4,130.0,129.1,128.7,127.7,127.7,127.6,127.1,126.1,126.1,125.2,125.2,125.1,125.1,125.0,123.5,52.1,37.0.HRMS(EI):m/z[M+H] + calcd for C 27 H 21 O 2 :377.1536,found:377.1536.
example 14
This example was conducted in the same manner as in example 1 except that the synthesis of an olefin compound was conducted in the same manner as in example 1,
the added raw material alcohol is N-Boc-4-phenethyl alcohol (71 mg,0.30 mmol), the added alkenyl sulfone is methyl 4- (2- (methylsulfonyl) vinyl) benzoate (180 mg,0.75 mmol), the mixture is subjected to column chromatography separation by petroleum ether/ethyl acetate (30:1), and the chromatographic liquid is removed under reduced pressure to obtain the disubstituted alkene compound with the structure shown in the formula I-14, which is a white solid with the yield of 65%.
The following is a nuclear magnetic resonance and high resolution mass spectrometry test of the product, and the results are as follows:
1 H NMR(400MHz,CDCl 3 )δ7.95(d,J＝8.1Hz,2H),7.35(d,J＝8.1Hz,2H),7.30(d,J＝8.1Hz,2H),7.12(d,J＝8.2Hz,2H),6.65(s,1H),6.45–6.28(m,2H),3.89(s,3H),2.73(t,J＝7.6Hz,2H),2.50(q,J＝6.7Hz,2H),1.50(s,9H). 13 C NMR(101MHz,CDCl 3 )δ167.1,153.0,142.3,136.4,136.1,133.0,129.9,129.7,128.9,128.4,125.9,118.8,80.4,52.1,35.0,35.0,28.4.IR(ATR):3374,1702,1518,1411,1273,1235,1162,1106,1055,969,827,766,726,618cm -1 .HRMS(EI):m/z[M+Na] + calcd for C 23 H 27 NO 4 Na:404.1832,found:404.1835.
example 15
This example was conducted in the same manner as in example 1 except that the synthesis of an olefin compound was conducted in the same manner as in example 1,
the added raw material alcohol is 3-thiopheneethanol (38 mg,0.30 mmol), the added alkenyl sulfone is 4- (2- (methylsulfonyl) vinyl) methyl benzoate (180 mg,0.75 mmol), the mixture is subjected to column chromatography separation by petroleum ether/ethyl acetate (30:1), and the chromatographic liquid is removed under reduced pressure to obtain the disubstituted alkene compound with the structure shown in the formula I-15, which is a white solid with the yield of 72%.
The following is a nuclear magnetic resonance and high resolution mass spectrometry test of the product, and the results are as follows:
1 H NMR(400MHz,CDCl 3 )δ7.96(d,J＝8.1Hz,2H),7.37(d,J＝8.1Hz,2H),7.26–7.22(m,1H),6.97(d,J＝5.1Hz,2H),6.44(d,J＝16.0Hz,1H),6.40–6.33(m,1H),3.89(s,3H),2.82(t,J＝7.7Hz,2H),2.56(q,J＝6.8Hz,2H). 13 C NMR(101MHz,CDCl 3 )δ167.0,142.3,141.9,132.9,130.0,129.9,128.5,128.2,125.9,125.5,120.4,52.1,34.1,30.0.HRMS(EI):m/z[M+H] + calcd for C 16 H 17 O 2 S:273.0944,found:273.0940.
example 16
This example was conducted in the same manner as in example 1 except that the synthesis of an olefin compound was conducted in the same manner as in example 1,
the added raw material alcohol is 1- (3-hydroxypropyl) pyrazole (38 mg,0.30 mmol), the added alkenyl sulfone is 4- (2- (methylsulfonyl) vinyl) methyl benzoate (180 mg,0.75 mmol), the column chromatography separation is carried out by petroleum ether/ethyl acetate (30:1), and the chromatographic liquid is removed under reduced pressure to obtain the disubstituted alkene compound with the structure shown in the formula I-16, which is a white solid with the yield of 68%.
The following is a nuclear magnetic resonance and high resolution mass spectrometry test of the product, and the results are as follows:
1 H NMR(400MHz,CDCl 3 )δ7.96(d,J＝8.1Hz,2H),7.52(s,1H),7.37(d,J＝8.2Hz,3H),6.42(d,J＝15.9Hz,1H),6.34–6.27(m,1H),6.25(t,J＝2.2Hz,1H),4.18(t,J＝6.9Hz,2H),3.90(s,3H),2.24(q,J＝7.1Hz,2H),2.12–2.02(m,2H). 13 C NMR(101MHz,CDCl 3 )δ167.0,142.0,139.4,132.1,130.3,130.0,129.1,128.6,125.9,105.4,52.1,51.4,30.1,29.8.HRMS(EI):m/z[M+H] + calcd for C 16 H 19 N 2 O 2 :271.1441,found:271.1438.
example 17
This example was conducted in the same manner as in example 1 except that the synthesis of an olefin compound was conducted in the same manner as in example 1,
4-Cyanophenylpropanol (48 mg,0.3 mmol) as alcohol, methyl 4- (2- (methylsulfonyl) vinyl) benzoate (180 mg,0.75 mmol) as alkenyl sulfone (4-cyano-phenyl-propanol) and petroleum ether/ethyl acetate (30:1) were added to conduct column chromatography separation, and the chromatographic liquid was removed under reduced pressure to obtain the product I-17 as a white solid with a yield of 68%.
