CN109180566A - A method of preparing 2- amino -3- methylene -1,2,3,6- 5,6-tetrahydropyridine derivative - Google Patents
A method of preparing 2- amino -3- methylene -1,2,3,6- 5,6-tetrahydropyridine derivative Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/92—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with a hetero atom directly attached to the ring nitrogen atom
- C07D211/96—Sulfur atom
Abstract
2- amino -3- methylene -1 is prepared the invention discloses a kind of, 2, the method of 3,6- 5,6-tetrahydropyridine derivatives is in reaction dissolvent, using N- allyl -4- methoxyl group-N- vinylbenzenesulfonamide compound and substituted alkenyl iodine compound as reaction raw materials, under metal palladium catalyst effect, reaction obtains polysubstituted 2- amino -3- methylene -1,2,3,6- tetrahydropyridine analog derivatives.Reaction condition of the present invention is mild, and raw material is cheap and easy to get, and operation is simple, yield is higher, and the route for synthesizing substrate is mature, strong operability, crucial skeleton structure is provided for multiclass drug molecule and efficiently synthesizing for natural products, and industrial-scale production can be widely used in.
Description
Technical field
2- amino -3- methylene -1,2 is prepared present invention relates particularly to a kind of, the method for 3,6- 5,6-tetrahydropyridine derivatives belongs to
In organic compound technique applied technical field.
Background technique
2- amino -3- methylene -1,2,3,6- tetrahydropyridine analog derivatives are a kind of extremely important chemical intermediates, simultaneously
2- amino -3- methylene -1,2,3,6- tetrahydropyridine analog derivative skeleton is widely present in various natural products and pharmaceutical activity
In molecule, the patent class drug of Beyer Co., Ltd's treatment asthma as shown in Figure 1 and shown in Fig. 4 it can improve chronic obstructive pulmonary
The drug aminopyridine ketone of disease, anti-diabetic shown in fig. 5 and anti-fat class drug and anti-tumor drug shown in Fig. 2 all contain
There is 2- amino -1,2, the skeleton structure of 3,6- tetrahydropyridines, 2- amino -1,2, the skeleton structure of 3,6- tetrahydropyridines is in Fig. 6 institute
The treatment Alzheimer disease shown, Parkinson's disease and increase β-glucocerebrosidase stability shown in Fig. 3
All there is important application in international monopoly class drug；The synthesis of such compound and Study on Transformation are to pharmaceutical developments and natural products
There is important meaning in the fields such as synthesis；The present invention has developed a kind of polysubstituted 2- amino -3- methylene -1,2,3,6- tetrahydropyridine
Efficient, the green synthesis method of analog derivative, application value with higher.
The traditional method for synthesizing 2- amino -3- methylene -1,2,3,6- tetrahydropyridines is usually that needs are more
Step synthesis, and hardly possible operates, yield is very low, and industrial applications are caused with very big limitation.
Summary of the invention
The present invention innovatively proposes a kind of inexpensive efficient preparation 2- amino -3- methylene -1,2,3,6- tetrahydropyridine class
The new method of derivative can efficiently realize the conversion of reaction by using metal palladium catalyst.Fig. 7 formula (I)
As shown in the above formula (I), the present invention utilizes N- allyl -4- methoxyl group-N- vinylbenzenesulfonamide compound (substrate 1)
It is used as starting material with alkenyl iodine compound (substrate 2), under the action of metal palladium catalyst, is carried out in reaction dissolvent anti-
It answers, synthesizes 2- amino -3- methylene -1,2,3,6- tetrahydropyridines.
In the present invention, R1It is allyl, methacrylic, phenyl；R2It is aromatic hydrocarbons, alkyl-substituted aromatic hydrocarbon, alkane；PG is Ts,
Ms。
Preferably, R1Allyl, phenyl.R2It is aromatic hydrocarbons, alkylaromatic hydrocarbon, alkane.PG is Ts.
In the present invention, R1, R2Above-mentioned group is included but are not limited to, for example, R1, R2It can also be multi-substituent,
All kinds of side chains.
In the present invention, the starting material alkenyl iodine and N- allyl -4- methoxyl group-N- vinylbenzenesulfonamide compound
Usage ratio be 1:1-2.0.Preferably, the two usage ratio is 1:1.
In the present invention, the palladium catalyst is Pd (OAc)2、Pd (PPh3)4、PdCl2(PPh3)2、Pd2(dba)3。
Preferably, the palladium catalyst is Pd2(dba)3。
The dosage of the catalyst is the 1-10 mol% of raw material 1.
