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Method for promoting reductive coupling reaction of imine and alkyne by means of alcohol to build allyl amine derivative

A technology for allylamine and derivatives, which is applied in the field of synthesis of allylamine derivatives, which can solve the problems of increased preparation costs, cumbersome steps, and strict operating requirements, and achieves convenient follow-up processing procedures, convenient operation and processing, and simple equipment requirements Effect

Inactive Publication Date: 2019-09-13
NANKAI UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0006] 2) Allylamine derivatives can be obtained by direct reductive coupling of cheap and easy-to-obtain imines and alkynes. When the catalyst is cheap metal Ni, the reaction requires an equivalent amount of Et 3 B. ZnEt 2 etc. as reductant, while using clean reductant H2, the reaction needs precious metal Rh as a catalyst: the system is very sensitive to water and oxygen, and the equivalent organic waste will be produced after the metal reductant reacts, and it will seriously pollute the environment; and hydrogen as When the reducing agent is used, the noble metal Rh must be used as the catalyst, the reaction cost is high, and the reaction substrate of the system is limited.
[0007] In summary, although allylamine derivatives are of great significance in the synthesis of drugs, the existing synthetic methods are cumbersome and require strict operations, and the use of equivalent metal reagents increases the cost of preparation and causes serious environmental pollution. Expensive, high production costs, unable to mass-produce

Method used

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  • Method for promoting reductive coupling reaction of imine and alkyne by means of alcohol to build allyl amine derivative
  • Method for promoting reductive coupling reaction of imine and alkyne by means of alcohol to build allyl amine derivative
  • Method for promoting reductive coupling reaction of imine and alkyne by means of alcohol to build allyl amine derivative

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0031] Example 1: Synthesis of (E)-4-Methyl-N-(1,2,3-triphenylallyl)benzenesulfonamide

[0032]

[0033] In a nitrogen atmosphere, the ligands AnIPr.HCl (5.5mg, 5mol%), t-BuOK (2.3mg, 10mol%), Ni(cod) were sequentially added to the reaction flask 2 (5.5mg, 10mol%), THF (1.0mL), i-PrOH (1.0mL), finally added raw materials 1a (35.6mg, 0.2mmol) and 2a (62mg, 0.24mmol), stirred at 100°C for 18 hours, cooled Return to room temperature, dilute with ethyl acetate, filter with celite, concentrate and separate by column chromatography to obtain the target product 3a as a white solid in a yield (81%). 1 H NMR (400MHz, CDCl 3 )δ7.69(d, J=8.4Hz, 2H), 7.29-7.24(m, 5H), 7.24-7.17(m, 3H), 7.13(t, J=7.6Hz, 2H), 7.09-6.99(m , 3H), 6.78-6.72(m, 2H), 6.8(d, J=6.8Hz, 2H), 6.48(s, 1H), 5.36(d, J=7.6Hz, 1H), 4.83(d, J= 7.6Hz, 1H), 2.36(s, 3H). 13 C NMR (100MHz, CDCl 3 ( C 28 h 29 N 2 o 2 S([M+NH 4 ] + ) 457.1944, Found 457.1942.

Embodiment 2

[0034]Example 2: Synthesis of (E)-2-Methyl-N-(1,2,3-triphenylallyl)propane-2-sulfonamide

[0035]

[0036] In a nitrogen atmosphere, the ligands AnIPr.HCl (5.5mg, 5mol%), t-BuOK (2.3mg, 10mol%), Ni(cod) were sequentially added to the reaction flask 2 (5.5mg, 10mol%), THF (1.0mL), i-PrOH (1.0mL), finally added raw materials 1a (35.6mg, 0.2mmol) and 2b (54mg, 0.24mmol), stirred at 100°C for 18 hours, cooled Return to room temperature, dilute with ethyl acetate, filter with diatomaceous earth, concentrate and separate by column chromatography to obtain the target product 3b as a white solid, yield (65%). 1 H NMR (400MHz, CDCl 3 ( d, J=6.8Hz, 2H), 6.78(s, 1H), 5.52(d, J=10.0Hz, 1H), 4.29(d, J=9.6Hz, 1H), 1.37(s, 9H). 13 C NMR (100MHz, CDCl 3 )δ141.7, 140.2, 137.4, 136.1, 129.7, 129.6, 129.4, 128.9, 128.8, 128.1, 128.0, 127.8, 127.3, 127.1, 65.5, 60.3, 24.3. HRMS (ESI) calcd.for C 25 h 31 N 2 o 2 S ([M+NH 4 ] + ) 423.2101, Found 423.2101.

