CN114380679B - Palladium catalytic oxidation coupling method - Google Patents

Palladium catalytic oxidation coupling method Download PDF

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CN114380679B
CN114380679B CN202011117880.2A CN202011117880A CN114380679B CN 114380679 B CN114380679 B CN 114380679B CN 202011117880 A CN202011117880 A CN 202011117880A CN 114380679 B CN114380679 B CN 114380679B
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陈庆安
赵朝阳
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Dalian Institute of Chemical Physics of CAS
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Abstract

The invention relates to a palladium catalytic oxidation coupling method. Specifically, 1-tetralone and isoamylenol are used as raw materials, and oxidation coupling of ketone and isoamylenol is realized under the condition of catalysis of palladium carbene. The invention has the advantages that the prenol is directly used as a coupling reagent, the oxidative coupling is selectively realized, the substrate range is wide, the yield is good, and the Z/E selectivity is good.

Description

Palladium catalytic oxidation coupling method
Technical Field
The invention relates to a palladium catalytic oxidation coupling method. Specifically, 1-tetralone and isoamylenol are used as raw materials, and oxidation coupling of ketone and isoamylenol is realized under the condition of catalysis of palladium carbene. The invention has the advantages that the isopentenol is directly used as an alkylating reagent, the oxidative coupling is selectively realized, the substrate range is wide, the yield is good, and the Z/E selectivity is good.
Background
Carbonyl groups are common functional groups in natural products and are also widely present in the first 200 prescribed drugs. And the alcohol is used as a natural product and an industrially abundant raw material, has the advantages of greenness and low price, and is a good coupling reagent. In the past years, alcohols have been used primarily as alkylating agents and allylating raw materials, such as: the Pd-catalyzed Tsuji allylation reaction synthesized the alpha-allyl ketone product (formula 1).
The method for the catalytic synthesis of alpha-allyl ketone products by allylpalladium chloride was independently reported by literature search (formula 1) by the Zhang Mobin group in 2014 (Huo, g.yang, d.liu, y.liu, i.gridnev, and w.zhang x.zhao, d.liu, h.guo, y.liu, w.zhang, angelw.chem.int.ed.2014, 53,6776.). The success of the above process depends on the formation of a pi-allylpalladium complex, one of the Tsuji allylation reactions, leading to a directly coupled product. In contrast, it is also important to achieve an oxidative coupling between them.
Figure BDA0002730968860000011
Disclosure of Invention
The invention aims to quickly realize the oxidation coupling between ketone and alcohol by using the ketone and the isopentenol as raw materials under the condition of palladium carbene catalysis, and the invention has good yield and good Z/E selectivity.
