CN108976122B - Method for producing 1, 3-dicarbonyl compounds based on metal hydride/palladium compound systems - Google Patents
Method for producing 1, 3-dicarbonyl compounds based on metal hydride/palladium compound systems Download PDFInfo
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- C07—ORGANIC CHEMISTRY
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- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/313—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of doubly bound oxygen containing functional groups, e.g. carboxyl groups
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/62—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by hydrogenation of carbon-to-carbon double or triple bonds
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- C07C2602/00—Systems containing two condensed rings
- C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
- C07C2602/04—One of the condensed rings being a six-membered aromatic ring
- C07C2602/08—One of the condensed rings being a six-membered aromatic ring the other ring being five-membered, e.g. indane
Abstract
The invention discloses a method for preparing a 1, 3-dicarbonyl compound based on a metal hydride/palladium compound system, which comprises the following steps of suspending a palladium compound and a metal hydride in a solvent under the protection of nitrogen, adding an electron-deficient alkene compound, reacting for 0.3-10 hours at 0-100 ℃, adding a saturated ammonium chloride aqueous solution to stop the reaction, extracting, evaporating to dryness, and purifying by column chromatography to obtain the product 1, 3-dicarbonyl compound. The hydride and palladium compound catalysts used in the invention are reagents which are easily obtained in a laboratory, and compared with the common hydrogen hydrogenation method, the method is easier to operate, higher in safety, mild in condition and high in reaction yield.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to an application of a metal hydride/palladium compound system in a Michael-Dieckmann series reaction of electron-deficient alkene compounds, in particular to a method for preparing a 1, 3-dicarbonyl compound based on the metal hydride/palladium compound system.
Background
Sodium hydride is a strong base frequently used in laboratories and industry, and there are few reports on the use of sodium hydride as a reducing agent for a long time. The prior art techniques utilizing sodium hydride all require a large excess of sodium hydride (over 5 equivalents) and at least 2 equivalents of sodium iodide as a promoter.
The reduction of electron deficient alkene compounds is a common chemical transformation to produce the corresponding saturated carbonyl compounds. Such reactions are typically reduced using hydrogen/palladium on carbon conditions; in addition, some hydrogen-negative agents, such as [ (Ph)3P)CuH]6 (Stryker reagent), R3SiH, Hantzsch esters, etc. can also accomplish this reduction of electron deficient double bonds. However, these reducing conditions are either hazardous, such as explosive hydrogen; or the reagents are expensive, the reaction lacks atom economy and more waste needs to be disposed of after the reaction, such as [ (Ph)3P)CuH]6 (Stryker reagent), R3SiH, Hantzsch ester, and the like.
Disclosure of Invention
The technical problem to be solved by the invention is to provide the application of a metal hydride/palladium compound catalytic reduction system, thereby providing a method for carrying out Michael-Dieckmann series reaction on an ortho-ester group substituted electron-deficient alkene compound 1 to generate a 1, 3-dicarbonyl compound 3.
The invention adopts the following technical scheme:
a method for preparing 1, 3-dicarbonyl compounds based on a metal hydride/palladium compound system comprises the following steps of suspending a palladium compound and a metal hydride in a solvent under the protection of nitrogen, adding an electron-deficient olefin compound, and reacting at 0-100 ℃ for 0.3-10 hours to obtain the 1, 3-dicarbonyl compounds.
The technical means of the present invention for realizing the above mentioned series reaction (Michael-Dieckmann) is to take metal hydride as a reducing agent, palladium and salts thereof as a catalyst, and take an electron-deficient alkene compound as a substrate to react in a solvent to obtain a series product 1, 3-dicarbonyl compound.
In the present invention, the metal hydride is sodium hydride, lithium hydride, potassium hydride and calcium hydride, preferably sodium hydride and lithium hydride, more preferably sodium hydride.
In the invention, the palladium compound is palladium chloride, palladium acetate and Pd2(dba)3、Pd(TFA)2、[(η3-C3H5)PdCl]2、Pd(dppp)Cl2、Pd(C6H5CN)2Cl2、Pd(OH)2Palladium chloride and palladium acetate are preferred, and palladium chloride is more preferred.
The sodium hydride/palladium Michael-Dieckmann tandem reaction has the following advantages: 1) sodium hydride is very cheap compared to other reducing agents; the sodium hydride process is safer than hydrogen reduction. 2) The sodium hydride has small molecular weight, simple composition and small using amount in the reaction, so the method using the sodium hydride as the reducing agent is an atom economic method; the by-products are not produced other than harmless sodium salts, and no other waste is produced. 3) Sodium hydride and palladium catalysts are common reagents in laboratories and are very convenient to use. 4) Compared with the Stryker reagent, the combination of sodium hydride/palladium is much cheaper, and the palladium reagent can be recycled, so the method is more suitable for laboratory and industrial application.
