CN111270260B - Method for alkenylating ortho-position of aromatic amide compound - Google Patents
Method for alkenylating ortho-position of aromatic amide compound Download PDFInfo
- Publication number
- CN111270260B CN111270260B CN202010083526.6A CN202010083526A CN111270260B CN 111270260 B CN111270260 B CN 111270260B CN 202010083526 A CN202010083526 A CN 202010083526A CN 111270260 B CN111270260 B CN 111270260B
- Authority
- CN
- China
- Prior art keywords
- reaction
- ortho
- aromatic amide
- group
- compound according
- 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.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/23—Oxidation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention discloses an ortho-alkenylation method of an aromatic amide compound, which comprises the following steps: the method utilizes current as an oxidant and Rh as a catalyst to activate a C-H bond of aromatic amide, efficiently performs olefin insertion reaction, eliminates beta-H to obtain a Heck type product, and can realize conversion to a high valence state under the action of current in the reaction process, thereby realizing catalytic cycle, reducing the use of rhodium and reducing pollution. The reaction is operated integrally, and the yield is high. Wherein, the reaction system is aqueous solution, has high conductivity, does not need extra electrolyte, is green and economic; the reaction substrate has better regioselectivity and wide selection range, and has stronger practicability and better universality.
Description
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a method for alkenylating an ortho-position of an aromatic amide compound assisted by a guide group (DG).
Background
Heck reaction is an important reaction for alkenylation of halogenated aromatic hydrocarbon to form new C-C bond. Heck first discovered in 1972, and the reaction is extremely valuable, so the method is very popular with researchers in the field of organic catalysis in recent years. Among them, Heck reaction in which a guide group assists a transition metal to catalyze C-H bond activation is also rapidly developing.
Conventional directing groups assist transition metal catalyzed reactions as shown below. Obviously, the method needs a large amount of inorganic or organic oxidant, so that not only harsh oxidation reaction conditions are required, but also waste metal is generated, and the environmental pollution is caused.
The electrochemical synthesis of organic compounds has been well developed in the last decade. To search for a greener synthetic route and achieve direct C-H activation/olefination electrochemical synthesis different from the traditional guide group assisted, we designed the following reaction: dissolving aromatic amide, non-activated olefin and additive in water phase medium, and oxidizing with weak current and using Rh (III) as catalyst to obtain Heck type product. Compared with the traditional Heck reaction which directly uses anode to oxidize Rh, the designed reaction is converted into Rh (I) by means of Rh (III) after beta-hydrogen elimination, and Rh (I) is oxidized into Rh (III) at a carbon electrode to realize catalytic cycle.
Disclosure of Invention
The invention provides an ortho-alkenylation method of an aromatic amide compound, which can be carried out in an aqueous solution, is simple and environment-friendly and has good yield; the reaction substrate has good regioselectivity and monoselectivity, wide range and stronger practicability and universality.
A method for ortho-alkenylation of aromatic amide compounds comprises the following steps: dissolving aromatic amide compounds, non-activated olefin and additives in an aqueous medium, reacting under the condition of weak current serving as an oxidant and Rh (III) serving as a catalyst, and after the reaction is finished, treating and purifying to obtain an alkenyl product;
the structure of the aromatic amide compound is shown as the formula (I):
the structure of the non-activated olefin is shown as a formula (II):
the structure of the alkenyl product is shown as the formula (III):
in the formulas (I) to (III), R is a hydrogen atom, an alkyl group or an alkoxy group (preferably a methyl group);
R1is trifluoromethyl, cyano, nitro, ester group, halogen atom, alkyl, alkoxy;
R2is an aromatic ring, alkoxy group, alkyl group (preferably aromatic ring);
wherein R is1The substitution position of (1) is arbitrary;
according to the invention, by synthesizing aromatic amide, dissolving aromatic amide, inactive olefin and additive in an aqueous medium, and reacting under the oxidation action of weak current and the catalytic action of Rh (III), a Heck type product can be obtained, and the specific reaction design is as shown in the following formula (Scheme 1). The reaction well expands the application range of the substrate, and has stronger regioselectivity and higher yield. Meanwhile, water with strong conductivity is used, no extra electrolyte is needed to be added, and particularly, the reaction only takes current as an oxidant, so that Rh is recycled, and green and energy-saving effects are achieved.