Embodiment 3

[0037] Example 3: Synthesis of (E)-N-(2,3-diphenyl-1-(p-tolyl)allyl)-4-methylbenzenesulfonamide

[0038]

[0039] In a nitrogen atmosphere, the ligands AnIPr.HCl (5.5mg, 5mol%), t-BuOK (2.3mg, 10mol%), Ni(cod) were sequentially added to the reaction flask 2 (5.5mg, 10mol%), THF (1.0mL), i-PrOH (1.0mL), finally added raw materials 1a (35.6mg, 0.2mmol) and 2c (65.5mg, 0.24mmol), stirred at 100°C for 18 hours, Cool to room temperature, dilute with ethyl acetate, filter with celite, concentrate and separate by column chromatography to obtain the target product 3c as a white solid in a yield (79%). 1 HNMR (400MHz, CDCl 3 )δ7.69 (d, J=8.4Hz, 2H), 7.24-7.17 (m, 3H), 7.17-7.10 (m, 4H), 7.10-7.01 (m, 5H), 6.79-6.72 (m, 2H) , 6.69(d, J=6.8Hz, 2H), 6.48(s, 1H), 5.31(d, J=8.0Hz, 1H), 4.77(d, J=8.0 Hz, 1H), 2.36(s, 3H) , 2.32(s, 3H). 13 C NMR (100MHz, CDCl 3 )δ143.4, 139.9, 137.7, 137.6, 137.5, 136.2, 136.1, 129.8, 129.6, 129.4, 129.4, 129.3, 128.8, 127.9, 127.8, 127.5, 127.3, 127....

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Abstract

The invention relates to a method for using alcohol as a green cheap reduction agent and carrying out an intermolecular reductive coupling reaction on ordinary imine and ordinary alkyne under catalysis of cheap transition metal to efficiently produce a polysubstituted allyl amine derivative. The method is economic and practical. The critical points of the method for solving problems lie in the facts that a large-steric hindrance high-electronegativity carbene ligand is found to improve the reaction activity, and meanwhile, by designing a chiral carbene ligand, chiral control of part of substrates is achieved; and the cheap metal nickle and the green reduction agent isopropyl alcohol are used jointly, so that the method is economic, practical and environmentally friendly, and is in accord with principles of sustainable development.

Description

technical field [0001] The invention relates to a synthesis method for generating allylamine derivatives from common internal alkynes and common imines, and belongs to the technical field of reductive coupling reactions. Background technique [0002] The allylamine structure not only exists in many pesticides and drug molecules, but also is an important intermediate in organic synthesis, especially drug synthesis. Therefore, how to construct multi-substituted allylamine structures cheaply and efficiently has high application and research value. Through this method, a series of three-substituted allylamine structures can be easily synthesized. The substituents on the alkenyl group can be either aryl or alkyl, and the aryl substituents are compatible with both the electron-donating group and the electro-absorbing group. ; The group connected to the α position of the alkenyl group can be either an aryl group or an alkyl group, and the aryl substituent can be either an electric-...

Claims

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Application Information

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IPC IPC(8): C07C303/36C07D333/20C07D295/135C07C311/16C07C311/17C07C311/18C07C311/03C07B45/04
CPCC07B45/04C07C303/36C07D295/135C07D333/20C07C2601/14C07C311/16C07C311/17C07C311/18C07C311/03
Inventor 叶萌春姚伟伟
Owner NANKAI UNIV
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