CN108976122A - The method for preparing 1,3- dicarbonyl compound based on metal hydride/palladium compound system - Google Patents
The method for preparing 1,3- dicarbonyl compound based on metal hydride/palladium compound system Download PDFInfo
- Publication number
- CN108976122A CN108976122A CN201811070607.1A CN201811070607A CN108976122A CN 108976122 A CN108976122 A CN 108976122A CN 201811070607 A CN201811070607 A CN 201811070607A CN 108976122 A CN108976122 A CN 108976122A
- Authority
- CN
- China
- Prior art keywords
- compound
- palladium
- hydride
- metal hydride
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/313—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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses based on metal hydride/palladium compound system preparation 1; the method of 3- dicarbonyl compound; include the following steps, under nitrogen protection, palladium compound and metal hydride are suspended in solvent; then Electron-poor olefin compound is added; it is reacted at 0 DEG C~100 DEG C 0.3~10 hour, saturated aqueous ammonium chloride stopped reaction is then added, then extracts, be evaporated, column chromatographic purifying; obtain product 1,3- dicarbonyl compound.Hydride used in the present invention and palladium compound catalyst are all the reagents being easy to get in laboratory, and compared to common hydrogen method for hydrogenation, the method is easier to operate, and safety is higher, mild condition, and reaction yield is high.
Description
Technical field
The invention belongs to technical field of organic synthesis, and in particular to metal hydride/palladium compound system is in Electron-poor olefin
Application in compound Michael-Dieckmann tandem reaction, more particularly to it is based on metal hydride/palladium compound system system
The method of standby 1,3- dicarbonyl compound.
Background technique
Sodium hydride is a kind of laboratory and the highly basic being industrially commonly used, for a long time, few as reducing agent quilt
The relevant report used.The existing technology using sodium hydride requires large excess of sodium hydride (more than 5 equivalents), and needs
At least the sodium iodide of 2 equivalents is as promotor.
The reduction of Electron-poor olefin compound is a kind of common chemical conversion, generates the carbonyls being saturated accordingly.
This kind of reaction is usually to be restored using hydrogen/palladium carbon condition；In addition, some negative reagents of hydrogen, such as [(Ph3P)CuH]6
(Stryker reagent), R3SiH, Hantzsch ester etc. can also complete the reduction of this electron deficient double bond.But these are restored
Condition or hydrogen with certain risk, such as explosive；Reagent is more expensive, reaction lack Atom economy and
It needs to handle more waste, such as [(Ph after reaction3P)CuH]6 (Stryker reagent), R3SiH, Hantzsch ester etc..
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of metal hydride/palladium compound catalytic reduction systems to answer
With, so that a kind of progress Michael-Dieckmann tandem reaction of Electron-poor olefin compound 1 that ortho position ester group replaces is provided, it is raw
At the method for 1,3- dicarbonyl compound 3.
The present invention adopts the following technical scheme:
Based on metal hydride/palladium compound system preparation 1,3- dicarbonyl compound method, include the following steps, nitrogen is protected
Under shield, palladium compound and metal hydride are suspended in solvent, Electron-poor olefin compound is then added, at 0 DEG C~100 DEG C
Reaction 0.3~10 hour, obtains 1,3- dicarbonyl compound.
The present invention realizes that the technological means of above-mentioned tandem reaction (Michael-Dieckmann) is with metal hydride
Object is reducing agent, and palladium and its esters are catalyst, and using Electron-poor olefin compound as substrate, reaction obtains concatemer production in a solvent
1,3- dicarbonyl compound.
In the present invention, the metal hydride is sodium hydride, lithium hydride, hydrofining and calcium hydride, preferably sodium hydride and hydrogen
Change lithium, more preferable sodium hydride.
In the present invention, the palladium compound is palladium chloride, palladium acetate, Pd2(dba)3、Pd(TFA)2、[(η3-C3H5)
PdCl]2、Pd(dppp)Cl2、Pd(C6H5CN)2Cl2、Pd(OH)2, preferably palladium chloride and palladium acetate, more preferable palladium chloride.
Sodium hydride/palladium, which carries out Michael-Dieckmann tandem reaction, following advantage: 1) compared to other reduction
Agent, sodium hydride are extremely cheap；Compared to hydrogen reducing, the safety of sodium hydride method is higher.2) sodium hydride molecular weight is small
And composition is simple, and usage amount is few in reaction, so being a kind of method of atom economy as reducing agent with sodium hydride；By-product
In addition to harmless sodium salt, generated without other wastes.3) sodium hydride and palladium catalyst are all the common reagents in laboratory, using rise
Come very convenient.4) compared to Stryker reagent, sodium hydride/palladium package price want it is cheap very much, and palladium reagent can return
It receives and utilizes, so being more suitable for laboratory and industrial application.