During the reaction, Rh (III) firstly forms Cp, Rh (III) and activates C-H bonds of the aromatic amide under the action of the additive to obtain an intermediate A with a cyclic structure. Then, an olefin insertion reaction occurs under the catalytic action of Rh (III) to obtain an intermediate C having a cyclic structure. C then undergoes β -H elimination to give a Heck-type product, along with Rh (I). Finally, Rh (I) is restored to Rh (III) again under the action of anodic oxidation, thereby realizing catalytic cycle, and concretely, the formula is shown in the specification.
Preferably, the rhodium catalyst is [ Cp RhCl ]2]2(CAS:12354-85-7), the dosage is 1% -5 mol%, the rhodium catalyst has stronger applicability to the substrate in the reaction process, and can catalyze the substrate efficiently.
Preferably, the ratio of the amount of the aromatic amide, the activated olefin and the additive is 1: 2: 2.
preferably, the additive may be a carboxylate such as NaOPiv, KOPiv, NaOAc, used to activate the catalyst, as further optimization of conditions, the carboxylate being NaOPiv, in an amount twice the molar mass of the amide compound, the reaction having the best yield when NaOPiv is used.
Preferably, the aqueous medium is a mixture of a higher-boiling organic solvent with good conductivity and water, the organic solvent is one of tert-amyl alcohol t-AmOH, dimethyl sulfoxide DMSO, dimethyl sulfoxide DMF and acetonitrile MeCN, and is beneficial to the breaking of C-H bonds in a substrate, and as a further condition, the preferable volume ratio of tert-amyl alcohol t-AmOH to water is 3:1, the yield of the reaction is optimal at this time.
Preferably, the current is controlled to be 2 to 15mA, and when the current is too large, the reaction may be oxidized vigorously to lower the yield, and when the current is too small, the reaction is not facilitated, and further, as a further condition, the reaction control current is preferably 4 mA.
Preferably, the electrode material adopted in the reaction, the anode can be graphite felt GF, reticular vitreous RV or glassy carbon electrode, and the cathode can be platinum Pt or nickel Ni electrode, as further optimization of conditions, the electrode surface material: the anode is graphite felt GF, and the cathode is Pt.
Preferably, the R directly linked to NH can be a hydrogen atom, a methyl group, an ethyl group, a n-propyl group, a p-toluenesulfonyl group, an aromatic ring, enabling the reaction to proceed with yields in a moderate to good range. Wherein, NH part has better regioselectivity due to steric hindrance effect, and is used as the optimization of further conditions, when R is methyl, the regioselectivity and the single selectivity are the best, and the reaction conversion rate is the highest.
Preferably, R is1Hydrogen atom, trifluoromethyl, cyano, nitro, ester group, halogen atom, alkyl, alkoxy, aromatic ring. R1Can be used as electron donating group or electron withdrawing group, and has no obvious influence on the reaction.
Preferably, R is2Is aromatic ring, alkyl or alkoxy. Wherein, the aromatic ring substituent group has good yield no matter being an electron withdrawing group or an electron withdrawing group. As a further optimization of the conditions, R2The phenyl group can realize intermolecular coupling between olefin and amide and has high conversion rate.
Preferably, the reaction temperature is controlled to 80-100 ℃, and when the reaction temperature is too high, side reactions increase, while when the temperature is too low, the reaction rate decreases, the time required for the reaction increases, and the conversion rate of the reaction decreases, and as further optimization of conditions, the reaction should be controlled to 100 ℃.
In the invention, the reaction time can be detected by TLC, and the reaction can be completed by stirring for 12-24 h at 100 ℃.