The invention is realized by the following technical scheme:
a method for coupling palladium catalytic oxidation,
the method takes ketone and isopentenol as raw materials, and under the condition of palladium carbene catalysis, the oxidation coupling of the alpha position of the ketone is quickly realized with good yield. The reaction formula is shown as follows:
Figure BDA0002730968860000021
the specific operation steps are as follows:
under the atmosphere of argon or nitrogen, adding allyl palladium chloride, carbene salt, sodium methoxide/sodium ethoxide and an anhydrous toluene solvent into a reactor, stirring at room temperature for reaction for 1h, and then adding ketone and isopentenol to react to generate a target product 3. And (3) monitoring a reaction system by using a point plate, and after the reaction is finished, spin-drying a solvent, and performing column chromatography on a mobile phase: petroleum ether/diethyl ether (volume ratio);
substituent R on reactant ketone 1 Can be one, two, three or four of phenyl, 3-methoxyphenyl, 4-methoxyphenyl, 5-methoxyphenyl, 3-methylphenyl and 3-fluorophenyl; reactant ketiminoacid ester substituent R 2 Can be one, two, three or four of methyl, ethyl, phenyl and benzyl.
The used metal copper salt is one or more than two of the following metal copper salts: allyl palladium chloride, palladium acetate, palladium trifluoroacetate, cinnamyl palladium chloride and palladium bis (acetylacetonate). Wherein the molar ratio of palladium salt to ketone is 0.001-1, preferably in the range of 0.01-0.2.
The carbene salt reagent is one or more than two of the following: the molar ratio of the carbene salt reagent to the ketone is 0.001-1, and the preferable range is 0.01-0.2.
Figure BDA0002730968860000022
The solvent is one or more of methanol, ethanol, isopropanol, tert-butanol, acetonitrile, toluene, chlorobenzene, p-methyl chlorobenzene, cyclohexane, tetrahydrofuran, 2-methyltetrahydrofuran, ethylene glycol dimethyl ether, methyl tert-butyl ether, dichloromethane, dichloroethane, 1,4-dioxane, ethyl acetate, N-dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide, the solvent is preferably one or two of toluene, tetrahydrofuran, 1,4-dioxane and dichloroethane, and the concentration range of the 1-tetralone in the solvent is preferably 0.01-1.5mol/L.
The amount of prenol used is between 0.5 and 10 times, preferably between 2 and 5 times, the molar amount.
The organic amine is aniline, cyclohexylamine, piperidine and/or tetrahydropyrrole, and the molar ratio of the organic amine to the ketone is 0.1-3.0, preferably 0.2-1.0; the reaction temperature is 70 ℃; the reaction time is between 0.5 and 36 hours, and the reaction time is preferably between 16 and 24 hours.
The invention has the following advantages:
the method has the advantages that the palladium carbene is prepared in situ by the metal palladium salt and the carbene salt under the alkali condition; the prenol is directly used as a coupling reagent to selectively realize oxidative coupling, and has wide substrate range and good yield. While having good Z/E selectivity. (if the double bond of the olefin has a certain configuration, the configuration of the double bond is labeled using Z/E, where Z is two large groups on one side of the double bond carbon of the olefin and two small groups on the other side, and E is likewise one large group on one olefinic carbon and one small group on the other olefinic carbon)
Drawings
FIG. 1 is a drawing of Compound 3a 1 H NMR and 13 c NMR chart;
FIG. 2 shows the preparation of compound 3b 1 H NMR and 13 c NMR chart;
FIG. 3 is a schematic diagram of a compoundOf object 3c 1 H NMR and 13 c NMR chart;
FIG. 4 is a drawing of Compound 3d 1 H NMR and 13 c NMR chart;
FIG. 5 is a drawing of Compound 3e 1 H NMR and 13 c NMR chart;
FIG. 6 is a drawing of Compound 3f 1 H NMR， 13 C NMR and 19 f NMR chart;
FIG. 7 shows 3g of compound 1 H NMR and 13 c NMR chart;
FIG. 8 is of compound 3h 1 H NMR and 13 c NMR chart;
FIG. 9 is a drawing of Compound 3i 1 H NMR and 13 c NMR chart;
Detailed Description
The invention will now be illustrated by means of specific examples, without restricting its scope to these examples.
1. Reaction for alpha-oxidation coupling of ketone catalyzed by palladium carbene
Allyl palladium chloride (2.5 mol% relative to the amount of ketone, 1.8 mg), carbene salt reagent L (5 mol% relative to the amount of ketone), organic base (3.0 equiv% relative to the amount of ketone), and chlorobenzene (1 mL) were added in this order to a 2.0mL sealed tube under a nitrogen atmosphere, and the reaction was stirred at room temperature for 1 hour, followed by addition of 1-tetralone (0.20mmol, 29.2mg), organic amine (0.10 mmol), and isopentenol (0.30mmol, 25.8 mg), reaction was carried out at 70 ℃ for 16 hours, and after completion, mesitylene was added as an internal standard, and the yield of the objective product was determined by GC-FID.
Figure BDA0002730968860000041
TABLE 1 influence of catalyst, solvent on the reaction
Figure BDA0002730968860000042
Figure BDA0002730968860000051
2. Type of substrate
In a 2.0mL sealed tube, allyl palladium chloride (2.5 mol%,1.8 mg), carbene salt L5 (5 mol%), sodium methoxide (3.0 equiv.,32.4 mg), and chlorobenzene 1mL were added in this order, and the reaction was stirred at room temperature for 1 hour, followed by addition of ketone (0.20mmol, 29.2mg), piperidine (0.10mmol, 8.6mg), and isopentenol (0.30mmol, 25.8mg), reaction at 70 ℃ for 16 hours, after completion, spin-drying, column chromatography separation, and a mobile phase of petroleum ether/ethyl acetate (volume ratio 20.
Figure BDA0002730968860000052
Figure BDA0002730968860000053
Figure BDA0002730968860000061
Figure BDA0002730968860000062
1H),7.45(td,J＝7.4,1.5Hz,1H),7.33(td,J＝7.6,1.2Hz,1H),7.24(t,J＝7.1Hz,1H), 6.23(dt,J＝12.2,1.5Hz,1H),3.01–2.83(m,4H),1.98(s,3H),1.95(s,3H). 13 C NMR(101 MHz,CDCl 3 )δ187.8,147.3,143.4,134.0,132.8,132.3,131.5,128.1,128.0,126.8,120.9, 28.8,27.2,25.4,19.1.HRMS calculated for C 15 H 16 O[M+H] + 213.1274,found 213.1274.
Figure BDA0002730968860000071
