CN104844429A - Method used for catalytic rearrangement of pinacol with gold - Google Patents

Method used for catalytic rearrangement of pinacol with gold Download PDF

Info

Publication number
CN104844429A
CN104844429A CN201510175333.2A CN201510175333A CN104844429A CN 104844429 A CN104844429 A CN 104844429A CN 201510175333 A CN201510175333 A CN 201510175333A CN 104844429 A CN104844429 A CN 104844429A
Authority
CN
China
Prior art keywords
reaction
catalysis
pinacol rearrangement
pinacol
rearrangement
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
Application number
CN201510175333.2A
Other languages
Chinese (zh)
Other versions
CN104844429B (en
Inventor
刘永祥
程卯生
石慧
王晓宇
杜川
金盛飞
刘洋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shenyang Pharmaceutical University
Original Assignee
Shenyang Pharmaceutical University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Shenyang Pharmaceutical University filed Critical Shenyang Pharmaceutical University
Priority to CN201510175333.2A priority Critical patent/CN104844429B/en
Publication of CN104844429A publication Critical patent/CN104844429A/en
Application granted granted Critical
Publication of CN104844429B publication Critical patent/CN104844429B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/52—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition by dehydration and rearrangement involving two hydroxy groups in the same molecule

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention provides a method used for catalytic rearrangement of pinacol with gold. A reaction general formula is disclosed in the invention, wherein R1, R2, R3, and R4 may be common alkyl, cycloalkyl, and aromatic rings. A gold catalyst needed by reaction is Ph3PAuCl, Ph3PAuNTf2, HAuCl4, NaAuCl4, Ph3PAuOTf, Ph3PAuSbF6, IPrAuCl, and nano gold. Mediums needed by reaction are methylbenzene, sym-trimethylbenzene, 1,2-dichloroethane, tetrahydrofuran, acetonitrile, and acetone. Microwave reactor heating is adopted; operation of the method is simple; application range is wide; and reaction is green.