Compared with the prior art, the invention has the beneficial effects that: the reaction uses aromatic amide as a guiding substance, in an aqueous medium, under the oxidation action of weak current, C-H bond of amide is activated under the catalysis of Rh (III), olefin insertion reaction occurs, and a Heck type product is obtained through beta-H elimination. The reaction catalysis system is a high-boiling point strong-conductivity water phase system, and no extra electrolyte is needed to be added, so that the method is economic. Meanwhile, the reaction only has the oxidation effect of current, and the use of Rh (III) with less equivalent in the circulating catalysis is more energy-saving and environment-friendly than the energy-saving and environment-friendly method. In addition, the reaction substrate has strong practicability and universality under the action of the catalyst in the reaction, and has good regioselectivity and moderate to excellent yield.
Drawings
FIG. 1 is a schematic view of a reaction apparatus according to the present invention;
FIG. 2 shows the product obtained in example 11HNMR spectrogram;
FIG. 3 shows the product obtained in example 113CNMR spectrogram;
FIG. 4 shows the product obtained in example 21HNMR spectrogram;
FIG. 5 shows the product obtained in example 213CNMR spectrogram;
FIG. 6 shows the product obtained in example 31HNMR spectrogram;
FIG. 7 shows the product obtained in example 313CNMR spectrogram;
FIG. 8 shows the product obtained in example 41HNMR spectrogram;
FIG. 9 shows the product obtained in example 413CNMR spectrogram.
Detailed Description
The reactant aromatic formamide used in the invention can be prepared by adopting the following method:
to a 100mL round bottom flask equipped with a stir bar were added methylamine hydrochloride (0.7g,11mmol) and dichloromethane (20 mL). Stirring was carried out at 0 ℃ and triethylamine (3.5mL,24mmol) was added. Then, the acid chloride (10.0mmol) prepared from oxalic acid molecule (0.93mL,11mmol) was added dropwise. After stirring at room temperature for 8 hours, the reaction mixture is quenched with water and CH2Cl2(20 mL. multidot.2) extraction, mixing the organic layers in anhydrous Na2SO4Air drying, and concentrating to obtain residue. The product with higher yield is obtained by performing column chromatography purification treatment on a silica gel column by taking EtOAc/n-hexane (v/v,1:1) as an eluent.
The method for ortho-alkenylation according to the invention is as follows:
accurately charged into the reaction tube were aromatic amide 1(0.4mmol,1.0equiv), olefin 2(0.8mmol,2.0equiv), NaOPiv (100mg,2.0equiv) and [ Cp. RhCl2]2(6.4mg,2.5 mol%) in a mixed solvent t-AmOH/H2O (3:1,4 mL). The anode is graphite felt GF, the electrode specification is (10mm multiplied by 15mm multiplied by 6mm), and the cathode is platinum sheet electrode specification is (10mm multiplied by 15mm multiplied by 0.25 mm). Electrocatalysis was carried out at 100 ℃ and the current was kept at 4.0mA for 12-24 hours. All solvents were transferred to a round bottom flask. Silica was added to the flask and the solvent was evaporated in vacuo. The corresponding product 3 was obtained by purification with silica gel column chromatography using EtOAc/n-hexane (v/v,1:2) as eluent. The reaction apparatus is shown in FIG. 1.
The invention is further described with reference to specific examples.
Example 1
In the reaction tube, 59.6mg (0.4mmol) of the aromatic amide 1a (1.0 equiv) and 83.2mg (0.8mmol) of styrene 2a (2.0 equiv), 100mg of NaOPiv (2.0 equiv) and 6.4mg of [ Cp. RhCl ] were accurately added2]2(2.5 mol%) in a solvent mixture t-AmOH/H2O (3:1,4 mL). The anode was kept as graphite felt GF, the electrode surface area was (10 mm. times.15 mm. times.6 mm), the cathode was platinum, and the electrode surface area was (10 mm. times.15 mm. times.0.25 mm). The reaction was carried out at 100 ℃ with a current of 4.0mA for 18 hours. After the completion of the TLC check reaction, all the solvent was transferred to a round-bottomed flask, silica was added to the flask, and the solvent was distilled off. Purification by column chromatography on silica gel (n-hexane/EtOAc ═ 2:1, v/v) gave 73mg of product 3a in 73mg yield. The reaction formula is as follows:
the physical properties and spectral data of the product are as follows: a colorless solid; the melting point is 151-153 ℃;1H-NMR(400MHz,CDCl3):δ=7.56(d,J=8.0Hz,1H),7.48(d,J=7.6Hz,2H),7.40(d,J=16.0Hz,1H),7.35(t,J=7.6Hz,2H),7.28–7.19(m,3H),6.99(d,J=16.4Hz,1H),6.01(s,1H),2.95(d,J=4.8Hz,3H),2.34(s,3H).13C-NMR(100MHz,CDCl3):δ=170.4(Cq),137.4(Cq),137.2(Cq),135.6(Cq),132.6(Cq),130.9(CH),130.3(CH),128.7(CH),128.2(CH),127.8(CH),126.7(CH),126.0(CH),125.9(CH),26.8(CH3),21.1(CH3).IR(ATR):3281,3023,1629,1541,1497,1448,1323,817,748cm-1.HR-MS(ESI)m/z calc.forC17H17NO[M+H]+:252.1383,found:252.1385.
example 2
In the reaction tube, 71.6mg (0.4mmol) of the aromatic amide 1b (1.0 equiv) and 83.2mg (0.8mmol) of styrene 2a (2.0 equiv), 100mg of NaOPiv (2.0 equiv) and 6.4mg of [ Cp. RhCl ] were accurately added2]2(2.5 mol%) was dissolved in a solvent mixture t-AmOH/H2O (3:1,4 mL). The anode was kept as graphite felt GF, the electrode surface area was (10 mm. times.15 mm. times.6 mm), the cathode was platinum, and the electrode surface area was (10 mm. times.15 mm. times.0.25 mm). The reaction was carried out at 100 ℃ with a current of 4.0mA for 24 hours. After the completion of the TLC check reaction, all the solvent was transferred to a round-bottomed flask, silica was added to the flask, and the solvent was distilled off. Purification by column chromatography on silica gel (n-hexane/EtOAc ═ 2:1, v/v) gave 69.2mg of product 3b in 62% yield. The reaction formula is as follows:
the physical properties and spectral data of the product are as follows: a yellow solid; the melting point is 202-204 ℃;1H-NMR(400MHz,CDCl3):δ=7.47(d,J=7.2Hz,2H),7.42(d,J=16.4Hz,1H),7.34-7.22(m,4H),6.96(d,J=8.0Hz,1H),6.66(d,J=8.0Hz,1H),6.06(s,2H),5.86(s,1H),2.95(d,J=5.2Hz,3H).13C-NMR(100MHz,CDCl3):δ=169.9(Cq),149.0(Cq),145.7(Cq),137.6(Cq),134.8(CH),130.4(Cq),128.1(CH),126.9(CH),122.0(CH),121.2(CH),118.8(Cq),106.8(CH),101.6(Cq),27.0(CH3).IR(ATR):3259,1634,1608,1536,1449,1306,1253,1078,962,820,755cm-1.HR-MS(ESI)m/z calc.for C17H15NO3[M+H]+:282.1125,found:282.1126.
example 3
In the reaction tube, exactly 56.4mg (0.4mmol) of the aromatic amide 1c (1.0 equiv) and 83.2mg (0.8mmol) of styrene 2a (2.0 equiv), 100mg of NaOPiv (2.0 equiv) and 6.4mg of [ Cp. RhCl ] were weighed in2]2(2.5 mol%) in a solvent mixture t-AmOH/H2O (3:1,4 mL). The anode was kept as graphite felt GF, the electrode surface area was (10 mm. times.15 mm. times.6 mm), the cathode was platinum, and the electrode surface area was (10 mm. times.15 mm. times.0.25 mm). The reaction was carried out at 100 ℃ with a current of 4.0mA for 24 hours. After the completion of the TLC check reaction, all the solvent was transferred to a round-bottomed flask, silica was added to the flask, and the solvent was distilled off. Purification by column chromatography on silica gel (n-hexane/EtOAc ═ 2:1, v/v) gave a product 3c content of 65.1mg, 67% yield. The reaction formula is as follows:
the physical properties and spectral data of the product are as follows: a white solid; melting point 103-105 ℃;1H-NMR(400MHz,CDCl3):δ=7.88(d,J=16.8Hz,1H),7.53(d,J=7.2Hz,2H),7.37-7.33(m,3H),7.29-7.26(m,2H),7.02(d,J=16.4Hz,1H),6.15(s,1H),2.96(d,J=4.8Hz,1H).13C-NMR(100MHz,CDCl3):δ=163.7(Cq),141.8(Cq),137.0(Cq),132.1(CH),131.2(Cq),128.7(CH),128.0(CH),126.8(CH),126.63(CH),126.62(CH),121.9(CH),26.9(CH3).IR(ATR):3273,2927,1619,1535,1445,1245,952,745,679,622cm-1.HR-MS(ESI)m/z calc.forC14H13NOS[M+H]+:244.0791,found:244.0793.
example 4 (gram-scale reaction)
In the reaction tube, exactly 0.9g (6mmol) of the aromatic amide 1a (1.0 equiv) and 1.66g (0.8mmol) of the olefin 2b (2.0 equiv), 1.5g of NaOPiv (2.0 equiv) and 90mg of [ Cp. RhCl2]2(1.5 mol%) in a solvent mixture t-AmOH/H2O (3:1,30 mL). The surface area of the electrode was varied, the anode was graphite felt GF, the surface area of the electrode was (25mm × 50mm × 6mm), the cathode was platinum, and the surface area of the electrode was (25mm × 50mm × 0.25 mm). The reaction was carried out at 100 ℃ with a current of 6.0mA for 48 hours. After the completion of the TLC check reaction, all the solvent was transferred to a round-bottomed flask, silica was added to the flask, and the solvent was distilled off. Purification by column chromatography on silica gel (n-hexane/EtOAc ═ 2:1, v/v) gave product 3d in a content of 1.2g, 70% yield. The reaction formula is as follows:
Claims (9)
1. a method for alkenylating the ortho position of an aromatic amide compound is characterized by comprising the following steps:
dissolving an aromatic amide compound, non-activated olefin and an additive in an aqueous medium, carrying out an ortho-olefination reaction under the catalysis of a rhodium catalyst under the action of weak current, and after the reaction is finished, carrying out treatment and purification to obtain an alkenylation product;
the structure of the aromatic amide compound is shown as the formula (I):
the structure of the non-activated olefin is shown as the formula (II):
the structure of the alkenyl product is shown as the formula (III):
in the formulas (I) to (III), R is a hydrogen atom, an alkyl group, an alkoxy group, a p-toluenesulfonyl group or an aryl group;
R1is H, trifluoromethyl, cyano, nitro, ester group, halogen atom, alkyl or alkoxy or aryl;
R2is an aromatic ring, alkoxy or alkyl;
the rhodium catalyst is [ Cp & RhCl2]2;
The additive for the reaction is carboxylate, and the carboxylate is NaOPiv;
the aqueous phase medium is a mixture of an organic solvent with higher boiling point and good conductivity and water, and the organic solvent is tert-amyl alcohol.
2. The method for ortho-alkenylation of an aromatic amide-based compound according to claim 1, wherein the amount of the rhodium catalyst is 1 to 5 mol%.
3. The method for ortho-alkenylating an aromatic amide-based compound according to claim 1 or 2, wherein R is a hydrogen atom or C1~C4Alkyl, methoxy, p-toluenesulfonyl, aryl.