In the present invention, the chemical structural formula of Electron-poor olefin compound is as follows:
R is aryl, alkyl, alkoxy, amido etc..
In the present invention, the palladium compound, metal hydride, Electron-poor olefin compound molar ratio be (0.01~1):
(1~5): 1, it is preferred that the palladium compound, metal hydride, Electron-poor olefin compound molar ratio be (0.05~0.15)
: (1~3): 1, it is furthermore preferred that the molar ratio of the palladium compound, metal hydride, Electron-poor olefin compound is 0.1: (1.5
~2.5): 1, most it is furthermore preferred that the palladium compound, metal hydride, Electron-poor olefin compound molar ratio be 0.1: 2: 1.
Above-mentioned technical proposal can be expressed as follows:
R therein is aryl, alkyl, alkoxy, amido etc.；M is the metals such as lithium, sodium, potassium, calcium.
The prior art can be completed step by step from the conversion of compound 1 to 3, for example first use hydrogen reducing double bond, then at alkali
Reason is to obtain 3；Also the one pot of series connection of Stryker reagent can be used to complete, that is, first the Electron-poor olefin in 1 is carried out
The conjugation reduction of Michael type, Dieckmann react to obtain 3；Wherein, stepwise reaction is complicated for operation, higher cost, generates
Waste it is more, although one pot of tandem reaction is simple, Stryker reagent is very expensive (1g > 500 yuan), so overall cost
It is in fact more taller than the method for fractional steps.
In above-mentioned technical proposal, saturated aqueous ammonium chloride stopped reaction is added after reaction, with solvent extraction, steams
Dry, column chromatographic purifying obtains product 1,3- dicarbonyl compound.
In above-mentioned technical proposal, the solvent is DMA (n,N-dimethylacetamide), DMF, THF, DME or dioxy six
Ring.
In above-mentioned technical proposal, preferably 25~60 DEG C of the temperature of the reaction；The time of the reaction preferably 0.3~2 is small
When.
The Electron-poor olefin compound 1 replaced from ortho position ester group prepares 1,3- dicarbonyl compound 3, generally uses two class sides
Method: one kind is to carry out hydro-reduction double bond using hydrogen/palladium carbon, Dieckmann condensation then occurs under alkalinity, in this mistake
Cheng Zhong, the use of hydrogen are a potential risk factors, and misoperation will cause kindling, explosion；Another kind of is using valence
The very expensive direct tandem reaction of Stryker reagent of lattice.So the present invention uses relatively safe and cheap gold
Belong to hydride to have great importance for Michael-Dieckmann tandem reaction；And importantly, the method is abundant
The reproducibility and alkalinity of sodium hydride is utilized, is the method for very atom economy.
Hydride used in the present invention and palladium compound catalyst are all the reagents being easy to get in laboratory, compared to normal
Hydrogen method for hydrogenation, the method is easier to operate, and safety is higher, mild condition, and reaction yield is high.
Specific embodiment
Embodiment 1
Under nitrogen protection, palladium chloride (5.3 mg, 0.03 mmol, 10 mol%) and sodium hydride (60% in oil, 24 mg,
0.6 mmol, 2 equiv) it is suspended in DMA (1.5 mL), 25 DEG C are stirred 5 minutes, and compound 1a (0.3 mmol) is added and exists
Then the solution of DMA (0.5 mL) reacts 2 hours at 25 DEG C, saturated aqueous ammonium chloride stopped reaction is added, with acetic acid second
Ester extraction, combining extraction liquid is dry with sodium sulphate, and revolving is evaporated, and column chromatographic purifying obtains product 3a, 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]+。
Embodiment 2
Under nitrogen protection, palladium acetate (2.7 mg, 0.015 mmol, 5 mol%) and lithium hydride (7.2 mg, 0.9 mmol,
3.0 equiv) it is suspended in DMF (1.5 mL), 25 DEG C are stirred 5 minutes, and compound 1a (0.3 mmol) is added in DMF (0.5
ML solution) then reacts 0.3 hour at 100 DEG C, and saturated aqueous ammonium chloride stopped reaction is added, is extracted with ethyl acetate,
Combining extraction liquid, dry with sodium sulphate, revolving is evaporated, and column chromatographic purifying obtains product 3a, yield 91%.