In the invention, the chemical structural formula of the electron-deficient alkene compound is as follows:
r is aryl, alkyl, alkoxy, amino, etc.
In the present invention, the molar ratio of the palladium compound, the metal hydride compound and the electron-deficient alkene compound is (0.01-1): (1-5): 1, preferably, the molar ratio of the palladium compound, the metal hydride compound and the electron-deficient alkene compound is (0.05-0.15): (1-3): 1, more preferably, the molar ratio of the palladium compound, the metal hydride compound and the electron-deficient alkene compound is 0.1: (1.5-2.5): 1, most preferably, the molar ratio of the palladium compound, the metal hydride compound and the electron-deficient alkene compound is 0.1: 2: 1.
The above technical solution can be expressed as follows:
wherein R is aryl, alkyl, alkoxy, amino, etc.; m is metal such as lithium, sodium, potassium, calcium and the like.
The prior art conversion of compounds 1 to 3 can be accomplished in steps, such as reducing the double bond with hydrogen and then treating with a base to give 3; the method can also be completed by using a Stryker reagent in series connection in one pot, namely, the electron-deficient alkene in the 1 is subjected to Michael type conjugate reduction and Dieckmann reaction to obtain 3; wherein, the step reaction operation is complex, the cost is higher, the generated waste is more, although the one-pot series reaction is simple, the Stryker reagent is very expensive (1 g is more than 500 yuan), so the comprehensive cost is actually higher than that of the step method.
In the technical scheme, after the reaction is finished, adding a saturated ammonium chloride aqueous solution to stop the reaction, extracting with a solvent, evaporating to dryness, and purifying by column chromatography to obtain the product 1, 3-dicarbonyl compound.
In the above technical scheme, the solvent is DMA (N, N-dimethylacetamide), DMF, THF, DME, or dioxane.
In the technical scheme, the reaction temperature is preferably 25-60 ℃; the reaction time is preferably 0.3 to 2 hours.
The 1, 3-dicarbonyl compound 3 is prepared from an ortho ester group substituted electron deficient alkene compound 1 by generally adopting two types of methods: one is that hydrogen/palladium carbon is used for hydrogenation reduction of double bonds, and then Dieckmann condensation is carried out under alkaline, in the process, the use of hydrogen is a potential dangerous factor, and ignition and explosion can be caused by improper operation; the other is direct tandem reaction using very expensive Stryker reagent. Therefore, the invention has important significance in using the relatively safe and low-cost metal hydride for the Michael-Dieckmann series reaction; and more importantly, the method fully utilizes the reducibility and alkalinity of sodium hydride, and is a very atom-economical method.
The hydride and palladium compound catalysts used in the invention are reagents which are easily obtained in a laboratory, and compared with the common hydrogen hydrogenation method, the method is easier to operate, higher in safety, mild in condition and high in reaction yield.
Detailed Description
Example 1
Palladium chloride (5.3 mg, 0.03 mmol, 10 mol%) and sodium hydride (60% in oil, 24 mg, 0.6 mmol, 2 equiv) were suspended in DMA (1.5 mL) under nitrogen, stirred at 25 ℃ for 5 minutes, a solution of compound 1a (0.3 mmol) in DMA (0.5 mL) was added, then reacted at 25 ℃ for 2 hours, saturated aqueous ammonium chloride was added to stop the reaction, extracted with ethyl acetate, the combined extracts were dried over sodium sulfate, evaporated to dryness by rotary evaporation, and purified by column chromatography to give product 3a in yield>99%。The mixture of enol and keto form, enol/keto = 16/84. 1H NMR (400 MHz, CDCl3): δ 10.37 (br, 1H, enol), 7.78 (d, J = 7.6 Hz, 1H), 7.63 (t, J = 7.2 Hz, 1H), 7.53-7.35 (m, 2H), 3.86 (s, 3H, enol), 3.79 (s, 3H, keto), 3.74 (dd, J = 8.1, 3.9 Hz, 1H, keto), 3.57 (dd, J = 17.3, 3.4 Hz, 1H, keto), 3.52 (s, 2H, enol), 3.38 (dd, J = 17.2, 8.2 Hz, 1H, keto). 13C NMR (151 MHz, CDCl3): δ 199.58, 169.68, 153.73, 143.33 (enol), 135.61, 135.32 (enol), 129.54 (enol), 127.97, 126.97 (enol), 126.68, 124.86, 120.89, 102.30 (enol), 53.27, 52.95, 51.39 (enol), 32.65 (enol), 30.40. LR-MS (ESI): m/z 191.2 [M+H]+。
Example 2
Palladium acetate (2.7 mg, 0.015 mmol, 5 mol%) and lithium hydride (7.2 mg, 0.9 mmol, 3.0 equiv) were suspended in DMF (1.5 mL) under nitrogen, stirred at 25 ℃ for 5 min, a solution of compound 1a (0.3 mmol) in DMF (0.5 mL) was added, then reacted at 100 ℃ for 0.3 h, saturated aqueous ammonium chloride was added to stop the reaction, extracted with ethyl acetate, the combined extracts were dried over sodium sulfate, evaporated to dryness by rotary evaporation, and purified by column chromatography to give product 3a, yield 91%.
Example 3
Under the protection of nitrogen, Pd2(dba)3(2.7 mg, 0.003 mmol, 1 mol%) and potassium hydride (30% in oil, 200 mg, 1.5 mmol, 5 equiv) were suspended in THF (1.5 mL), stirred at 25 ℃ for 5 minutes, a solution of compound 1a (0.3 mmol) in THF (0.5 mL) was added and then reacted at 0 ℃ for 10 hours, a saturated aqueous ammonium chloride solution was added to quench the reaction, extracted with ethyl acetate, the combined extracts were dried over sodium sulfate, rotary evaporated to dryness, and purified by column chromatography to give product 3a in 82% yield.
Example 4
Pd (TFA) under nitrogen protection2(100 mg, 0.3 mmol, 100 mol%) and calcium hydride (24 mg, 0.6 mmol, 2.0 equiv) were suspended in DME (1.5 mL) and stirred at 25 ℃ for 5 minAfter that, a solution of compound 1a (0.3 mmol) in DME (0.5 mL) was added, followed by reaction at 90 ℃ for 0.3 hour, addition of a saturated aqueous solution of ammonium chloride to terminate the reaction, extraction with ethyl acetate, combination of extracts, drying with sodium sulfate, rotary evaporation to dryness, and purification by column chromatography to give product 3a in 83% yield.
Example 5
Under the protection of nitrogen, [ (eta ]3-C3H5)PdCl]2(2.1 mg, 0.006 mmol, 2 mol%) and sodium hydride (60% in oil, 12 mg, 0.30 mmol, 1.0 equiv) were suspended in dioxane (1.5 mL), stirred at 25 ℃ for 5 minutes, a solution of compound 1a (0.3 mmol) in dioxane (0.5 mL) was added, then reacted at 30 ℃ for 2 hours, saturated aqueous ammonium chloride was added to stop the reaction, extracted with ethyl acetate, the extracts were combined, dried over sodium sulfate, rotary evaporated to dryness and purified by column chromatography to give product 3a in 65% yield.
Example 6
Pd (dppp) Cl under nitrogen protection2(18 mg, 0.03 mmol, 10 mol%) and sodium hydride (60% in oil, 24 mg, 0.6 mmol, 2 equiv) were suspended in DMA (1.5 mL), stirred at 25 ℃ for 5 minutes, a solution of compound 1a (0.3 mmol) in DMA (0.5 mL) was added, then reacted at 25 ℃ for 2 hours, a saturated aqueous ammonium chloride solution was added to terminate the reaction, extracted with ethyl acetate, the combined extracts were dried over sodium sulfate, rotary evaporated to dryness, purified by column chromatography to give product 3a in 63% yield.
Example 7
Pd (C) under nitrogen protection6H5CN)2Cl2(11.4 mg, 0.03 mmol, 10 mol%) and sodium hydride (60% in oil, 24 mg, 0.6 mmol, 2 equiv) were suspended in DMA (1.5 mL), stirred at 25 ℃ for 5 minutes, a solution of compound 1a (0.3 mmol) in DMA (0.5 mL) was added, then reacted at 25 ℃ for 2 hours, saturated aqueous ammonium chloride solution was added to quench the reaction, extracted with ethyl acetate, the combined extracts were dried over sodium sulfate, rotary evaporated to dryness, purified by column chromatography to give product 3a in 77% yield.
Example 8
Under the protection of nitrogen, Pd (OH)2(4.2 mg, 0.03 mmol, 10 mol%) and sodium hydride (60% in oil, 24 mg, 0.6 mmol, 2 equiv) were suspended in DMA (1.5 mL), stirred at 25 ℃ for 5 minutes, a solution of compound 1a (0.3 mmol) in DMA (0.5 mL) was added, then reacted at 25 ℃ for 2 hours, saturated aqueous ammonium chloride solution was added to quench the reaction, extracted with ethyl acetate, the combined extracts were dried over sodium sulfate, rotary evaporated to dryness, purified by column chromatography to give product 3a in 69% yield.
Example 9
Palladium chloride (5.3 mg, 0.03 mmol, 10 mol%) and sodium hydride (60% in oil, 24 mg, 0.6 mmol, 2 equiv) were suspended in DMA (1.5 mL) under nitrogen, stirred at 25 ℃ for 5 minutes, a solution of compound 1b (0.3 mmol) in DMA (0.5 mL) was added, then reacted at 25 ℃ for 2 hours, saturated aqueous ammonium chloride was added to stop the reaction, extracted with ethyl acetate, the combined extracts were dried over sodium sulfate, evaporated to dryness by rotary evaporation, and purified by column chromatography to give product 3b in 98% yield.1H NMR (400 MHz, CDCl3): δ 7.69 (d, J = 7.6 Hz, 1H), 7.59-7.40 (m, 6H), 7.38-7.29 (m, 2H), 3.74 (dd, J = 8.0, 4.3 Hz, 1H), 3.56 (dd, J = 16.9, 3.9 Hz, 1H), 3.37 (s, 3H), 3.13 (dd, J = 16.8, 8.1 Hz, 1H). 13C NMR (151 MHz, CDCl3): δ 202.19, 169.67, 154.41, 143.94, 135.80, 135.10, 129.94, 128.24, 127.95, 127.61, 126.46, 124.42, 51.10, 37.92, 31.80. LR-MS (ESI): m/z 266.1 [M+H]+。
Example 10
Palladium chloride (5.3 mg, 0.03 mmol, 10 mol%) and sodium hydride (60% in oil, 24 mg, 0.6 mmol, 2 equiv) were suspended in DMA (1.5 mL) under nitrogen, stirred at 25 ℃ for 5 minutes, a solution of compound 1c (0.3 mmol) in DMA (0.5 mL) was added, then reacted at 25 ℃ for 2 hours, saturated aqueous ammonium chloride was added to stop the reaction, extracted with ethyl acetate, the combined extracts were dried over sodium sulfate, evaporated to dryness by rotary evaporation, and purified by column chromatography to give product 3c in 98% yield. The mixture of alcohol and keto form, alcohol/keto = 84/16. 1H NMR (400 MHz, CDCl3): δ 7.81 (d, J = 7.6 Hz, 1H, enol), 7.72 (d, J = 7.6 Hz, 1H, keto), 7.63-7.46 (m, 2H, enol and keto), 7.44-7.33 (m, 1H, enol and keto), 4.11-3.92 (m, 1H, keto), 3.77-3.68 (m, 1H, keto), 3.58 (s, 2H, enol), 3.12 (dd, J = 17.4, 7.7 Hz, 1H, keto), 2.49 (s, 3H, keto), 2.17 (s, 3H, enol). 13C NMR (151 MHz, CDCl3): δ 201.52 (keto), 199.85 (keto), 191.56, 177.60, 154.24 (keto), 147.63, 138.31, 135.52 (keto), 135.14 (keto), 132.88, 127.76 (keto), 127.43, 126.73 (keto), 125.85, 124.61 (keto), 123.28, 110.56, 62.07 (keto), 30.38, 29.82 (keto), 28.00 (keto), 21.18. LR-MS (ESI): m/z 175.1 [M+H]+。
Example 11
Palladium chloride (5.3 mg, 0.03 mmol, 10 mol%) and sodium hydride (60% in oil, 24 mg, 0.6 mmol, 2 equiv) were suspended in DMA (1.5 mL) under nitrogen, stirred at 25 ℃ for 5 min, and Compound 1d (0.3 mmol, 2 equiv) was added) After 2 hours of reaction in DMA (0.5 mL) at 25 ℃, saturated aqueous ammonium chloride was added to quench the reaction, ethyl acetate was used for extraction, the combined extracts were dried over sodium sulfate, evaporated to dryness and purified by column chromatography to give the product 3d in 99% yield. The mixture of alcohol and keto form, alcohol/keto = 87/13.1H NMR (400 MHz, CDCl3): δ 15.08 (br, 1H, enol), 8.14 (d, J = 7.6 Hz, 2H, keto), 8.00-7.92 (m, 2H, enol), 7.89 (d, J = 7.6 Hz, 1H, enol), 7.73 (d, J = 7.6 Hz, 1H, keto), 7.62-7.48 (m, 5H, enol and keto), 7.44 (t, J = 7.2 Hz, 1H, enol), 7.40-7.35 (m, 1H, keto), 4.87 (dd, J = 7.4, 2.6 Hz, 1H, keto), 3.94 (s, 2H, enol), 3.90-3.75 (m, 1H, keto), 3.34 (dd, J = 17.1, 7.7 Hz, 1H, keto). 13C NMR (151 MHz, CDCl3): δ 200.12 (keto), 195.95, 194.40 (keto), 170.91, 154.47 (keto), 148.70, 145.81 (keto), 138.03, 136.43 (keto), 135.41 (keto), 134.94 (keto), 133.68 (keto), 133.47, 131.40, 129.96, 128.74, 128.25, 127.83 (keto), 127.59, 126.65 (keto), 125.73, 124.77(keto), 123.57, 109.58, 56.69 (keto), 32.37, 30.20 (keto). LR-MS (ESI): m/z 237.0 [M+H]+。
Claims (7)
1. A method for preparing a 1, 3-dicarbonyl compound based on a metal hydride/palladium compound system comprises the following steps of suspending a palladium compound and a metal hydride in a solvent under the protection of nitrogen, adding an electron-deficient alkene compound, and reacting at 0-100 ℃ for 0.3-10 hours to obtain the 1, 3-dicarbonyl compound; the metal hydride is sodium hydride or lithium hydride; the palladium compound is palladium chloride or palladium acetate; the chemical structural formula of the electron-deficient alkene compound is as follows:
2. the method of claim 1, wherein the metal hydride is sodium hydride; the palladium compound is palladium chloride.
3. The method according to claim 1, wherein the molar ratio of the palladium compound, the metal hydride compound and the electron-deficient ene compound is (0.01-1): (1-5): 1.
4. The method according to claim 3, wherein the molar ratio of the palladium compound, the metal hydride and the electron-deficient alkylene compound is (0.05-0.15): (1-3): 1.
5. The method of claim 1, wherein after the reaction is completed, a saturated aqueous solution of ammonium chloride is added to terminate the reaction, and then the product 1, 3-dicarbonyl compound is obtained by extraction, evaporation to dryness and column chromatography purification.
6. The method of claim 1, wherein the solvent is DMA, DMF, THF, DME, or dioxane.
7. The method according to claim 1, wherein the reaction temperature is 25-60 ℃; the reaction time is 0.3-2 hours.
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2010057865A1 (en) * | 2008-11-19 | 2010-05-27 | Glaxo Group Limited | N- inden- 2 -yl- isopropylsulfonamides as ampa receptor potentiators |
CN102491886A (en) * | 2011-12-01 | 2012-06-13 | 上海化工研究院 | Method for synthetizing indanone compound |
CN102863376A (en) * | 2012-09-27 | 2013-01-09 | 上海师范大学 | N-substituted methyl-3,5-disubstituted benzylidene base-4-piperidone and preparation method and application thereof |
WO2018079759A1 (en) * | 2016-10-31 | 2018-05-03 | 塩野義製薬株式会社 | Fused heterocycle having trka inhibitory activity and fused carbocycle derivative |
-
2018
- 2018-09-13 CN CN201811070607.1A patent/CN108976122B/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2010057865A1 (en) * | 2008-11-19 | 2010-05-27 | Glaxo Group Limited | N- inden- 2 -yl- isopropylsulfonamides as ampa receptor potentiators |
CN102491886A (en) * | 2011-12-01 | 2012-06-13 | 上海化工研究院 | Method for synthetizing indanone compound |
CN102863376A (en) * | 2012-09-27 | 2013-01-09 | 上海师范大学 | N-substituted methyl-3,5-disubstituted benzylidene base-4-piperidone and preparation method and application thereof |
WO2018079759A1 (en) * | 2016-10-31 | 2018-05-03 | 塩野義製薬株式会社 | Fused heterocycle having trka inhibitory activity and fused carbocycle derivative |
Non-Patent Citations (3)
Title |
---|
《1,4-Addition of arylboronic acids to β-aryl-α,β-unsaturated ketones and esters catalyzed by a rhodium(I)–chiraphos complex for catalytic and enantioselective synthesis of selective endothelin A receptor antagonists》;Itoh, Takahiro et al.;《Tetrahedron》;20061009;第62卷(第41期);第9610-9621页 * |
《Solvent Effect in Reactions Using Stryker"s Reagent》;Sass, Daiane Cristina et al.;《Journal of Organic Chemistry 》;20120918;第77卷(第20期);第9374-9378页 * |
《钯催化的串联反应构建苯并五元杂环的研究进展》;丁刚等;《有机化学》;20151109;第36卷;第43-59页 * |
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