4. The method for ortho-alkenylating an aromatic amide-based compound according to claim 1 or 2, wherein R is1Is hydrogen atom, trifluoromethyl, cyano, nitro, ester group, F, Cl, Br, C1~C4Alkyl radical, C1~C4Alkoxy, phenyl.
5. The method for ortho-alkenylating an aromatic amide-based compound according to claim 1 or 2, wherein R is2Is an aromatic ring substituted by an electron-withdrawing group, an aromatic ring substituted by an electron-donating group, C1~C4Alkoxy radical, C1~C4An alkyl group.
6. The method for ortho-alkenylation of an aromatic amide-based compound according to claim 1 or 2, wherein the current for the reaction is controlled to 2 to 15 mA.
7. The method for ortho-alkenylation of an aromatic amide-based compound according to claim 1 or 2, wherein the reaction is carried out using an electrode material: the anode is a carbon electrode, and the cathode is a platinum Pt or nickel Ni electrode.
8. The method of claim 7, wherein the carbon electrode is graphite felt, reticulated vitreous carbon, or glassy carbon.
9. The method for ortho-alkenylation of an aromatic amide compound according to claim 1 or 2, wherein the reaction temperature is controlled to 80 to 100 ℃.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010083526.6A CN111270260B (en) | 2020-02-09 | 2020-02-09 | Method for alkenylating ortho-position of aromatic amide compound |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010083526.6A CN111270260B (en) | 2020-02-09 | 2020-02-09 | Method for alkenylating ortho-position of aromatic amide compound |
Publications (2)
Publication Number | Publication Date |
---|---|
CN111270260A CN111270260A (en) | 2020-06-12 |
CN111270260B true CN111270260B (en) | 2021-05-25 |
Family
ID=70995108
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202010083526.6A Active CN111270260B (en) | 2020-02-09 | 2020-02-09 | Method for alkenylating ortho-position of aromatic amide compound |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN111270260B (en) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102600892A (en) * | 2012-02-17 | 2012-07-25 | 北京工业大学 | Application of triarylimidazole compound serving as catalyst in electroorganic synthesis |
CN106831414A (en) * | 2017-01-24 | 2017-06-13 | 江汉大学 | The method of the adjacent alkenyl phenol derivatives of synthesis |
CN109232529A (en) * | 2018-10-10 | 2019-01-18 | 浙江师范大学 | A kind of preparation method of compound of Rh (III) catalysis with azepine ring skeleton |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2014001154A (en) * | 2012-06-15 | 2014-01-09 | Showa Denko Kk | Method for producing 2-alkenyl ether compound |
US10227355B2 (en) * | 2015-02-03 | 2019-03-12 | Council Of Scientific And Industrial Research | Quinoline derivatives and preparation thereof |
-
2020
- 2020-02-09 CN CN202010083526.6A patent/CN111270260B/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102600892A (en) * | 2012-02-17 | 2012-07-25 | 北京工业大学 | Application of triarylimidazole compound serving as catalyst in electroorganic synthesis |
CN106831414A (en) * | 2017-01-24 | 2017-06-13 | 江汉大学 | The method of the adjacent alkenyl phenol derivatives of synthesis |
CN109232529A (en) * | 2018-10-10 | 2019-01-18 | 浙江师范大学 | A kind of preparation method of compound of Rh (III) catalysis with azepine ring skeleton |
Non-Patent Citations (3)
Title |
---|
Rh(III)-Catalyzed Directed C-H Olefination Using an Oxidizing Directing Group: Mild, Efficient, and Versatile;Souvik Rakshit et al.;《Journal of the American Chemical Society》;20110128;第133卷;第2350-2353页 * |
Rhodium(III)-Catalyzed C—H Vinylation of Arenes: Access to Functionalized Styrenes;Jun Zhou et al.;《Chin. J. Chem.》;20181005;第36卷;第1143-1146页 * |