Description

A kind of method of golden catalysis pinacol rearrangement
Technical field
The present invention relates to a kind of under the effect of Au catalyst, tetramethyl ethylene ketone dewaters and forms the method for corresponding aldehydes or ketones under microwave mediation.
Background technology
Pinacol rearrangement is 1,2-glycol issues the dehydration of raw intramolecular rearrangement in acid catalysis and generates the reaction of carbonyl compound (aldehydes or ketones), product Pinacolone is a kind of important organic chemical industry's intermediate, is widely used in the synthesis of the multiple fine chemicals such as agricultural chemicals medical science dyestuff.(J.Org.Chem.2000,65 (22), 7438-7446.) are usual, and pinacol rearrangement is as H at inorganic acid 2sO 4carry out under catalysis, not only selectivity is not high, and serious to equipment corrosion, to environment.Therefore, replace with solid acid the development trend that the strong mineral acid of corrodibility is this field.Solid acid common at present has:
(1) samarium diodide, (S.J.Jong et.al.J.Organomet.Chem., 1999,590,42-45.), the method is published in 1999, utilizes samarium diodide reflux with substrate in tetrahydrofuran (THF) and substrate is reset.But the substrate applicability of the method is not high, from reaction formula, the substrate of the method is only limitted to symmetrical vicinal diamines, and the structure that ferrocene must be had in substituted radical such, therefore this solid acid does not have good range of application.
(2) iron trichloride (A.B.Shinde et.al.Synth.Commun., 2004,34,309-314.), first by FeCl 3immobilized on polynite K10, the polynite K10 then modified with this Fe (III) for catalyzer, reflux in toluene.The method has only done five substrates, and the preparation of catalyzer some is time-consuming, selectivity is very bad.Wherein the ratio of Ph and Ar migration is close to 1:1, is separated very difficult, does not have good using value.
(3) high molecular polymer (C.Pavlik et.al.Synlett., 2011,15,2191-2194.).The main drawback of this reaction is that the reaction times is oversize, needs to spend the night.And polymer catalyst still needs preparation.In substrate applicability, different substrates also will add different acid and carry out further deactivated catalyst, such as: Glacial acetic acid, and the vitriol oil etc.Yield neither be very high, about 70%.Sometimes temperature of reaction even reaches 160 DEG C.Applicability is not high.
(4)ZnCl 2/SiO 2(D.J.Upadhyaya et.al.Applied Catalysis A:General.,2008,340,42-51.)。A kind of method utilizing carrier solid-carried catalyst, by ZnCl 2grinding SiO 2on.The early-stage preparations of this method are more consuming time, need SiO 2drying more than 3 hours under the high temperature of 120 DEG C.And the time is many at a hours, and the longest reaches more than six hours, and efficiency is not high.
In sum, in the solid acid of known catalysis pinacol rearrangement, or temperature required for reaction is higher, or reaction preference is not high, or the preparation more complicated in catalyzer early stage, or the time of reaction is long.Therefore find that a kind of selectivity is high and the catalyzer of reaction conditions gentleness is very urgent.Au catalyst water stability, is better, and catalysis pinacol rearrangement is a kind of green, environmental protection, have no the brand-new method of bibliographical information to utilize it to come, and has good application prospect.
Summary of the invention
The present invention relates to a kind of novel method of pinacol rearrangement, namely using gold as catalyzer, under microwave mediation, vicinal diamines is directly rearranged into ketone or aldehyde, and reaction expression is:
Wherein R 1, R 2, R 3, R 4, can be hydrogen, C1-C10 alkyl, C3-C8 cycloalkyl, C1-C10 alkoxyl group, or C6-C10 aromatic base, be preferably hydrogen, C1-C4 alkyl, C3-C8 cycloalkyl, C1-C4 alkoxyl group or C6-C10 aromatic base, more preferably: hydrogen, phenyl, oxyethyl group, cyclopropyl.C6-C10 aromatic base can be the aromatic compounds such as phenyl, thienyl, furyl, pyridine, or C1-C4 alkyl, halogen, C1-C4 alkoxyl group, nitro, cyano group replace C6-C10 aromatic base.
Wherein can be following structure:
The catalyzer used is Au catalyst, is preferably wherein Ph 3pAuNTf 2, but be not limited to: Ph 3pAuCl, Ph 3pAuNTf 2, HAuCl 4, NaAuCl 4, Ph 3pAuOTf, Ph 3pAuSbF 6, IPrAuCl, nanometer gold.
The consumption of described catalyzer is the 0.5%-1% of the amount of substance of reactant.Selected solvent is preferably 1,2-ethylene dichloride, but is not limited to: toluene, sym-trimethylbenzene, tetrahydrofuran (THF), acetonitrile, dioxane, acetone.Preparation process is:
(1) reinforced
Joined by reaction substrate in reaction microwave tube, adding consumption is that the solvent of 1-10 times of reactant is as reaction medium.Reaction medium is 1,2-ethylene dichloride, but is not limited to: the one of solvent-free, toluene, sym-trimethylbenzene, tetrahydrofuran (THF), acetonitrile, acetone.Then the 0.5%-5% Au catalyst that consumption is the amount of substance of reactant is added.Preferably 1%.The Au catalyst used is preferably wherein Ph 3pAuNTf 2, but be not limited to: Ph 3pAuCl, Ph 3pAuNTf 2, HAuCl 4, NaAuCl 4, Ph 3pAuOTf, Ph 3pAuSbF 6, IPrAuCl, nanometer gold.The addition sequence of reactant, reaction medium and Au catalyst can exchange arbitrarily.
(2) react
In microwave reactor, make temperature of charge at 50 DEG C – 150 DEG C, stirring reaction 3 Fen Zhong – 60 minutes, with thin-layer chromatography detection reaction process.The developping agent of thin-layer chromatography is the mixed solution of sherwood oil, ethyl acetate, normal hexane, methyl alcohol, chloroform, methylene dichloride, acetone, tetrahydrofuran (THF), water or both or three wherein.Preferred: petrol ether/ethyl acetate (v:100/1 ~ 5/1) or n-hexane/ethyl acetate (v:100/1 ~ 5/1) system.
(3) reaction solution aftertreatment
Cooled reaction solution Rotary Evaporators is steamed reaction medium, directly carry out column chromatography for separation with silica gel or aluminum oxide to reaction mixture to purify and obtain target product, the system of developping agent is: the mixed solution of sherwood oil, ethyl acetate, normal hexane, methyl alcohol, chloroform, methylene dichloride, acetone, tetrahydrofuran (THF), water or both or three wherein.Preferred: petrol ether/ethyl acetate (v:100/1 ~ 5/1) or n-hexane/ethyl acetate (v:100/1 ~ 5/1) system.
The invention has the advantages that, angle chemically, reaction conditions is gentle, and the reaction times is short, simple to operate, and from angle that is industrial and environment, aftertreatment is simple, environmental protection.
Embodiment
Contact following example, will understand advantage of the present invention and preparation process better, these embodiments are intended to set forth instead of limit the scope of the invention.
Embodiment 1:
In the microwave tube of 10mL, add substrate 1 (1mmol, 27.4mg) add Ph simultaneously 3pAuCl (0.01mmol, 0.5mg), adds 0.2mL 1, reaction mixture microwave reactor, as reaction solvent, is heated to 80 DEG C by 2 ethylene dichloride, stirring reaction 20 minutes, after having reacted, be separated by the method for rapid column chromatography and obtain target product I, yield 93%.
Reaction formula is:
The spectral data of product II is: ESI-MS (m/z): 273.25 [M+H] +; 1h NMR (600MHz, DMSO) δ 9.87 (d, J=1.8Hz, 1H), 7.20 – 7.13 (m, 4H), 6.97 – 6.91 (m, 4H), 4.99 (d, J=1.6Hz, 1H), 3.73 (s, 6H).
Embodiment 2:
Replace substrate 1 with substrate 2, other obtain target compound II with embodiment 1, yield 96%.
Reaction formula is:
The spectral data of product II is: ESI-MS (m/z): 377.15 [M+H] +; 1h NMR (600MHz, DMSO) δ 9.94 (d, J=2.1Hz, 1H), 6.66 (s, 4H), 4.90 (d, J=2.0Hz, 1H), 3.76 (s, 12H), 3.64 (s, 6H).
Embodiment 3:
Replace substrate 1 with substrate 3, other obtain target compound III with embodiment 1, yield 67%.