Embodiment 3
Under nitrogen protection, Pd2(dba)3(2.7 mg, 0.003 mmol, 1 mol%) and hydrofining (30% in oil,
200 mg, 1.5 mmol, 5 equiv) it is suspended in THF (1.5 mL), 25 DEG C are stirred 5 minutes, and compound 1a (0.3 is added
Mmol it) in the solution of THF (0.5 mL), is then reacted 10 hours at 0 DEG C, saturated aqueous ammonium chloride stopped reaction is added,
It is extracted with ethyl acetate, combining extraction liquid, dry with sodium sulphate, revolving is evaporated, and column chromatographic purifying obtains product 3a, yield
82%。
Embodiment 4
Under nitrogen protection, Pd (TFA)2(100 mg, 0.3 mmol, 100 mol%) and calcium hydride (24 mg, 0.6
Mmol, 2.0 equiv) it is suspended in DME (1.5 mL), 25 DEG C are stirred 5 minutes, and compound 1a (0.3 mmol) is added and exists
Then the solution of DME (0.5 mL) reacts 0.3 hour at 90 DEG C, saturated aqueous ammonium chloride stopped reaction is added, uses acetic acid
Ethyl ester extraction, combining extraction liquid is dry with sodium sulphate, and revolving is evaporated, and column chromatographic purifying obtains product 3a, yield 83%.
Embodiment 5
Under nitrogen protection, [(η3-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) it is suspended in dioxane (1.5 mL), 25 DEG C are stirred 5 minutes, additionization
Object 1a (0.3 mmol) is closed in the solution of dioxane (0.5 mL), is then reacted 2 hours at 30 DEG C, saturated ammonium chloride is added
Aqueous solution stopped reaction, is extracted with ethyl acetate, combining extraction liquid, dry with sodium sulphate, and revolving is evaporated, and column chromatographic purifying obtains
To product 3a, yield 65%.
Embodiment 6
Under nitrogen protection, Pd (dppp) Cl2(18 mg, 0.03 mmol, 10 mol%) and sodium hydride (60% in oil,
24 mg, 0.6 mmol, 2 equiv) it is suspended in DMA (1.5 mL), 25 DEG C are stirred 5 minutes, and compound 1a (0.3 is added
Mmol it) in the solution of DMA (0.5 mL), is then reacted 2 hours at 25 DEG C, saturated aqueous ammonium chloride stopped reaction is added,
It is extracted with ethyl acetate, combining extraction liquid, dry with sodium sulphate, revolving is evaporated, and column chromatographic purifying obtains product 3a, yield
63%。
Embodiment 7
Under nitrogen protection, Pd (C6H5CN)2Cl2(11.4 mg, 0.03 mmol, 10 mol%) and sodium hydride (60% in
Oil, 24 mg, 0.6 mmol, 2 equiv) it is suspended in DMA (1.5 mL), 25 DEG C are stirred 5 minutes, and compound 1a is added
Then (0.3 mmol) reacts 2 hours in the solution of DMA (0.5 mL) at 25 DEG C, saturated aqueous ammonium chloride is added and stops
Reaction, is extracted with ethyl acetate, combining extraction liquid, dry with sodium sulphate, and revolving is evaporated, and column chromatographic purifying obtains product 3a, receives
Rate 77%.