Rhodium-Catalyzed Electrooxidative C–H Olefination of Benzamides;Yan Zhang et al.;《Angew. Chem. Int. Ed.》;20200429;第59卷(第35期);第15706-15080页 * |
Also Published As
Publication number | Publication date |
---|---|
CN111270260A (en) | 2020-06-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Li et al. | Weinreb amide directed cross-coupling reaction between electron-deficient alkenes catalyzed by a rhodium catalyst | |
Wang et al. | Palladium-catalyzed α-regioselective allylic amination of Morita–Baylis–Hillman acetates with simple aromatic amines | |
Chai et al. | Asymmetric allylation of aldehydes with allyltrichlorosilane using aza-paracyclophane-oxazoline-N-oxide catalysts | |
WO2005044805A1 (en) | A novel process for preparing donepezil and its derivatives | |
Shen et al. | Highly efficient Cu-catalyzed oxidative coupling of tertiary amines and siloxyfurans | |
Ballini et al. | Cetyltrimethylammonium hydroxide (CTAOH) as a general, ecofriendly catalyst for the formation of carbon–carbon bond through nitroalkanes | |
CN111808023B (en) | Method for preparing 3-aryl isoquinoline derivative | |
CN111270260B (en) | Method for alkenylating ortho-position of aromatic amide compound | |
CN112301370B (en) | Electrochemical synthesis method of 1, 3-dimethyl-3-difluoroethyl-2-oxindole compound | |
Wang et al. | Access to Saturated Oxygen Heterocycles and Lactones via Electrochemical Sulfonylative Oxycyclization of Alkenes with Sulfonyl Hydrazides | |
WO2005121111A1 (en) | Method for producing 3-aminomethyltetrahydrofuran derivative | |
CN110627734A (en) | Preparation method of 3-alkoxy substituted quinoxalinone derivative | |
CN113897631B (en) | Method for electrochemical synthesis of pyridin-2-one derivatives | |
Kitagawa et al. | Alkaline metallic reagent-catalyzed hydrocarbocyclization reaction ofvarious active methine compounds having an unactivated 4-alkynyl or allenyl group | |
Morrow et al. | Intramolecular cyclization of 2'-olepinic side-chains on anodically oxidized 4-phenylphenols. The effect of olefin substituents on carbon—carbon bond formation | |
JP2004537405A (en) | Palladium catalyst | |
Chen et al. | Electrochemical-induced radical allylation via the fragmentation of alkyl 1, 4-dihydropyridines | |
Jiang et al. | Stereoselective synthesis of tetrasubstituted olefins via palladium-catalyzed three-component coupling of aryl iodides, internal alkynes, and arylboronic acids in supercritical carbon dioxide | |
CN101503358A (en) | Method for preparing chiral alpha-hydroxy-beta-dicarbonyl compound with lappaconitine as catalyst | |
CN110317160B (en) | Novel method for activating sulfonylated 2-phenylisoisatin through C-H | |
Zhang et al. | Aerobic alcohol ammoxidation catalyzed by copper (I)/amino acid: a scalable protocol to nitriles | |
CN114409714B (en) | Method for synthesizing 1, 3-disubstituted plane chiral metallocene compound | |
CN115928114B (en) | Synthetic method of aromatic hydrocarbon pyrazole compound | |
Shinde | Synthesis and Functionalization of Heterocyclic Compounds via Palladium Rhodium Catalyzed Cross Dehydrogenative Coupling Reactions | |
CN110183362B (en) | Process for producing aromatic alkenyl compound |
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 | ||
EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20200612 Assignee: ZHEJIANG YUEXU MATERIAL TECHNOLOGY CO.,LTD. Assignor: ZHEJIANG NORMAL University Contract record no.: X2022980008291 Denomination of invention: A method of ortho alkenylation of aromatic amide compounds Granted publication date: 20210525 License type: Common License Record date: 20220627 |
|
EE01 | Entry into force of recordation of patent licensing contract |