Reaction formula is:
The spectral data of product III is: ESI-MS (m/z): 233.07 [M+H] +; 1h NMR (600MHz, CDCl 3) δ 9.90 (d, J=2.1Hz, 1H), 7.20 – 7.14 (m, 4H), 7.10 – 7.05 (m, 4H), 4.87 (d, J=1.4Hz, 1H).
Embodiment 4:
Replace substrate 1 with substrate 4, other obtain target compound IV with embodiment 1, yield 57%.
Reaction formula is:
The spectral data of product IV is: ESI-MS (m/z): 265.01 [M+H] +; 1h NMR (600MHz, DMSO) δ 9.79 (d, J=5.7Hz, 1H), 7.36 (d, J=8.6Hz, 2H), 7.32 (t, J=8.0Hz, 4H), 7.14 (d, J=8.5Hz, 2H), 6.97 (d, J=5.8Hz, 1H).
Embodiment 5:
In the microwave tube of 10mL, add substrate 5 (1mmol, 24.2mg) add Ph simultaneously 3pAuNTf 2(0.01mmol, 0.7mg), adds 0.2mL 1, reaction mixture microwave reactor, as reaction solvent, is heated to 90 DEG C by 2 ethylene dichloride, stirring reaction 10 minutes, after having reacted, be separated to obtain target compound V by the method for rapid column chromatography, yield 87%.
Reaction formula is:
The spectral data of product V is: ESI-MS (m/z): 243.13 [M+H] +; 1h NMR (600MHz, CDCl 3) δ 7.35 (dd, J=10.4,4.7Hz, 4H), 7.31 – 7.26 (m, 2H), 7.23 – 7.19 (m, 4H), 2.12 (s, 3H), 1.89 (s, 3H).
Embodiment 6:
Replace substrate 5 with substrate 6, other obtain target compound VI with embodiment 5, yield 89%.
Reaction formula is:
The spectral data of product VI is: ESI-MS (m/z): 271.16 [M+H] +; 1h NMR (600MHz, CDCl 3) δ 7.14 (d, J=8.1Hz, 4H), 7.08 (d, J=8.2Hz, 4H), 2.35 (s, 6H), 2.10 (s, 3H), 1.83 (s, 3H).
Embodiment 7:
Replace substrate 5 with substrate 7, other obtain target compound VII with embodiment 5, yield 96%.
Reaction formula is:
The spectral data of product VII is: ESI-MS (m/z): 303.15 [M+H] +; 1h NMR (600MHz, CDCl 3) δ 7.16 – 6.97 (m, 4H), 6.86 (d, J=8.9Hz, 4H), 3.81 (s, 6H), 2.09 (s, 3H), 1.82 (s, 3H).
Embodiment 8:
Replace substrate 5 with substrate 8, other obtain target compound VIII with embodiment 5, yield 76%.
Reaction formula is:
The spectral data of product VII I is: ESI-MS (m/z): 279.11 [M+H] +; 1h NMR (600MHz, CDCl 3) δ 7.16 – 7.11 (m, 4H), 7.06 – 7.00 (m, 4H), 2.11 (s, 3H), 1.86 (s, 3H).
Embodiment 9:
In the microwave tube of 10mL, add substrate 9 (1mmol, 18.2mg) add Ph simultaneously 3pAuNTf 2(0.01mmol, 0.7mg), adds 0.2mL 1, reaction mixture microwave reactor, as reaction solvent, is heated to 100 DEG C by 2 ethylene dichloride, stirring reaction 10 minutes, after having reacted, be separated to obtain target compound IX by the method for rapid column chromatography, yield 81%.
Reaction formula is:
The spectral data of product IX is: ESI-MS (m/z): 163.11 [M+H] +; 1h NMR (600MHz, CDCl 3) δ 7.39 – 7.33 (m, 2H), 7.29 – 7.25 (m, 3H), 1.93 (s, 3H), 1.49 (s, 6H).
Embodiment 10:
Replace substrate 9 with substrate 10, other obtain target compound X with embodiment 9, yield 71%.
The spectral data of product X is: ESI-MS (m/z): 177.12 [M+H] +; 1h NMR (600MHz, CDCl 3) δ 7.15 (s, 4H), 2.34 (s, 3H), 1.92 (s, 3H), 1.46 (s, 6H).
Embodiment 11:
In the microwave tube of 10mL, add substrate 11 (1mmol, 19.4mg) add Ph simultaneously 3pAuNTf 2(0.05mmol, 3.5mg), adds 0.2mL 1, reaction mixture microwave reactor, as reaction solvent, is heated to 100 DEG C by 2 ethylene dichloride, stirring reaction 10 minutes, after having reacted, be separated to obtain target compound IX by the method for rapid column chromatography, yield 70%
The spectral data of product X is: ESI-MS (m/z): 177.12 [M+H] +; 1h NMR (600MHz, CDCl 3) δ 7.15 (s, 4H), 2.34 (s, 3H), 1.92 (s, 3H), 1.46 (s, 6H).
Embodiment 12:
In the microwave tube of 10mL, add substrate 11 (1mmol, 19.4mg) add Ph simultaneously 3pAuNTf 2(0.005mmol, 0.35mg), adds 0.2mL 1, reaction mixture microwave reactor, as reaction solvent, is heated to 100 DEG C by 2 ethylene dichloride, stirring reaction 10 minutes, after having reacted, be separated to obtain target compound IX by the method for rapid column chromatography, yield 49%
The spectral data of product X is: ESI-MS (m/z): 177.12 [M+H] +; 1h NMR (600MHz, CDCl 3) δ 7.15 (s, 4H), 2.34 (s, 3H), 1.92 (s, 3H), 1.46 (s, 6H).

Claims (10)

1. a method for golden catalysis pinacol rearrangement, is characterized in that: take gold as catalyzer, and under microwave mediation, pinacol rearrangement generates corresponding aldehydes or ketones.
2. the new catalysis process of which alcohol rearrangement reaction as claimed in claim 1, is characterized in that: reaction expression is:
Wherein R 1,r 2,r 3,r 4,can be hydrogen, C1-C10 alkyl, C3-C8 cycloalkyl, C1-C10 alkoxyl group, or C6-C10 aromatic base, is preferably hydrogen, C1-C4 alkyl, C3-C8 cycloalkyl, C1-C4 alkoxyl group or C6-C10 aromatic base, more preferably: hydrogen, phenyl, oxyethyl group, cyclopropyl, C6-C10 aromatic base can be phenyl, thienyl, furyl, the aromatic compounds such as pyridine, or C1-C4 alkyl, halogen, C1-C4 alkoxyl group, nitro, cyano group replace C6-C10 aromatic base.
3. the new catalysis process of pinacol rearrangement as claimed in claim 1 or 2, is characterized in that: described Au catalyst, comprises Ph 3pAuCl, Ph 3pAuNTf 2, HAuCl 4, NaAuCl 4, Ph 3pAuOTf, Ph 3pAuSbF 6, IPrAuCl, nanometer gold.
The new catalysis process of a kind of catalysis pinacol rearrangement of 4.1-3 described in any one, it is characterized in that: reaction is tetrahydrofuran (THF), 1 without medium or reaction medium, 2-ethylene dichloride, toluene, sym-trimethylbenzene, methyl alcohol, acetonitrile, N, dinethylformamide or dimethyl sulfoxide (DMSO), preferably 1,2-ethylene dichloride.
5., as the novel method of a kind of catalysis pinacol rearrangement of claim 1-4 as described in any one, it is characterized in that: the consumption of catalyzer is the 0.5%-5% of the amount of substance of reactant.
6., as the new catalysis process of a kind of catalysis pinacol rearrangement of claim 1-5 as described in any one, it is characterized in that: at described reaction microwave reactor is heated to 50 DEG C-150 DEG C, stirring reaction 3 Fen Zhong – 60 minutes.
7., as the new catalysis process of a kind of catalysis pinacol rearrangement of claim 1-6 as described in any one, it is characterized in that: its preparation process is as follows:
(1) joined by tetramethyl ethylene ketone in reaction microwave tube, adding consumption is that reactant 1-10 solvent is doubly as reaction medium;
(2) in microwave reactor, make temperature of charge at 50 DEG C – 150 DEG C, stirring reaction 3 Fen Zhong – 60 minutes, with thin-layer chromatography detection reaction process, the system of developping agent is: the mixed solution of sherwood oil, ethyl acetate, normal hexane, methyl alcohol, chloroform, methylene dichloride, acetone, tetrahydrofuran (THF), water or both or three wherein.
8. the new catalysis process of a kind of catalysis pinacol rearrangement as claimed in claim 7, it is characterized in that: steam reaction medium with Rotary Evaporators after step (2) being obtained reaction solution cooling, with silica gel or aluminum oxide, directly column chromatography for separation purification is carried out to reaction mixture.
9. the new catalysis process of a kind of catalysis pinacol rearrangement as claimed in claim 8, is characterized in that: the system of chromatography developping agent is: the mixed solution of sherwood oil, ethyl acetate, normal hexane, methyl alcohol, chloroform, methylene dichloride, acetone, tetrahydrofuran (THF), water or both or three wherein.
10. the new catalysis process of a kind of catalysis pinacol rearrangement as claimed in claim 7 or 8, is characterized in that: described developping agent is petrol ether/ethyl acetate=100/1 ~ 5/1 or n-hexane/ethyl acetate=100/1 ~ 5/1.
CN201510175333.2A 2015-04-14 2015-04-14 A kind of method of gold catalysis pinacol rearrangement Expired - Fee Related CN104844429B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510175333.2A CN104844429B (en) 2015-04-14 2015-04-14 A kind of method of gold catalysis pinacol rearrangement

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510175333.2A CN104844429B (en) 2015-04-14 2015-04-14 A kind of method of gold catalysis pinacol rearrangement

Publications (2)

Publication Number Publication Date
CN104844429A true CN104844429A (en) 2015-08-19
CN104844429B CN104844429B (en) 2017-03-01

Family

ID=53844471

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510175333.2A Expired - Fee Related CN104844429B (en) 2015-04-14 2015-04-14 A kind of method of gold catalysis pinacol rearrangement

Country Status (1)

Country Link
CN (1) CN104844429B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111606793A (en) * 2020-06-10 2020-09-01 华东师范大学 Method for preparing substituted carbonyl compound by using molecular sieve to catalyze pinacol rearrangement reaction