Preferably, the dosage of the catalyst is 5 mol%.
In the present invention, the ligand is PCy3, PPh3。
The dosage of the ligand is the 20-30 mol% of raw material 1.
Preferably, described is PPh3, the dosage of institute's metal catalyst is 20 mol%.
In the present invention, the alkali be TEA(triethylamine), DIPEA(N, N- diisopropylethylamine), DMAP(4- dimethylamino
Pyridine).
Preferably, the alkali is TEA.
Preferably, the dosage of the alkali is 2.0 equivalents.
In the present invention, the reaction dissolvent is DMF, toluene, nitrile or dioxane.
It preferably, is reacted in dioxane.
The reaction dissolvent can also be dimethylbenzene, Isosorbide-5-Nitrae-dioxane, DMF, DMSO more than including but is not limited to.
In the present invention, the synthetic reaction is in 50-100oIt is carried out at a temperature of C.
It preferably, is 80oIt is reacted at a temperature of C.
In the present invention, the synthesising reacting time is 2-5 hours.
It preferably, is reaction 5 hours.
Specifically, synthetic reaction of the present invention is in reaction flask A, by N- allyl -4- methoxyl group-N- vinyl benzene sulphur
Amide compound (substrate 1, X mmol) is dissolved in Z mL reaction dissolvent, at room temperature, sequentially adds alkenyl iodohydrin class chemical combination
Object (substrate 2, Y mmol), catalyst Pd2(dba)3(W mol%), alkali TEA (2.0 equiv)；Reaction is in 50-100oC is lazy
Property gas shield under react 2-5 hour；Reaction process is detected with TLC.After completion of the reaction, directly plus silica gel, dry chromatography is revolved,
Isolated target product 3.
The advantages of synthetic reaction of the present invention includes: that reaction substrate used in synthetic method of the present invention is all simple and easy to get, is closed
Simply easy to operate at step, raw material sources are extensive, and performance is stablized, in addition, synthetic route is also all mature classical conjunction
At reaction；Various metallic catalysts used in the present invention are also all common commercial reagents, highly stable, and have yield
The few characteristic of height, simple process, pollution, is applicable to industrialized production completely.
2- amino -3- methylene -1,2,3,6- the tetrahydropyridines that the present invention synthesizes are a kind of very important
The core skeleton of natural products and modern medicines, the reaction route of innovative design of the present invention provide one to synthesize this kind of compound
A generally applicable preparation method；Synthesize traditional method of 2- amino -3- methylene -1,2,3,6- tetrahydropyridines
General difficult operation, yield are very low, and industrial applications are caused with very big limitation.
The invention patent, based on commercialization, cheap simple raw material, through post-mature classics synthetic reaction system
All kinds of alkenyl iodine class compounds are obtained as reaction substrate, under metal palladium catalyst effect, reaction obtains polysubstituted 2- amino-
3- methylene -1,2,3,6- tetrahydropyridines；Operation is fairly simple, and reaction condition is mild, and yield is higher, is suitble to
Large-scale industrial production.
Detailed description of the invention
Fig. 1 is the 2003/76406 A1,2003 pharmaceutical chemistry structural representation of Patent No. WO of Beyer Co., Ltd's treatment asthma
Figure.
Fig. 2 is 2007077543 A2,2007 pharmaceutical chemistry structural schematic diagram of anti-tumor drug Patent No. WO.
Fig. 3 is that the international monopoly class drug patent number of increase β-glucocerebrosidase stability is WO
2007150064 A2,2007 chemical structure schematic diagrames.
Fig. 4 is the change of drug aminopyridine ketone Patent No. WO 2,003,076,405 2003 for improving Chronic Obstructive Pulmonary Disease
Learn structural schematic diagram.
Fig. 5 is anti-diabetic and anti-fat class drug patent number is the signal of 2000039140 A1 of WO, 2000 chemical structure
Figure.
Fig. 6 is treatment Alzheimer disease, 2016038379 A1 of Parkinsonian drugs Patent No. WO, 2006 chemistry
Structural schematic diagram.
Fig. 7 is formula (I) in a kind of method formula for preparing 2- amino -3- methylene -1,2,3,6- 5,6-tetrahydropyridine derivative
Chemical equation schematic diagram.
Fig. 8 is a kind of method formula embodiment 1 for preparing 2- amino -3- methylene -1,2,3,6- 5,6-tetrahydropyridine derivative
Chemical equation schematic diagram.
Fig. 9 is a kind of method formula embodiment 2 for preparing 2- amino -3- methylene -1,2,3,6- 5,6-tetrahydropyridine derivative
Chemical equation schematic diagram.
Figure 10 is a kind of method formula embodiment 3 for preparing 2- amino -3- methylene -1,2,3,6- 5,6-tetrahydropyridine derivative
Chemical equation schematic diagram.
Figure 11 is a kind of method formula embodiment 4 for preparing 2- amino -3- methylene -1,2,3,6- 5,6-tetrahydropyridine derivative
Chemical equation schematic diagram.
Figure 12 is a kind of method formula embodiment 5 for preparing 2- amino -3- methylene -1,2,3,6- 5,6-tetrahydropyridine derivative
Chemical equation schematic diagram.
Figure 13 is a kind of method formula embodiment 6 for preparing 2- amino -3- methylene -1,2,3,6- 5,6-tetrahydropyridine derivative
Chemical equation schematic diagram.
Specific embodiment
In conjunction with following specific embodiments, the present invention is described in further detail, and of the invention protects content not limit to
In following embodiment.Without departing from the spirit and scope of the invention, those skilled in the art it is conceivable that variation and excellent
Point is all included in the present invention, and using appended claims as protection scope；Implement process of the invention, condition,
Reagent, experimental method etc. are among the general principles and common general knowledge in the art, this hair in addition to what is specifically mentioned below
It is bright that there are no special restrictions to content；Data given by following embodiment include concrete operations and reaction condition and product.Product is pure
Degree is identified by nuclear-magnetism.
Embodiment 1
N- allyl -4- methyl-N-(3- methylene -5- phenyl -1- tolysulfonyl -1,2,3,6- tetrahydropyridine) benzene sulfonyl
Amine: Fig. 8
In the test tube reactor of 25 mL, with nitrogen exchange of air 3 times.By substrate 1a (0.2 mmol, 49.7 mg), 2c
(0.2 mmol, 82.7 mg), Pd2(dba)3(0.01 mmol, 9.1 mg) are successively weighed into reaction tube, and nitrogen is changed in evacuation,
And dioxane (2 mL) is added under nitrogen atmosphere, 56 μ L triethylamines are added in liquid-transfering gun.Reaction system is heated to 80oC,
Reaction 5 hours.TLC is detected after reaction, and system is cooled to room temperature.Directly plus it is solid to obtain brown for silica gel, rotation dry chromatography
Body 3ca (50%).1H NMR (400 MHz, CDCl3): δ 7.68 (d, J=8.4 Hz, 1H), 7.64 (d,J =
8.0 Hz, 2H), 7.35-7.28 (m, 9H), 6.89 (s, 1H), 5.70-5.60 (m, 1H), 5.32 (s,
1H), 5.14 (dd, J = 11.2, 1.2 Hz, 1H), 5.11-5.10 (m, 1H), 4.15 (s, 2H), 3.89
(s, 2H), 3.76 (d, J = 6.4 Hz, 2H), 2.42 (s, 3H), 2.40 (s, 3H). 13C-NMR (100
MHz, CDCl3): δ 143.9, 143.8, 137.3, 136.9, 134.9, 133.5, 133.1, 132.3, 129.8,
128.7, 128.6, 127.6, 127.5, 125.5, 121.7, 119.1, 119.0, 54.0, 46.8, 46.2,
21.5, 21.48. MS (EI) m/z 535 (M+);HRMS calculated value is C29H30N2O4S2534.1647 actual value is
534.1648。
Embodiment 2
N- allyl-N-(5- ethyl -3- methylene -1- tolysulfonyl -1,2,3,6- tetrahydropyridine) -4- Methyl benzenesulfonyl
Amine: Fig. 9
In the test tube reactor of 25 mL, with nitrogen exchange of air 3 times.By substrate 1a (0.2 mmol, 49.7 mg), 2d
(0.2 mmol, 73.0 mg), Pd2(dba)3(0.01 mmol, 9.1 mg) are successively weighed into reaction tube, and nitrogen is changed in evacuation,
And dioxane (2 mL) is added under nitrogen atmosphere, 56 μ L triethylamines are added in liquid-transfering gun.Reaction system is heated to 80oC reacts 5 hours.TLC is detected after reaction, and system is cooled to room temperature.Directly plus silica gel, rotation dry chromatography obtain palm fibre
Color solid 3da (71%).1H NMR (400 MHz, CDCl3): δ 7.42 (d, J = 8.0 Hz 2H), 7.61 (d, J
= 8.0 Hz, 2H), 7.28 (d, J = 8.0 Hz, 4H), 6.31 (s, 1H), 5.67-5.57 (m, 1H),
5.15 (s, 1H), 5.12-5.07 (m, 2H), 3.75 (s, 2H), 3.71 (d, J = 6.4 Hz, 2H), 3.63
(s, 2H), 3.95 (s, 2H), 2.42 (s, 3H), 2.41 (s, 3H), 2.06 (m, 2H), 0.98 (t, J =
7.6 Hz, 3H).13C-NMR (100 MHz, CDCl3): δ 143.7, 141.9, 134.9, 133.7, 133.3,
132.3, 129.7, 127.6, 127.5, 119.4, 118.8, 116.7, 53.9, 47.9, 46.3, 27.7,
21.48, 21.46. MS (EI) m/z 487 (M+);HRMS calculated value is C25H30N2O4S2 397.1048, actual value
It is 486.1647.
Embodiment 3
The p- tolyl of N- allyl -4- methyl-N-(3- methylene -5() -1- tosyl -1,2,3,6- tetrahydropyridine) -
4- benzsulfamide: Figure 10
In the test tube reactor of 25 mL, with nitrogen exchange of air 3 times.By substrate 1a (0.2 mmol, 49.7 mg), 2e
(0.2 mmol, 85.5 mg), Pd2(dba)3(0.01 mmol, 9.1 mg) are successively weighed into reaction tube, and nitrogen is changed in evacuation,
And dioxane (2 mL) is added under nitrogen atmosphere, 56 μ L triethylamines are added in liquid-transfering gun.Reaction system is heated to 80oC reacts 5 hours.TLC is detected after reaction, and system is cooled to room temperature.Directly plus silica gel, rotation dry chromatography obtain palm fibre
Color solid 3ea (43%).1H NMR (400 MHz, CDCl3): δ 7.67 (d, J=8.4 Hz, 2H), 7.64 (d,J
= 8.0 Hz, 2H), 7.31 (d, J = 8.0 Hz, 2H), 7.28 (d, J=8.4 Hz, 2H), 7.22 (d,J
=8.0 Hz, 2H), 7.15 (d,J = 7.6 Hz, 2H), 6.85 (s, 1H), 5.70-5.60 (m, 1H), 5.31
(s, 1H), 5.15-5.09 (m, 2H), 4.13 (s, 2H), 3.88 (s, 2H), 3.76 (d, J = 6.0 Hz,
2H), 2.42 (s, 3H), 2.39 (m, 3H), 2.35 (m, 3H).13C-NMR (100 MHz, CDCl3): δ
143.9, 143.8, 138.8, 136.9, 135.0, 134.4, 133.6, 133.2, 132.3, 129.7, 129.3,
127.7,125.4,121.3,119.0,118.3,54.0,46.8,46.2,21.51,21.49,21.2. MS
(EI) m/z 549 (M+);HRMS calculated value is C30H32N2O4S2 548.1803 actual value 548.1805.
Embodiment 4
N- allyl-N-(5- dodecyl -3- methylene -1- tolysulfonyl -1,2,3,6- tetrahydropyridine) -4- methylbenzene sulphur
Amide: Figure 11
In the test tube reactor of 25 mL, with nitrogen exchange of air 3 times.By substrate 1a (0.2 mmol, 49.7 mg), 2f
(0.2 mmol, 101.1 mg), Pd2(dba)3(0.01 mmol, 9.1 mg), are successively weighed into reaction tube, and nitrogen is changed in evacuation
Gas, and dioxane (2 mL) is added under nitrogen atmosphere, 56 μ L triethylamines are added in liquid-transfering gun.Reaction system is heated to 80oC reacts 5 hours.TLC is detected after reaction, and system is cooled to room temperature.Directly plus silica gel, rotation dry chromatography obtain palm fibre
Color solid 3fa (56%).1H NMR (400 MHz, CDCl3): δ 7.64 (d, J=8.0 Hz, 2H), 7.61 (d,J
= 8.4 Hz, 2H), 7.31-7.29 (m, 4H), 6.31 (s, 1H), 6.32 (s, 1H), 5.66-5.56 (m,
1H), 5.14-5.12 (m, 2H), 5.08-5.07 (m, 1H), 3.76 (s, 2H), 3.71 (d, J = 6.4 Hz,
2H), 3.63 (s, 2H), 2.42 (d, J = 8.0 Hz, 6H), 1.99 (t, J = 7.2 Hz, 2H), 1.33-
1.26 (m, 20H), 0.88 (t, J = 6.8 Hz, 3H).13C-NMR (100 MHz, CDCl3): δ 143.68,
143.67, 140.8, 134.9, 133.7, 133.5, 132.3, 129.7, 127.6, 127.5, 119.3, 118.8,
117.7, 53.9, 47.9, 46.3, 35.0, 31.9, 29.62, 29.60, 29.5, 29.4, 29.31, 29.29,
27.5, 22.6, 21.50, 21.48, 14.1. MS (EI) m/z 627 (M+);HRMS calculated value is
C35H50N2O4S2 626.3212 actual value 626.3211.
Embodiment 5
N- allyl-N-(5-(3- methoxyphenyl) -3- methylene -1- tolysulfonyl -1,2,3,6- tetrahydropyridine) -4- first
Base benzsulfamide: Figure 12
In the test tube reactor of 25 mL, with nitrogen exchange of air 3 times.By substrate 1a (0.2 mmol, 49.7 mg), 2g
(0.2 mmol, 88.7 mg), Pd2(dba)3(0.01 mmol, 9.1 mg) are successively weighed into reaction tube, and nitrogen is changed in evacuation,
And dioxane (2 mL) is added under nitrogen atmosphere, 56 μ L triethylamines are added in liquid-transfering gun.Reaction system is heated to 80oC reacts 5 hours.TLC is detected after reaction, and system is cooled to room temperature.Directly plus silica gel, rotation dry chromatography obtain palm fibre
Color solid 3ga (30%).1H NMR (400 MHz, CDCl3): δ 7.69 (d, J=8.4 Hz, 2H), 7.66 (d,J
= 8.0 Hz, 2H), 7.34-7.28 (m, 6H), 6.94-6.71 (m, 1H), 6.89-6.87 (m, 2H), 6.85-
6.84 (m, 1H), 5.72-5.62 (m, 1H), 5.37 (s, 1H), 5.16 (dd, J = 10.8, 1.2 Hz,
1H), 5.13-5.12 (m, 1H), 4.14 (s, 2H), 3.90 (s, 2H), 3.84 (s, 2H), 3.78 (d, J
= 6.4 Hz, 2H), 2.44 (s, 3H), 2.42 (s, 3H). 13C-NMR (100 MHz, CDCl3): δ 159.7,
143.9, 143.8, 138.9, 136.8, 134.9, 133.5, 132.7, 132.3, 132.3, 129.77, 129.6,
127.7, 127.5, 121.8, 119.4, 119.0, 118.1, 113.6, 111.7, 55.3, 54.0, 46.9,
46.3, 21.50, 21.49. MS (EI) m/z 565 (M+);HRMS calculated value is C30H32N2O5S2 564.1753,
Actual value is 564.1755.
Embodiment 6
N-(5- dodecyl -3- methylene -1- tosyl -1,2,3,6- tetrahydropyridine) -4- Methyl-N-phenyl benzene sulfonyl
Amine: Figure 13
In the test tube reactor of 25 mL, with nitrogen exchange of air 3 times.By substrate 1b (0.2 mmol, 82.7 mg), 2f
(0.2 mmol, 101.1 mg), Pd2(dba)3(0.01 mmol, 9.1 mg) are successively weighed into reaction tube, and nitrogen is changed in evacuation,
And dioxane (2 mL) is added under nitrogen atmosphere, 56 μ L triethylamines are added in liquid-transfering gun.Reaction system is heated to 80oC reacts 5 hours.TLC is detected after reaction, and system is cooled to room temperature.Directly plus silica gel, rotation dry chromatography obtain palm fibre
Color solid 3fb (55%).1H NMR (400 MHz, CDCl3): δ 7.59 (d, J=8.0 Hz, 2H), 7.44 (d,J
= 8.4 Hz, 2H), 7.26-7.24 (m, 5H), 7.17 (d, J=8.0 Hz, 1H), 7.02-6.99 (m, 2H),
6.13 (s, 1H), 5.67 (s, 1H), 3.78 (s, 2H), 3.56 (s, 2H), 2.43 (s, 3H), 2.37
(s, 3H), 1.76 (t, J = 6.8 Hz, 2H), 1.31-1.18 (m, 20H), 0.89 (t, J = 6.8 Hz,
3H). 13C-NMR (100 MHz, CDCl3): δ 144.0, 143.5, 140.9, 139.2, 134.2, 133.6,
129.5, 127.74, 127.71, 127.5, 127.4, 123.9, 120.7, 116.5, 48.0, 47.1, 34.5,
31.8, 29.60, 29.57, 29.4, 29.3, 28.9, 26.9, 22.6, 21.5, 21.4, 14.0. MS (EI)
m/z 663 (M+);HRMS calculated value is C38H50N2O4S2 662.3212 actual value 662.3214.