6.33–6.15(m,1H),3.13(h,J＝6.3Hz,1H),2.90(dd,J＝14.7,4.3Hz,1H),2.79(dd,J＝ 14.8,5.6Hz,1H),1.98(s,3H),1.96(s,3H),1.29(d,J＝7.0Hz,3H). 13 C NMR(100MHz, CDCl 3 )δ187.8,148.5,147.3,133.5,133.0,130.0,128.2,126.9,126.8,120.9,33.1,32.9,27.2, 22.0,19.1.HRMS calculated for C 16 H 18 O[M+H] + 227.1430,found 227.1426
Figure BDA0002730968860000072
1H),7.14(d,J＝8.3Hz,1H),7.03(dd,J＝8.3,2.9Hz,1H),6.27–6.19(m,1H),3.85(s,3H), 2.92–2.81(m,4H),1.98(s,3H),1.95(s,3H). 13 C NMR(101MHz,CDCl 3 )δ187.7,158.5, 147.1,136.1,134.8,132.3,131.5,129.3,121.0,120.8,110.3,55.5,27.9,27.2,25.6, 19.1.HRMS calculated for C 16 H 18 O 2 [M+H] + 243.1380,found 243.1382
Figure BDA0002730968860000073
1H),6.85(dd,J＝8.7,2.6Hz,1H),6.70(d,J＝2.5Hz,1H),6.22(dt,J＝12.1,1.5Hz,1H), 3.86(s,3H),2.99–2.81(m,4H),1.97(s,3H),1.94(s,3H). 13 C NMR(101MHz,CDCl 3 )δ 186.8,163.2,146.6,145.9,131.6,130.5,128.4,127.5,120.9,113.1,112.3,55.4,29.2,27.2, 25.5,19.1.HRMS calculated for C 16 H 18 O 2 [M+H] + 243.1380,found 243.1383
Figure BDA0002730968860000074
J＝12.1,1.6Hz,1H),7.32–7.22(m,1H),7.12(d,J＝7.7Hz,1H),6.23(dt,J＝12.2,1.4Hz, 1H),2.94–2.82(m,4H),2.37(s,3H),1.98(s,3H),1.94(s,3H). 13 C NMR(101MHz,CDCl 3 ) δ188.0,147.0,140.6,136.5,133.8,133.7,132.1,131.8,128.2,128.0,121.0,28.4,27.2,25.6, 21.0,19.1.HRMS calculated for C 16 H 18 O[M+H] + 227.1430,found 227.1437
Figure BDA0002730968860000081
7.69(d,J＝12.1Hz,1H),7.22(dd,J＝8.4,5.2Hz,1H),7.15(td,J＝8.3,2.8Hz,1H),6.23 (dt,J＝12.3,1.6Hz,1H),2.97–2.79(m,4H),1.98(s,3H),1.96(s,3H). 13 C NMR(101 MHz,CDCl 3 )δ186.8(d,J＝1.9Hz),161.8(d,J＝245.7Hz),148.0,139.1(d,J＝2.9Hz), 135.6(d,J＝6.3Hz),133.0,130.7(d,J＝0.9Hz),129.8(d,J＝7.0Hz),120.9,119.9(d,J＝ 22.1Hz),114.0(d,J＝22.0Hz),28.0,27.2,25.4,19.1. 19 F NMR(376MHz,CDCl 3 )δ-115.2. HRMS calculated for C 15 H 15 FO[M+H] + 231.1180,found 231.1180
Figure BDA0002730968860000082
1.98(s,3H),1.96(s,3H). 13 C NMR(100MHz,CDCl 3 )δ194.2,149.0,148.8,139.4,134.1, 133.4,129.7,127.3,126.2,124.0,122.1,30.3,27.1,19.2.HRMS calculated for C 14 H 14 O [M+H] + 199.1117,found 199.1121
Figure BDA0002730968860000083
1.98(s,3H),1.96(s,3H). 13 C NMR(101MHz,CDCl 3 )δ194.3,148.5,146.4,139.6,137.3, 135.3,134.0,129.5,125.9,124.1,122.1,29.9,27.1,21.2,19.2.HRMS calculated for C 15 H 16 O[M+H] + 213.1274,found 213.1279.
Figure BDA0002730968860000084
Hz,1H),6.20(d,J＝12.1Hz,1H),2.76(t,J＝6.9Hz,2H),2.43(t,J＝6.8Hz,2H),1.97(s, 3H),1.94(s,3H),1.90(t,J＝6.9Hz,2H). 13 C NMR(101MHz,CDCl 3 )δ198.4,147.3,139.5, 139.4,134.9,133.0,132.0,128.9,128.8,126.8,120.7,31.3,27.2,26.4,24.1,19.1.HRMS calculated for C 16 H 18 O[M+H] + 227.1430,found 227.1437
Figure BDA0002730968860000085
Pd/C (Pd mass content 5%,4 mg) and 1mL of solvent methanol are sequentially added into a 2.0mL small bottle, the small bottle is placed into an autoclave, hydrogen is introduced, the pressure is 500psi, the reaction is carried out for 16h at 50 ℃, after the reaction is finished, spin-drying and column chromatography separation are carried out, the target product 4 can be obtained by using petroleum ether/ethyl acetate (the volume ratio is 1:0) as a mobile phase, and the yield is 95%,76.8mg.