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57142938A (en) * 1981-02-27 1982-09-03 Sumitomo Chem Co Ltd Preparation of pinacolone
US4628120A (en) * 1983-10-19 1986-12-09 Toyo Stauffer Chemical Co., Ltd. Preparing method of optically active ketones
CN104039759A (en) * 2012-01-10 2014-09-10 科勒研究有限公司 Chiral Imidodiphosphates And Derivatives Thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57142938A (en) * 1981-02-27 1982-09-03 Sumitomo Chem Co Ltd Preparation of pinacolone
US4628120A (en) * 1983-10-19 1986-12-09 Toyo Stauffer Chemical Co., Ltd. Preparing method of optically active ketones
CN104039759A (en) * 2012-01-10 2014-09-10 科勒研究有限公司 Chiral Imidodiphosphates And Derivatives Thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
L. C. HENDERSON ET AL.: "Rapid and efficient protic ionic liquid-mediated pinacol rearrangements under microwave irradiation", 《GREEN CHEM.》, vol. 13, 21 February 2011 (2011-02-21), pages 813 - 816 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111606793A (en) * 2020-06-10 2020-09-01 华东师范大学 Method for preparing substituted carbonyl compound by using molecular sieve to catalyze pinacol rearrangement reaction

Also Published As

Publication number Publication date
CN104844429B (en) 2017-03-01

Similar Documents

Publication Publication Date Title
Li et al. Improving the catalytic activity of Au25 nanocluster by peeling and doping
Sedighipoor et al. Unsymmetrical palladium (II) N, N, O, O-Schiff base complexes: Efficient catalysts for Suzuki coupling reactions
Kolla et al. Efficient one-pot synthesis of β-phosphono malonates and 2-amino-4H-chromen-4-ylphosphonate derivatives by ethylenediamine diacetate-catalyzed three-component reactions
Tabatabaeian et al. Ru (II) complexes bearing tertiary phosphine ligands: A novel and efficient homogeneous catalyst for one‐pot synthesis of dihydropyrano [3, 2‐c] chromene and tetrahydrobenzo [b] pyran derivatives
Tang et al. A facile synthesis of α-aminophosphonates catalyzed by ytterbium perfluorooctanoate under solvent-free conditions
CN106496067B (en) Buzane base azine structural compounds and its preparation method and application based on meta position link
Bhattacharjee et al. L-proline as an efficient asymmetric induction catalyst in the synthesis of chromeno [2, 3-d] pyrimidine-triones, xanthenes in water
Jin et al. An efficient and convenient approach to the synthesis of benzopyrans by a three-component coupling of one-pot reaction
Yang et al. Highly efficient synthesis of primary amides via aldoximes rearrangement in water under air atmosphere catalyzed by an ionic ruthenium pincer complex
Qiu et al. Highly Efficient and Selective Synthesis of (E)‐α, β‐Unsaturated Ketones by Crossed Condensation of Ketones and Aldehydes Catalyzed by an Air‐Stable Cationic Organobismuth Perfluorooctanesulfonate
Elamathi et al. Nanoporous AlSBA-15 catalysed Claisen–Schmidt condensation for the synthesis of novel and biologically active chalcones
CN113548998A (en) N- (2-aryl formaldehyde) -1-aminoindole derivative and synthesis method and application thereof
Li et al. An efficient proline-based homogeneous organocatalyst with recyclability
Li et al. Bifunctional gyroidal MOFs: highly efficient Lewis base and Lewis acid catalysts
CN110252400A (en) A kind of preparation method of walnut shell graft beta-cyclodextrin type catalyst and 2- Amino 3 cyano -4H- pyran derivate
Tabatabaeian et al. Anchoring of ruthenium onto imine-functionalized zeolite beta: an efficient route for the synthesis of 4 H-benzo [b] pyrans and pyrano [c] chromenes
CN104844429A (en) Method used for catalytic rearrangement of pinacol with gold
Luo et al. One-pot production of chiral α, β-epoxy ketones from benzaldehydes and acetophenones by recyclable poly (amino acid) catalysis
CN101921258B (en) Preparation method of 5-( arylmethylene) meldrum's acid
CN104909970A (en) Novel catalytic method for Meyer-Schuster rearrangement
You et al. Catalytic Enantioselective Inverse-Electron-Demand Diels–Alder Reaction of 2-Pyrones and Vinyl Selenides
CN109369448A (en) A kind of method that bimetal composite oxide catalyzes and synthesizes azobenzene compound
Guo et al. Investigation of Hydrophosphorylation Reaction of Pentacoordinate Hydrospirophosphorane and Electron‐Deficient Alkenes Catalyzed by Organic Phosphine
CN112940047B (en) Tri-dish alkene carbene palladium pyridine complex and application thereof
CN109331867B (en) Application of 2, 6-dimethylanilinium to catalysis of imine and borane hydroboration reaction

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
EXSB Decision made by sipo to initiate substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20170301