Claims (8)
1. a kind of prepare 2- amino -3- methylene -1,2, the method for 3,6- 5,6-tetrahydropyridine derivatives, which is characterized in that with N- alkene
Propyl -4- methoxyl group-N- vinylbenzenesulfonamide compound and substituted alkenyl iodine derivative are reaction raw materials, are urged in Metal Palladium
Under the action of agent, reaction obtains 2- amino -3- methylene -1,2,3,6- tetrahydropyridine analog derivatives in reaction dissolvent；Instead
Answer process as shown in the formula (I)；
Formula (I)；
Wherein, PG is Ts；R1It is allyl, phenyl; R2It is aromatic hydrocarbons, alkyl-substituted aromatic hydrocarbon, alkane.
2. preparation 2- amino -3- methylene -1,2 as described in claim 1, the method for 3,6- 5,6-tetrahydropyridine derivatives is special
Sign is that the palladium catalyst is Pd (OAc)2、Pd(PPh3)4、PdCl2(dppf) or Pd2(dba)3；The dosage of the catalyst
For 1-10%.
3. preparation 2- amino -3- methylene -1,2 as described in claim 1, the method for 3,6- 5,6-tetrahydropyridine derivatives is special
Sign is that the ligand is PCy3、PPh3The ligand dosage is 1-30%.
4. preparation 2- amino -3- methylene -1,2 as described in claim 1, the method for 3,6- 5,6-tetrahydropyridine derivatives is special
Sign is that the alkali is TEA, DIPEA, Cy2NMe、K2CO3、DMAP。
5. preparation 2- amino -3- methylene -1,2 as described in claim 1, the method for 3,6- 5,6-tetrahydropyridine derivatives is special
Sign is that the solvent is acetonitrile, n,N-Dimethylformamide, dioxane, toluene.
6. preparation 2- amino -3- methylene -1,2 as described in claim 1, the method for 3,6- 5,6-tetrahydropyridine derivatives is special
Sign is that the synthetic reaction is in 50-100oC is carried out.
7. preparation 2- amino -3- methylene -1,2 as described in claim 1, the method for 3,6- 5,6-tetrahydropyridine derivatives is special
Sign is that the reaction time is 2-5h.
8. 2- amino -3- methylene -1,2,3,6- tetrahydropyridine analog derivative is prepared as described in claim 1.
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| CN101044116A (en) * | 2004-10-14 | 2007-09-26 | 欧洲凯尔特公司 | 4-phenylsulfonamidopiperidines as calcium channel blockers |
| CN103951541A (en) * | 2008-01-25 | 2014-07-30 | 波士顿学院董事会 | Method for catalyzing metathesis reactons including enantioselective olefin metathesis |
| JP5764771B2 (en) * | 2011-03-09 | 2015-08-19 | 公立大学法人大阪市立大学 | Azadirs-Alder reaction catalyst and method for producing tetrahydropyridine compound using the same |
| CN106518752A (en) * | 2016-05-12 | 2017-03-22 | 山东理工大学 | Synthesis method of 5-phenyl-1, 2, 3, 6-tetrahydropyridine derivative |
| CN106146388A (en) * | 2016-07-05 | 2016-11-23 | 山东理工大学 | A kind of 3 phenylpiperidine derivative synthesizing process |
| CN108503574A (en) * | 2018-04-10 | 2018-09-07 | 山东理工大学 | A method of synthesis 3- vinyl -4- acetenyl -2,3- dihydro pyrrole derivates |
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| CN114380736A (en) * | 2020-10-21 | 2022-04-22 | 复旦大学 | Synthetic method of 2,3,4, 5-tetrahydropyridine compound |
| CN114380736B (en) * | 2020-10-21 | 2023-10-03 | 复旦大学 | Synthesis method of 2,3,4, 5-tetrahydropyridine compound |
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