Embodiment 8
Under nitrogen protection, Pd (OH)2(4.2 mg, 0.03 mmol, 10 mol%) and sodium hydride (60% in oil, 24
Mg, 0.6 mmol, 2 equiv) it is suspended in DMA (1.5 mL), 25 DEG C are stirred 5 minutes, and compound 1a (0.3 is added
Mmol it) in the solution of DMA (0.5 mL), is then reacted 2 hours at 25 DEG C, saturated aqueous ammonium chloride stopped reaction is added,
It is extracted with ethyl acetate, combining extraction liquid, dry with sodium sulphate, revolving is evaporated, and column chromatographic purifying obtains product 3a, yield
69%。
Embodiment 9
Under nitrogen protection, palladium chloride (5.3 mg, 0.03 mmol, 10 mol%) and sodium hydride (60% in oil, 24 mg,
0.6 mmol, 2 equiv) it is suspended in DMA (1.5 mL), 25 DEG C are stirred 5 minutes, and compound 1b (0.3 mmol) is added and exists
Then the solution of DMA (0.5 mL) reacts 2 hours at 25 DEG C, saturated aqueous ammonium chloride stopped reaction is added, with acetic acid second
Ester extraction, combining extraction liquid is dry with sodium sulphate, and revolving is evaporated, and column chromatographic purifying obtains product 3b, yield 98%.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]+。
Embodiment 10
Under nitrogen protection, palladium chloride (5.3 mg, 0.03 mmol, 10 mol%) and sodium hydride (60% in oil, 24 mg,
0.6 mmol, 2 equiv) it is suspended in DMA (1.5 mL), 25 DEG C are stirred 5 minutes, and compound 1c (0.3 mmol) is added and exists
Then the solution of DMA (0.5 mL) reacts 2 hours at 25 DEG C, saturated aqueous ammonium chloride stopped reaction is added, with acetic acid second
Ester extraction, combining extraction liquid is dry with sodium sulphate, and revolving is evaporated, and column chromatographic purifying obtains product 3c, yield 98%.The
mixture of enol and keto form, enol/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]+。
Embodiment 11
Under nitrogen protection, palladium chloride (5.3 mg, 0.03 mmol, 10 mol%) and sodium hydride (60% in oil, 24 mg,
0.6 mmol, 2 equiv) it is suspended in DMA (1.5 mL), 25 DEG C are stirred 5 minutes, and compound 1d (0.3 mmol) is added and exists
Then the solution of DMA (0.5 mL) reacts 2 hours at 25 DEG C, saturated aqueous ammonium chloride stopped reaction is added, with acetic acid second
Ester extraction, combining extraction liquid is dry with sodium sulphate, and revolving is evaporated, and column chromatographic purifying obtains product 3d, yield 99%.The
mixture of enol and keto form, enol/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 (10)
1. being included the following steps, nitrogen based on metal hydride/palladium compound system preparation 1,3- dicarbonyl compound method
Under protection, palladium compound and metal hydride are suspended in solvent, Electron-poor olefin compound is then added, at 0 DEG C~100 DEG C
Lower reaction 0.3~10 hour, obtains 1,3- dicarbonyl compound.
2. the method according to claim 1, wherein the metal hydride includes sodium hydride, lithium hydride, hydrogenation
Potassium, calcium hydride；The palladium compound includes palladium chloride, palladium acetate, Pd2(dba)3、Pd(TFA)2、[(η3-C3H5)PdCl]2、Pd
(dppp)Cl2、Pd(C6H5CN)2Cl2、Pd(OH)2。
3. according to the method described in claim 2, it is characterized in that, the metal hydride is sodium hydride or lithium hydride；Institute
Stating palladium compound is palladium chloride or palladium acetate.
4. according to the method described in claim 3, it is characterized in that, the metal hydride is sodium hydride；The palladium compound
For palladium chloride.
5. the method according to claim 1, wherein the chemical structural formula of the Electron-poor olefin compound is as follows:
R is selected from aryl, alkyl, alkoxy, amido.
6. the method according to claim 1, wherein the palladium compound, metal hydride, Electron-poor olefin chemical combination
The molar ratio of object is (0.01~1): (1~5): 1.
7. according to the method described in claim 6, it is characterized in that, the palladium compound, metal hydride, Electron-poor olefin chemical combination
The molar ratio of object is (0.05~0.15): (1~3): 1.
8. the method according to claim 1, wherein after reaction, saturated aqueous ammonium chloride being added and stops
Reaction, then extracts, is evaporated, column chromatographic purifying, obtaining product 1,3- dicarbonyl compound.
9. the method according to claim 1, wherein the solvent is DMA, DMF, THF, DME or dioxy six
Ring.