The following is a nuclear magnetic resonance and high resolution mass spectrometry test of the product, and the results are as follows:
1 H NMR(400MHz,CDCl 3 )δ7.97(d,J＝8.3Hz,2H),7.57(d,J＝8.2Hz,2H),7.38(d,J＝8.1Hz,2H),7.29(d,J＝8.0Hz,2H),6.43(d,J＝16.0Hz,1H),6.37–6.30(m,1H),3.90(s,3H),2.73(t,J＝7.7Hz,2H),2.28(q,J＝7.0Hz,2H),1.87–1.79(m,2H). 13 C NMR(101MHz,CDCl 3 )δ167.0,147.9,142.1,132.8,132.3,130.0,129.3,128.6,125.9,119.2,109.8,52.1,35.6,32.5,30.3.HRMS(EI):m/z[M+H] + calcd for C 20 H 20 NO 2 :306.1489,found:306.1494.
example 18
This example was conducted in the same manner as in example 1 except that the synthesis of an olefin compound was conducted in the same manner as in example 1,
the alcohol was 2-adamantanol (46 mg,0.3 mmol) and alkenyl sulfone was methyl 4- (2- (methylsulfonyl) vinyl) benzoate (180 mg,0.75 mmol) to give the product of formula I-18 as a colorless liquid in 82% yield.
The following is a nuclear magnetic resonance and high resolution mass spectrometry test of the product, and the results are as follows:
1 H NMR(400MHz,CDCl 3 )δ7.97(d,J＝8.2Hz,2H),7.42(d,J＝8.2Hz,2H),6.69–6.57(m,1H),6.48–6.39(m,1H),3.91(s,3H),2.59(d,J＝6.5Hz,1H),2.03–1.95(m,2H),1.95–1.91(m,3H),1.91–1.77(m,5H),1.76(d,J＝3.1Hz,2H),1.59(d,J＝12.1Hz,2H). 13 C NMR(101MHz,CDCl 3 )δ167.2,142.9,138.2,130.0,128.4,128.3,125.9,52.1,47.7,38.8,38.1,33.1,32.4,28.2,27.9.HRMS(EI):m/z[M+H] + calcd for C 20 H 25 O 2 :297.1849,found:297.1847.
example 19
This example was conducted in the same manner as in example 1 except that the synthesis of an olefin compound was conducted in the same manner as in example 1,
the alcohol was tetrahydrothiopyran-4-ol (35 mg,0.3 mmol) and alkenyl sulfone was methyl 4- (2- (methylsulfonyl) vinyl) benzoate (180 mg,0.75 mmol) to give the product of formula I-19 as a white solid in 71% yield.
The following is a nuclear magnetic resonance and high resolution mass spectrometry test of the product, and the results are as follows:
1 H NMR(400MHz,CDCl 3 )δ7.96(d,J＝8.1Hz,2H),7.39(d,J＝8.1Hz,2H),6.39(d,J＝16.0Hz,1H),6.30–6.20(m,1H),3.90(s,3H),2.80–2.61(m,4H),2.25–2.16(m,1H),2.14–2.04(m,2H),1.67–1.57(m,2H). 13 C NMR(101MHz,CDCl 3 )δ167.0,142.1,137.9,129.9,128.6,127.7,126.0,52.1,40.8,33.5,28.4.HRMS(EI):m/z[M+H] + calcd for C 15 H 19 O 2 S:263.1100,found:263.1104.
example 20
This example was conducted in the same manner as in example 1 except that the synthesis of an olefin compound was conducted in the same manner as in example 1,
the alcohol was added as 2-indenol (40 mg,0.3 mmol) and the alkenyl sulfone was added as methyl 4- (2- (methylsulfonyl) vinyl) benzoate (180 mg,0.75 mmol) to give the product of formula I-20 as a white solid in 87% yield.
The following is a nuclear magnetic resonance and high resolution mass spectrometry test of the product, and the results are as follows:
1 H NMR(400MHz,CDCl 3 )δ7.96(d,J＝8.1Hz,2H),7.40(d,J＝8.1Hz,2H),7.26–7.19(m,2H),7.19–7.12(m,2H),6.54–6.42(m,2H),3.89(s,3H),3.32–3.21(m,1H),3.20–3.08(m,2H),2.93–2.81(m,2H). 13 C NMR(101MHz,CDCl 3 )δ167.1,142.9,142.2,137.1,130.0,128.6,128.6,126.5,126.0,124.5,52.1,44.0,39.6.HRMS(EI):m/z[M+H] + calcd for C 19 H 19 O 2 :279.1380,found:279.1381.
example 21
This example was conducted in the same manner as in example 1 except that the synthesis of an olefin compound was conducted in the same manner as in example 1,
the alcohol was dimethylbenzene ethyl alcohol (49 mg,0.3 mmol) and alkenyl sulfone was methyl 4- (2- (methylsulfonyl) vinyl) benzoate (180 mg,0.75 mmol) to give the product of formula I-21 as a colorless liquid in 70% yield.
The following is a nuclear magnetic resonance and high resolution mass spectrometry test of the product, and the results are as follows:
1 H NMR(400MHz,CDCl 3 )δ7.97(d,J＝8.3Hz,2H),7.41(d,J＝8.3Hz,2H),7.25(d,J＝7.3Hz,2H),7.17(d,J＝6.8Hz,3H),6.36(s,2H),3.90(s,3H),2.61–2.51(m,2H),1.76–1.68(m,2H),1.18(s,6H). 13 C NMR(101MHz,CDCl 3 )δ167.1,143.2,143.0,142.6,130.0,128.5,128.4,126.0,125.8,125.7,125.7,52.1,45.2,36.9,31.4,27.2.HRMS(EI):m/z[M+H] + calcd for C 21 H 25 O 2 :309.1849,found:309.1846.
example 22
This example was conducted in the same manner as in example 1 except that the synthesis of an olefin compound was conducted in the same manner as in example 1,
the alcohol was 3-adamantanol (50 mg,0.3 mmol) and alkenyl sulfone was methyl 4- (2- (methylsulfonyl) vinyl) benzoate (180 mg,0.75 mmol) to give the product of formula I-22 as a colorless liquid in 40% yield.
The following is a nuclear magnetic resonance and high resolution mass spectrometry test of the product, and the results are as follows:
1 H NMR(400MHz,CDCl 3 )δ7.95(d,J＝8.2Hz,2H),7.40(d,J＝8.2Hz,2H),6.36–6.14(m,2H),3.90(s,3H),2.04(s,3H),1.72(d,J＝22.8Hz,12H). 13 C NMR(101MHz,CDCl 3 )δ167.2,145.0,143.0,130.0,128.3,126.0,124.1,52.1,42.2,37.0,35.6,28.5.HRMS(EI):m/z[M+H] + calcd for C 20 H 25 O 2 :297.1849,found:297.1846.
example 23
This example was conducted in the same manner as in example 1 except that the synthesis of an olefin compound was conducted in the same manner as in example 1,
the alcohol was isoprene glycol (31 mg,0.3 mmol) and alkenyl sulfone was methyl 4- (2- (methylsulfonyl) vinyl) benzoate (180 mg,0.75 mmol) to give the product of formula I-23 as a white solid with 81% yield.
The following is a nuclear magnetic resonance and high resolution mass spectrometry test of the product, and the results are as follows:
1 H NMR(400MHz,CDCl 3 )δ7.95(d,J＝8.3Hz,2H),7.37(d,J＝8.3Hz,2H),6.50–6.30(m,2H),3.89(s,3H),2.41–2.24(m,2H),1.69–1.60(m,2H),1.48(s,1H),1.26(s,6H). 13 C NMR(101MHz,CDCl 3 )δ167.1,142.4,134.0,130.0,129.2,128.4,125.9,70.9,52.1,43.1,29.4,28.2.HRMS(EI):m/z[M+H] + calcd for C 15 H 21 O 3 :249.1485,found:249.1481.
example 24
This example was conducted in the same manner as in example 1 except that the synthesis of an olefin compound was conducted in the same manner as in example 1,
2-methyl-2, 4-pentanediol (35.4 mg,0.3 mmol) was added as alcohol and methyl 4- (2- (methylsulfonyl) vinyl) benzoate (180 mg,0.75 mmol) as alkenyl sulfone was added to give the product of formula I-24 as a colorless liquid in 61% yield.
The following is a nuclear magnetic resonance and high resolution mass spectrometry test of the product, and the results are as follows:
1 H NMR(400MHz,CDCl 3 )δ7.95(d,J＝8.2Hz,2H),7.39(d,J＝8.2Hz,2H),6.43(d,J＝15.9Hz,1H),6.35–6.25(m,1H),3.90(s,3H),2.69–2.58(m,1H),1.77–1.63(m,2H),1.63–1.53(m,1H),1.24(d,J＝12.5Hz,6H),1.13(d,J＝6.7Hz,3H). 13 C NMR(101MHz,CDCl 3 )δ167.1,142.2,140.8,130.0,128.6,127.6,126.0,71.5,52.2,50.6,34.6,30.3,29.9,23.0.HRMS(EI):m/z[M+H] + calcd for C 16 H 23 O 3 :263.1642,found:263.1642.
example 25
This example was conducted in the same manner as in example 1 except that the synthesis of an olefin compound was conducted in the same manner as in example 1,
1, 3-butanediol (27 mg,0.3 mmol) was added and alkenyl sulfone methyl 4- (2- (methylsulfonyl) vinyl) benzoate (180 mg,0.75 mmol) to give the product of formula I-25 as a white solid in 64% yield.
The following is a nuclear magnetic resonance and high resolution mass spectrometry test of the product, and the results are as follows:
1 H NMR(400MHz,CDCl 3 )δ7.95(d,J＝8.2Hz,2H),7.38(d,J＝8.2Hz,2H),6.49–6.24(m,2H),3.89(s,3H),3.88–3.82(m,1H),2.45–2.20(m,2H),1.73(s,1H),1.67–1.60(m,2H),1.23(d,J＝6.2Hz,3H). 13 C NMR(101MHz,CDCl 3 )δ167.1,142.3,133.5,130.0,129.6,128.5,125.9,67.7,52.2,38.6,29.6,23.8.HRMS(EI):m/z[M+H] + calcd for C 14 H 19 O 3 :235.1329,found:235.1326.
example 26
This example was conducted in the same manner as in example 1 except that the synthesis of an olefin compound was conducted in the same manner as in example 1,
the alcohol was methyl-2, 3-O-isopropylidene-beta-D-ribofuranoside (61 mg,0.3 mmol) and alkenyl sulfone was methyl 4- (2- (methylsulfonyl) vinyl) benzoate (180 mg,0.75 mmol) to give the product of formula I-26 as a white solid in 50% yield.
The following is a nuclear magnetic resonance and high resolution mass spectrometry test of the product, and the results are as follows:
1 H NMR(600MHz,CDCl 3 )δ7.98–7.94(m,2H),7.40(d,J＝8.3Hz,2H),6.50(d,J＝15.9Hz,1H),6.33(d,J＝15.9Hz,1H),4.98(s,1H),4.64(d,J＝5.9Hz,1H),4.61(d,J＝5.9Hz,1H),4.33(s,1H),3.90(s,3H),3.36(s,3H),2.63–2.55(m,1H),2.52–2.44(m,1H),1.48(s,3H),1.31(s,3H). 13 C NMR(151MHz,CDCl 3 )δ167.0,141.9,131.9,130.0,129.1,128.9,126.1,112.5,109.7,86.6,85.7,83.6,55.1,52.2,38.9,26.6,25.2.HRMS(EI):m/z[M+H] + calcd for C 19 H 25 O 6 :349.1646,found:349.1648.
example 27
This example was conducted in the same manner as in example 1 except that the synthesis of an olefin compound was conducted in the same manner as in example 1,
the alcohol was diacetone galactose (78 mg,0.3 mmol) and the alkenyl sulfone was methyl 4- (2- (methylsulfonyl) vinyl) benzoate (180 mg,0.75 mmol) to give the product of formula I-27 as a white solid in 52% yield.
The following is a nuclear magnetic resonance and high resolution mass spectrometry test of the product, and the results are as follows:
1 H NMR(400MHz,CDCl 3 )δ7.96(d,J＝8.1Hz,2H),7.41(d,J＝8.1Hz,2H),6.58(d,J＝15.9Hz,1H),6.42–6.35(m,1H),5.56(d,J＝5.1Hz,1H),4.65–4.58(m,1H),4.35–4.29(m,1H),4.21–4.16(m,1H),3.90(s,4H),2.66–2.50(m,2H),1.51(d,J＝16.2Hz,6H),1.35(d,J＝12.0Hz,6H). 13 C NMR(101MHz,CDCl 3 )δ167.1,142.2,131.5,130.0,129.2,128.6,126.1,109.3,108.6,96.7,72.5,71.0,70.6,67.5,52.1,34.0,26.2,26.2,25.0,24.6.HRMS(EI):m/z[M+H] + calcd for C 22 H 29 O 7 :405.1908,found:405.1911.
example 28
This example was conducted in the same manner as in example 1 except that the synthesis of an olefin compound was conducted in the same manner as in example 1,
the alcohol was 7- (. Beta. -hydroxyethyl) theophylline (67 mg,0.3 mmol) and the alkenyl sulfone was methyl 4- (2- (methylsulfonyl) vinyl) benzoate (180 mg,0.75 mmol) to give the product as formula I-28 as a white solid in 45% yield.
The following is a nuclear magnetic resonance and high resolution mass spectrometry test of the product, and the results are as follows:
1 H NMR(400MHz,CDCl 3 )δ7.96(d,J＝8.3Hz,2H),7.55(s,1H),7.34(d,J＝8.3Hz,2H),6.43(d,J＝15.9Hz,1H),6.30–6.22(m,1H),4.44(t,J＝6.8Hz,2H),3.91(s,3H),3.59(s,3H),3.42(s,3H),2.82(q,J＝6.9Hz,2H). 13 C NMR(101MHz,CDCl 3 )δ166.9,155.3,151.8,149.1,141.2,141.0,133.0,130.1,129.2,127.5,126.2,107.0,52.2,46.9,34.7,29.9,28.1.HRMS(EI):m/z[M+H] + calcd for C 19 H 21 N 4 O 4 :369.1557,found:369.1562.
example 29
This example was conducted in the same manner as in example 1 except that the synthesis of an olefin compound was conducted in the same manner as in example 1,
the alcohol was perillyl alcohol (46 mg,0.3 mmol) and alkenyl sulfone was methyl 4- (2- (methylsulfonyl) vinyl) benzoate (180 mg,0.75 mmol) to give the product of formula I-29 as a white solid in 55% yield.
The following is a nuclear magnetic resonance and high resolution mass spectrometry test of the product, and the results are as follows:
1 H NMR(400MHz,CDCl 3 )δ7.96(d,J＝8.4Hz,2H),7.40(d,J＝8.4Hz,2H),6.42(d,J＝15.9Hz,1H),6.37–6.30(m,1H),5.54–5.48(m,1H),4.73–4.71(m,2H),3.90(s,3H),2.86(d,J＝6.6Hz,2H),2.19–2.03(m,4H),2.02–1.88(m,1H),1.85–1.79(m,1H),1.73(s,3H),1.54–1.43(m,1H). 13 C NMR(101MHz,CDCl 3 )δ167.1,150.1,142.3,135.9,131.9,130.3,130.0,128.5,126.0,122.3,108.7,52.1,41.3,41.2,31.0,29.2,28.0,20.9.HRMS(EI):m/z[M+H] + calcd for C 20 H 25 O 2 :297.1849,found:297.1852.
example 30
This example was conducted in the same manner as in example 1 except that the synthesis of an olefin compound was conducted in the same manner as in example 1,
the alcohol was added as L-menthol (47 mg,0.3 mmol) and the alkenyl sulfone as methyl 4- (2- (methylsulfonyl) vinyl) benzoate (180 mg,0.75 mmol) to give the product as formula I-30 as a white solid in 84% yield.
The following is a nuclear magnetic resonance and high resolution mass spectrometry test of the product, and the results are as follows:
1 H NMR(400MHz,CDCl 3 )δ7.96(d,J＝8.1Hz,2H),7.39(d,J＝8.1Hz,2H),6.37(d,J＝15.8Hz,1H),6.20–6.10(m,1H),3.90(s,3H),2.16–2.03(m,1H),1.87–1.80(m,1H),1.79–1.71(m,1H),1.70–1.63(m,2H),1.47–1.36(m,1H),1.17–0.91(m,4H),0.89(dd,J＝6.8,3.5Hz,6H),0.74(d,J＝6.9Hz,3H). 13 C NMR(101MHz,CDCl 3 )δ167.1,142.6,139.1,130.0,128.2,128.1,125.8,52.1,47.5,45.5,43.0,35.2,32.5,28.6,24.3,22.7,21.5,15.6.IR(ATR):2921,1723,1607,1437,1277,1179,1108,967,867,763,699cm -1 .HRMS(EI):m/z[M+H] + calcd for C 20 H 29 O 2 :301.2162,found:301.2164.
example 31
This example was conducted in the same manner as in example 1 except that the synthesis of an olefin compound was conducted in the same manner as in example 1,
2-camphol (46 mg,0.3 mmol) was added and alkenyl sulfone methyl 4- (2- (methylsulfonyl) vinyl) benzoate (180 mg,0.75 mmol) was added to give the product of formula I-31 as a white solid in 67% yield with a 2.3:1 ratio of diastereoselectivity
The following is a nuclear magnetic resonance and high resolution mass spectrometry test of the product, and the results are as follows:
characterization data for one isomer of this example: 1 H NMR(400MHz,CDCl 3 )δ8.00–7.92(m,2H),7.42(d,J＝8.3Hz,2H),6.49–6.27(m,2H),3.91(s,3H),2.59–2.42(m,1H),2.15–2.03(m,1H),1.79–1.67(m,2H),1.60–1.52(m,1H),1.35–1.10(m,3H),0.94(d,J＝5.2Hz,3H),0.88(d,J＝15.3Hz,3H),0.83(d,J＝12.1Hz,3H). 13 C NMR(101MHz,CDCl 3 )δ167.1,142.6,137.1,130.0,129.8,128.3,126.0,52.1,50.1,48.8,47.9,45.6,35.9,29.6,28.8,19.6,18.7,14.3.
characterization data for the other isomer of this example: 1 H NMR(400MHz,CDCl 3 )δ8.00–7.92(m,2H),7.37(d,J＝8.3Hz,2H),6.49–6.27(m,2H),3.91(s,3H),2.59–2.42(m,1H),2.15–2.03(m,1H),1.79–1.67(m,2H),1.60–1.52(m,1H),1.35–1.10(m,3H),0.94(d,J＝5.2Hz,3H),0.88(d,J＝15.3Hz,3H),0.83(d,J＝12.1Hz,3H). 13 C NMR(101MHz,CDCl 3 )δ167.1,142.8,139.3,130.0,128.7,128.3,126.0,52.0,49.5,47.9,45.6,39.5,36.9,27.6,20.7,20.6,14.0.HRMS(EI):m/z[M+H] + calcd for C 20 H 26 O 2 Na:321.1825,found:321.1819.
example 32
This example was conducted in the same manner as in example 1 except that the synthesis of an olefin compound was conducted in the same manner as in example 1,
the alcohol was added as cyclohexylmethanol (34 mg,0.3 mmol) and the alkenyl sulfone was added as 1-fluoro-4- (2- (methylsulfonyl) vinyl) benzene (150 mg,0.75 mmol) to give the product of formula I-32 as a colorless liquid in 60% yield.
The following is a nuclear magnetic resonance and high resolution mass spectrometry test of the product, and the results are as follows:
1 H NMR(400MHz,CDCl 3 )δ7.37–7.27(m,2H),7.02–6.93(m,2H),6.31(d,J＝15.8Hz,1H),6.18–6.08(m,1H),2.13–2.05(m,2H),1.80–1.64(m,5H),1.43–1.35(m,1H),1.27–1.15(m,3H),1.02–0.91(m,2H). 13 C NMR(101MHz,CDCl 3 )δ163.2,160.8,134.2(d,J＝3.3Hz),129.6,127.4(d,J＝7.9Hz),115.4(d,J＝21.5Hz).41.1,38.3,33.4,26.7,26.5. 19 F NMR(376MHz,CDCl 3 )δ116.0.HRMS(EI):m/z[M+H] + calcd for C 15 H 20 F:219.1544,found:219.1546.
example 33
This example was conducted in the same manner as in example 1 except that the synthesis of an olefin compound was conducted in the same manner as in example 1,
the alcohol was added as cyclohexylmethanol (34 mg,0.3 mmol) and the alkenyl sulfone was added as 1-cyano-4- (2- (methylsulfonyl) vinyl) benzene (155 mg,0.75 mmol) to give the product as formula I-33 as a colorless liquid in 86% yield.
The following is a nuclear magnetic resonance and high resolution mass spectrometry test of the product, and the results are as follows:
1 H NMR(400MHz,CDCl 3 )δ7.55(d,J＝8.4Hz,2H),7.40(d,J＝8.4Hz,2H),6.42–6.31(m,2H),2.18–2.08(m,2H),1.78–1.64(m,5H),1.48–1.35(m,1H),1.29–1.15(m,3H),1.01–0.90(m,2H). 13 C NMR(101MHz,CDCl 3 )δ142.5,134.4,132.4,129.5,126.5,119.3,110.0,41.2,38.1,33.3,26.6,26.4.HRMS(EI):m/z[M+H] + calcd for C 16 H 20 N:226.1590,found:226.1592.
example 34
This example was conducted in the same manner as in example 1 except that the synthesis of an olefin compound was conducted in the same manner as in example 1,
the alcohol was added as cyclohexylmethanol (34 mg,0.3 mmol) and the alkenyl sulfone as 2- (2- (methylsulfonyl) vinyl) thiophene (141 mg,0.75 mmol) to give the product of formula I-34 as a colorless liquid in 60% yield.
The following is a nuclear magnetic resonance and high resolution mass spectrometry test of the product, and the results are as follows:
1 H NMR(400MHz,CDCl 3 )δ7.08(d,J＝4.9Hz,1H),6.97–6.91(m,1H),6.86(d,J＝3.0Hz,1H),6.48(d,J＝15.6Hz,1H),6.14–5.97(m,1H),2.10–2.02(m,2H),1.78–1.65(m,5H),1.43–1.34(m,1H),1.27(s,1H),1.23–1.14(m,2H),0.99–0.90(m,2H). 13 C NMR(101MHz,CDCl 3 )δ143.3,130.0,127.3,124.2,124.1,123.1,41.0,38.3,33.3,26.7,26.5.HRMS(EI):m/z[M+H] + calcd for C 13 H 19 S:207.1202,found:207.1207.
example 35
This example was conducted in the same manner as in example 1 except that the synthesis of an olefin compound was conducted in the same manner as in example 1,
the alcohol was added as cyclohexylmethanol (34 mg,0.3 mmol) and the alkenyl sulfone as 2- (2- (methylsulfonyl) vinyl) benzofuran (67 mg,0.75 mmol) to give the product of formula I-35 as a yellow liquid in 50% yield.
The following is a nuclear magnetic resonance and high resolution mass spectrometry test of the product, and the results are as follows:
1 H NMR(400MHz,CDCl 3 )δ7.53–7.35(m,2H),7.25–7.13(m,2H),6.46(d,J＝7.5Hz,2H),6.30(d,J＝15.8Hz,1H),2.19–2.10(m,2H),1.81–1.66(m,5H),1.50–1.39(m,1H),1.29–1.19(m,3H),1.03–0.92(m,2H). 13 C NMR(101MHz,CDCl 3 )δ155.3,154.7,132.8,129.3,124.1,122.8,120.7,119.6,110.9,102.7,41.2,38.2,33.4,26.7,26.5.HRMS(EI):m/z[M+H] + calcd for C 17 H 21 O:241.1587,found:241.1585.
example 36
This example was conducted in the same manner as in example 1 except that the synthesis of an olefin compound was conducted in the same manner as in example 1,
the alcohol was added as cyclohexylmethanol (34 mg,0.3 mmol) and the alkenyl sulfone as 4- (2- (methylsulfonyl) vinyl) pyridine (137 mg,0.75 mmol) to give the product of formula I-36 as a yellow liquid in 53% yield.
The following is a nuclear magnetic resonance and high resolution mass spectrometry test of the product, and the results are as follows:
1 H NMR(400MHz,CDCl 3 )δ8.48(d,J＝5.1Hz,2H),7.19(d,J＝5.6Hz,2H),6.53–6.38(m,1H),6.28(d,J＝15.8Hz,1H),2.17–2.09(m,2H),1.76–1.60(m,5H),1.48–1.36(m,1H),1.27–1.12(m,3H),1.01–0.89(m,2H). 13 C NMR(101MHz,CDCl 3 )δ150.1,145.3,135.2,128.8,120.7,41.2,38.1,33.3,26.6,26.4.HRMS(EI):m/z[M+H] + calcd for C 14 H 20 N:202.1590,found:202.1591.
example 37
This example was conducted in the same manner as in example 1 except that the synthesis of an olefin compound was conducted in the same manner as in example 1,
the alcohol was added as cyclohexylmethanol (34 mg,0.3 mmol) and the alkenyl sulfone as 3- (2- (methylsulfonyl) -1-phenylvinyl) pyridine (194 mg,0.75 mmol) to give the product of formula I-37 as a yellow liquid in 42% yield.
The following is a nuclear magnetic resonance and high resolution mass spectrometry test of the product, and the results are as follows:
1 H NMR(400MHz,CDCl 3 )δ8.61(d,J＝4.7Hz,2H),7.29(d,J＝6.5Hz,1H),7.25(d,J＝9.9Hz,2H),7.17(d,J＝6.6Hz,2H),7.11(d,J＝5.6Hz,2H),6.23–6.13(m,1H),2.03–1.94(m,2H),1.75–1.62(m,5H),1.44–1.35(m,1H),1.26–1.17(m,3H),0.91–0.82(m,2H). 13 C NMR(101MHz,CDCl 3 )δ149.9,148.8,141.5,139.8,130.9,128.4,127.4,127.2,125.3,38.8,37.5,33.4,26.6,26.4.HRMS(EI):m/z[M+H] + calcd for C 20 H 24 N:278.1903,found:278.1908.
example 38
This example was conducted in the same manner as in example 1 except that the synthesis of an olefin compound was conducted in the same manner as in example 1,
the alcohol was added as cyclohexylmethanol (34 mg,0.3 mmol) and the allylsulfone was added as (3- (methylsulfonyl) -2-phenyl-1-propene (147 mg,0.75 mmol) to give the product of formula II-1 as a yellow liquid in 57% yield.
The following is a nuclear magnetic resonance and high resolution mass spectrometry test of the product, and the results are as follows:
1 H NMR(400MHz,CDCl 3 )δ7.40(d,J＝7.9Hz,2H),7.36–7.28(m,2H),7.27–7.23(m,1H),5.25(s,1H),5.04(s,1H),2.55–2.46(m,2H),1.77–1.62(m,5H),1.36–1.29(m,2H),1.29–1.14(m,4H),0.93–0.85(m,2H). 13 C NMR(101MHz,CDCl 3 )δ149.2,141.6,128.4,127.4,126.2,111.9,37.7,36.3,33.4,32.9,26.8,26.5.HRMS(EI):m/z[M+H] + calcd for C 16 H 23 :215.1794,found:215.1796.
example 39
This example was conducted in the same manner as in example 1 except that the synthesis of an olefin compound was conducted in the same manner as in example 1,
the alcohol was added as cyclohexylmethanol (34 mg,0.3 mmol) and the allylsulfone was added as methyl 2- ((methylsulfonyl) methyl) acrylate (134 mg,0.75 mmol) to give the product as formula II-2 in 51% yield as a colorless liquid.
The following is a nuclear magnetic resonance and high resolution mass spectrometry test of the product, and the results are as follows:
1 H NMR(400MHz,CDCl 3 )δ6.11(s,1H),5.51(s,1H),3.74(s,3H),2.33–2.25(m,2H),1.77–1.64(m,5H),1.37–1.30(m,2H),1.25–1.17(m,4H),0.94–0.86(m,2H). 13 C NMR(101MHz,CDCl 3 )δ168.1,141.3,124.4,51.9,37.5,36.2,33.4,29.4,26.8,26.5.
example 40
This example was conducted in the same manner as in example 1 except that the synthesis of an olefin compound was conducted in the same manner as in example 1,
the alcohol was added as cyclohexylmethanol (34 mg,0.3 mmol) and the allylsulfone was added as 2- ((benzenesulfonyl) methyl) acrylonitrile (109 mg,0.75 mmol) to give the product as formula II-3 in 62% yield as a colorless liquid.
The following is a nuclear magnetic resonance and high resolution mass spectrometry test of the product, and the results are as follows:
1 H NMR(400MHz,CDCl 3 )δ6.04(d,J＝15.2Hz,2H),4.40(d,J＝6.4Hz,2H),3.95(s,2H),1.93–1.81(m,1H),1.76(s,4H),1.69(d,J＝12.6Hz,1H),1.32–1.18(m,3H),1.08–0.97(m,2H). 13 C NMR(101MHz,CDCl 3 )δ133.3,118.3,117.5,80.0,38.2,37.0,29.7,26.3,25.7.HRMS(EI):m/z[M+H] + calcd for C 11 H 18 N:164.1434,found:164.1439.
the present invention also conducted performance comparison with respect to the use of a base in the synthesis method, and synthesis of an olefin compound was conducted in the same manner as in example 1, except that the base was different from example 1. Specific results are shown in Table 1, using 1,2,4, 5-tetramethylbenzene as an internal standard, as determined by gas chromatography.
Figure BDA0003429500230000281
Table 1: deoxidisation of alcohols-Table for screening of bases
Figure BDA0003429500230000282
It can be seen that KO is to t Bu was used as a base in the synthesis method of the present invention, and a yield of 91% was obtained.
The present invention also performed performance comparison for the use of the organic solvent in step (2) in the synthesis method, and synthesis of an olefin compound was performed in the same manner as in example 1, except that the second organic solvent was different from example 1. Specific results are shown in Table 2, using 1,2,4, 5-tetramethylbenzene as an internal standard, as determined by gas chromatography.
Figure BDA0003429500230000283
Table 2: deoxidisation of alcohols-screening of second organic solvents
Figure BDA0003429500230000284
Figure BDA0003429500230000291
It can be seen that the use of 1,4-dioxane/DME/MeCN (2.0 mL/1.0mL/0.5 mL) as the organic solvent in step (2) of the synthesis method of the present invention gave a yield of 91%.
The present invention also conducted performance comparison for the use of a trivalent phosphorus compound in the synthesis method, and synthesis of an olefin compound was conducted in the same manner as in example 1, except that the trivalent phosphorus compound was different from example 1. Specific results are shown in Table 3, using 1,2,4, 5-tetramethylbenzene as an internal standard, as determined by gas chromatography.
Figure BDA0003429500230000292
Table 3: deoxidisation of alcohols-screening of phosphinous compounds
Figure BDA0003429500230000293
It can be seen that the use of tris (4-methoxyphenyl) phosphine as the phosphine in the synthesis method of the present invention gives a yield of 91%.
The present invention also conducted performance comparison for the use of alkenyl sulfone in the synthesis method, and synthesis of an olefin compound was conducted in the same manner as in example 1, except that alkenyl sulfone was different from example 1. Specific results are shown in Table 4, using 1,2,4, 5-tetramethylbenzene as an internal standard, as determined by gas chromatography.
Figure BDA0003429500230000294
Table 4: deoxidisation of alcohols-screening of alkenyl sulfones
Figure BDA0003429500230000301
It can be seen that the use of (2- (methylsulfonyl) vinyl) benzene as an alkenyl sulfone in the synthetic method of the present invention gives a yield of 91%.
It will be readily appreciated by those skilled in the art that the foregoing description is merely a preferred embodiment of the invention and is not intended to limit the invention, but any modifications, equivalents, improvements or alternatives falling within the spirit and principles of the invention are intended to be included within the scope of the invention.

Claims (10)

1. A method for promoting the synthesis of an olefin compound from an alcohol by visible light, the method comprising the steps of:
(1) Under the protection of inert gas, dissolving alcohol and alkali in a first organic solvent, adding carbon disulfide at the temperature of 0-26 ℃ to enable the alcohol and the carbon disulfide to generate xanthate in situ, and then removing the organic solvent in vacuum; wherein the alcohol does not include a group having an active hydrogen at the a-position;
(2) Adding a sulfone compound, a trivalent phosphine compound, a second organic solvent and a drying agent into the xanthate serving as an alkyl radical precursor under the protection of inert gas;
(3) Under the condition of the temperature of 26-60 ℃, under the irradiation of visible light, the alkyl radical precursor and the sulfone compound are subjected to radical coupling reaction to obtain an olefin compound; wherein the sulfone compound is alkenyl sulfone or allyl sulfone.
2. The method according to claim 1, wherein the first organic solvent in the step (1) is one of tetrahydrofuran, isopropyl ether, diethyl ether, methylene chloride, petroleum ether, n-pentane, n-hexane, cyclohexane, and 1, 4-dioxane.
3. The method according to claim 1, wherein the base is one of cesium carbonate, cesium fluoride, sodium hydroxide, sodium carbonate, sodium acetate, sodium bicarbonate, sodium hydride, potassium phosphate, potassium hydroxide, potassium carbonate, potassium tert-butoxide, sodium tert-butoxide, lithium tert-butoxide, triethylamine, diisopropylethylamine, potassium bis (trimethylsilyl) amide, preferably wherein the base is one of potassium tert-butoxide, sodium tert-butoxide, lithium tert-butoxide, triethylamine, diisopropylethylamine, potassium bis (trimethylsilyl) amide.
4. The method according to claim 1, wherein the second organic solvent in the step (2) is at least one of methanol, trifluoroethanol, N-hexane, acetonitrile, dimethyl sulfoxide, diethyl ether, N-dimethylformamide, N-dimethylacetamide, ethylene glycol dimethyl ether, tetrahydrofuran, benzotrifluoride, methylene chloride, chloroform, 1, 4-dioxane; preferably, the second organic solvent in the step (2) is at least two of methanol, n-hexane, acetonitrile, ethylene glycol dimethyl ether and 1, 4-dioxane.
5. The method of any one of claims 1-4, wherein the phosphine compound is a trialkylphosphine, triarylphosphine, phosphite or phosphoramidite; preferably, the phosphine compound is one of tricyclohexylphosphine, tributylphosphine, triisopropylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, tris (4-methoxyphenyl) phosphine, tris (2-methoxyphenyl) phosphine, triethyl phosphite, triphenyl phosphite, tris (pentafluorophenyl) phosphine, and hexaethylphosphorous triamine, and preferably, the phosphine compound is one of tricyclohexylphosphine, tributylphosphine, diphenylcyclohexylphosphine, tris (4-methylphenyl) phosphine, tris (4-methoxyphenyl) phosphine, and triethyl phosphite.
6. The method of any one of claims 1-4, wherein the alkenyl sulfone is (2- (arylsulfonyl) vinyl) benzene, (2- (alkylsulfonyl) vinyl) benzene or (2- (alkylsulfonyl) vinyl) arene; the allyl sulfone is (3- (arylsulfonyl) -2-aryl-1-propene, 2- ((alkylsulfonyl) methyl) acrylate, 2- ((arylsulfonyl) methyl) acrylate or 2- ((arylsulfonyl) methyl) acrylonitrile, preferably the alkenyl sulfone is one of (2- (phenylsulfonyl) vinyl) benzene, 1-methyl-4- (2- (phenylsulfonyl) vinyl) benzene, 1-fluoro-4- (2- (phenylsulfonyl) vinyl) benzene, 1-chloro-4- (2- (phenylsulfonyl) vinyl) benzene, 1-methoxy-4- (2- (phenylsulfonyl) vinyl) benzene, 1- (tert-butyl) -4- (2- (phenylsulfonyl) vinyl) benzene, 2- (2- (phenylsulfonyl) vinyl) naphthalene, (2- (methylsulfonyl) vinyl) benzene, (2- (propylsulfonyl) vinyl) benzene, and the allyl sulfone is (3- (methylsulfonyl) -2-phenyl-1-propene, 2- ((methylsulfonyl) methyl) acrylate or 2- ((benzenesulfonyl) methyl) acrylonitrile.
7. The method of any one of claims 1-4, wherein the desiccant is
Figure FDA0003429500220000021
Molecular sieves, & gt>
Figure FDA0003429500220000022
Molecular sieves, & gt>
Figure FDA0003429500220000023
One of molecular sieve, sodium sulfate and magnesium sulfate; the wavelength of the visible light is 400-500nm.
8. The method according to any one of claims 1 to 4, wherein the molar ratio of the alcohol, base, carbon disulfide, sulfone compound to the phosphine compound is 1 (1.0 to 1.1): 1.0 to 5.0): 1.0 to 3.5): 1.0 to 3.0.
9. An olefinic compound obtained by the synthetic method according to any one of claims 1 to 8.
10. The olefinic compound according to claim 9, characterized in that the compound is represented by the following formula I:
Figure FDA0003429500220000031
wherein R is 1 Is an alkyl, benzyl or allyl group containing no active hydrogen in the a position;
R 2 is aryl, naphthyl or heteroaryl;
R 3 is hydrogen, methyl, ester, cyano, aryl or alkyl.
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