Claims (15)

1. A method of palladium-catalyzed oxidative coupling, characterized by:
under the action of a palladium carbene reagent, ketone and isopentenol can realize the oxidative coupling of the ketone and the isopentenol;
the specific operation steps are as follows:
adding metal palladium salt, carbene salt, organic base and solvent into a reactor under the atmosphere of argon and/or nitrogen, stirring and reacting for more than 1h at room temperature, and then adding ketone, isopentenol and organic amine to react to generate a target product;
the reaction formula is shown as follows:
Figure DEST_PATH_IMAGE001
；
the reactant ketone has no substituent or the substituent R in the formula 1 can be one, two, three or four of 4-methyl, 6-methyl, 7-methyl, 5-methoxy, 6-methoxyphenyl, 7-methoxyphenyl and 7-fluorine;
the organic base is one or more of sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium tert-butoxide and lithium tert-butoxide; the carbene salt reagent is one or more than two of the following: the structural formulas of L1, L2, L4 and L5 are shown as follows;
Figure 764248DEST_PATH_IMAGE002
。
2. the method of claim 1, wherein:
and (3) monitoring a reaction system by using a point plate, and after the reaction is finished, spin-drying a solvent, and performing column chromatography on a mobile phase: 1-10 volume ratio of petroleum ether/diethyl ether.
3. The method of claim 1, wherein:
the metal palladium salt is one or more than two of the following metals: allyl palladium chloride, palladium acetate, palladium trifluoroacetate, cinnamyl palladium chloride or palladium bis (acetylacetonate); wherein the molar ratio of the palladium salt to the ketone is 0.001-1.
4. The method of claim 3, wherein:
wherein the molar ratio of the palladium salt to the ketone is 0.01-0.2.
5. The method of claim 1, wherein:
the molar ratio of carbene salt reagent to ketone is 0.001-1.
6. The method of claim 5, wherein:
the molar ratio of the carbene salt reagent to the ketone is 0.01 to 0.2.
7. The method of claim 1, wherein:
the solvent is selected from methanol, ethanol, isopropanol, tert-butanol, acetonitrile, toluene, chlorobenzene, p-methyl-chlorobenzene, cyclohexane, tetrahydrofuran 2-methyltetrahydrofuran, ethylene glycol dimethyl ether, methyl tert-butyl ether, dichloromethane, dichloroethane, 1,4-dioxane, ethyl acetate,N,N-one or more of dimethylformamide, N-methylpyrrolidone and dimethylsulfoxide;
the concentration of the ketone in the solvent is in the range of 0.01-1.5mol/L.
8. The method of claim 7, wherein:
the solvent is one or more of toluene, tetrahydrofuran, 1,4-dioxane and dichloroethane.
9. The method of claim 1, wherein:
the dosage of the prenol is 0.5-10 times of the molar weight of the ketone;
the reaction temperature after adding the ketone, the isopentenol and the organic amine is 20-100 DEG o C, the reaction time is between 0.5 and 36 h.
10. The method of claim 9, wherein:
the dosage of the prenol is 2-5 times of the molar weight of the ketone;
the reaction temperature after adding the ketone, the isopentenol and the organic amine is 40-70 o C, the reaction time is between 16 and 24 hours.
11. The method of claim 1, wherein:
the organic amine is one or more of aniline, cyclohexylamine, piperidine or tetrahydropyrrole, and the molar ratio of the organic amine to the ketone is 0.1-3.0.
12. The method of claim 11, wherein:
the molar ratio of organic amine to ketone is 0.2-1.0.
13. The method of claim 1, wherein:
the molar ratio of the organic base to the ketone is 0.1-5.0.
14. The method of claim 13, wherein:
the molar ratio of the organic base to the ketone is 1.0-3.0.
15. The method of claim 1, wherein: the ketone is 1-tetralone.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD293805A5 (en) * 1990-04-26 1991-09-12 Adw,Forschungsstelle F. Chemische Toxikologie,De PROCESS FOR PREPARING SUBSTITUTED 2- (5-OXO-PENT-2-EN-1-YLIDENES) -INDAN-1-ONE
WO2016013976A1 (en) * 2014-07-23 2016-01-28 Nanyang Technological University Method of forming a multi-substituted benzene compound
CN110790649A (en) * 2019-11-07 2020-02-14 西北大学 Method for synthesizing polysubstituted α unsaturated ketone

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD293805A5 (en) * 1990-04-26 1991-09-12 Adw,Forschungsstelle F. Chemische Toxikologie,De PROCESS FOR PREPARING SUBSTITUTED 2- (5-OXO-PENT-2-EN-1-YLIDENES) -INDAN-1-ONE
WO2016013976A1 (en) * 2014-07-23 2016-01-28 Nanyang Technological University Method of forming a multi-substituted benzene compound
CN110790649A (en) * 2019-11-07 2020-02-14 西北大学 Method for synthesizing polysubstituted α unsaturated ketone

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Palladium-Catalyzed Allylic Alkylation of Simple Ketones with Allylic Alcohols and Its Mechanistic Study;HUo Xiaohong等;《Angewandte Chemie International Edition》;20140521;第53卷;全文 *

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