10. the method according to claim 1, wherein the temperature of the reaction is 25~60 DEG C；The reaction
Time is 0.3~2 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811070607.1A CN108976122B (en) | 2018-09-13 | 2018-09-13 | Method for producing 1, 3-dicarbonyl compounds based on metal hydride/palladium compound systems |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811070607.1A CN108976122B (en) | 2018-09-13 | 2018-09-13 | Method for producing 1, 3-dicarbonyl compounds based on metal hydride/palladium compound systems |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108976122A true CN108976122A (en) | 2018-12-11 |
| CN108976122B CN108976122B (en) | 2021-01-12 |
Family
ID=64545984
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811070607.1A Active CN108976122B (en) | 2018-09-13 | 2018-09-13 | Method for producing 1, 3-dicarbonyl compounds based on metal hydride/palladium compound systems |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108976122B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020056565A1 (en) * | 2018-09-17 | 2020-03-26 | 南通纺织丝绸产业技术研究院 | Application of metal hydride/palladium compound system in preparation of 1,3-dicarbonyl compound in cascade reaction of electron-deficient alkene compound |
| WO2020056564A1 (en) * | 2018-09-17 | 2020-03-26 | 南通纺织丝绸产业技术研究院 | Method for preparing 1,3-dicarbonyl compound based on metal hydride/palladium compound system |
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 |
|---|
| ITOH, TAKAHIRO ET AL.: "《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》", 《TETRAHEDRON》 * |
| SASS, DAIANE CRISTINA ET AL.: "《Solvent Effect in Reactions Using Stryker"s Reagent》", 《JOURNAL OF ORGANIC CHEMISTRY 》 * |
| 丁刚等: "《钯催化的串联反应构建苯并五元杂环的研究进展》", 《有机化学》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020056565A1 (en) * | 2018-09-17 | 2020-03-26 | 南通纺织丝绸产业技术研究院 | Application of metal hydride/palladium compound system in preparation of 1,3-dicarbonyl compound in cascade reaction of electron-deficient alkene compound |
| WO2020056564A1 (en) * | 2018-09-17 | 2020-03-26 | 南通纺织丝绸产业技术研究院 | Method for preparing 1,3-dicarbonyl compound based on metal hydride/palladium compound system |
| US11180437B2 (en) | 2018-09-17 | 2021-11-23 | Soochow University | Method for preparing 1,3-dicarbonyl compound based on metal hydride/palladium compound system |
| US11795132B2 (en) | 2018-09-17 | 2023-10-24 | Soochow University | Application of metal hydride/palladium compound system in preparation of 1,3-dicarbonyl compound in cascade reaction of electron-deficient alkene compound |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108976122B (en) | 2021-01-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112174782B (en) | Application of metal deuteride/palladium compound catalytic reduction system in deuteration reaction | |
| CN108358760B (en) | Application of metalate/palladium compound catalytic reduction system in debenzylation reaction and deuteration reaction | |
| CN108976122A (en) | The method for preparing 1,3- dicarbonyl compound based on metal hydride/palladium compound system | |
| CN109053446A (en) | Metal hydride/palladium compound system prepares the application in 1,3- dicarbonyl compound in Electron-poor olefin compound tandem reaction | |
| CN102584820A (en) | Preparation method for 5-bromo-7-azaindole | |
| CN113509947B (en) | Catalyst for synthesizing p-methylanisole as well as preparation method and application thereof | |
| CN111320587A (en) | Preparation method of 1H-1,2, 3-triazole | |
| CN109020864A (en) | Application and restoring method of the metal hydride/palladium compound catalytic reduction system in the reduction of alkenyl active methylene compound | |
| US11180437B2 (en) | Method for preparing 1,3-dicarbonyl compound based on metal hydride/palladium compound system | |
| US11420925B2 (en) | Reduction method and reduction product of alkenyl active methylene compound | |
| CN109096105B (en) | Reduction method of alkenyl active methylene compound and reduction product | |
| CN109020865B (en) | 3, 3-disubstituted oxindole and preparation method thereof | |
| CN114644587A (en) | Synthesis process of intermediate bicyclic imine of anti-novel coronavirus pneumonia medicine Paxlovid | |
| CN101139254A (en) | Method for manufacturing 1,2-dioles from carbonyl compounds | |
| CN112939893B (en) | Synthesis method of 4- (4-aminophenyl) -3-morpholinone | |
| US11795132B2 (en) | Application of metal hydride/palladium compound system in preparation of 1,3-dicarbonyl compound in cascade reaction of electron-deficient alkene compound | |
| CN103755706B (en) | A kind of environment-friendly preparation method synthesizing folic acid | |
| JP2003313171A (en) | Method for producing n-alkyl-n'-alkylimidazolium salt | |
| WO2020051853A1 (en) | 3,3-disubstituted oxindole and preparation method thereof | |
| CN103254111B (en) | Preparation method of 2,5-dihydropyrrole | |
| CN108069897B (en) | Method for synthesizing nicotinic acid by using carbon dioxide | |
| CN110950865B (en) | Synthetic method of medical intermediate 8-chloro-1, 7-naphthyridine-3-formaldehyde | |
| CN107540548B (en) | Method for preparing dibutyl carbonate | |
| JPS6039349B2 (en) | Method for producing 2-cyanophenol derivatives | |
| CN116003422A (en) | Synthesis method of 6-bromofuro [3,2-b ] pyridine-2-formaldehyde |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |