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Allylation coupling reaction method and application thereof

A technology of allylation coupling and coupling reaction, which is applied in chemical instruments and methods, condensation/addition reactions to prepare amino compounds, organic chemistry, etc., and can solve problems such as the inability to realize secondary amine allylation reactions

Active Publication Date: 2021-08-24
SOUTH UNIVERSITY OF SCIENCE AND TECHNOLOGY OF CHINA
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

According to reports, the Ritter research group used primary amines as raw materials and oxythianthymine as a substrate to realize the allylic amination of terminal olefins under the catalysis of Ir metal and light, but this reaction is limited to primary amine substrates and cannot Enabling the allylation of secondary amines and other types of substrates (J.Am.Chem.Soc.doi.org / 10.1021 / jacs.0c08248)

Method used

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  • Allylation coupling reaction method and application thereof
  • Allylation coupling reaction method and application thereof
  • Allylation coupling reaction method and application thereof

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0065]

[0066] First weigh compound M01 (29.3mg, 0.24mmol), K 2 CO 3 (27.6mg, 0.20mmol) and compound A01 (82.4mg, 0.20mmol) were added to the reaction tube, and the gas was purged three times through the vacuum line. Under nitrogen atmosphere, DCM (2.0mL) was added and reacted at room temperature for 24h. After the reaction was completed, the solvent was removed by rotary evaporation, and the sample was applied by dry method. Column chromatography (300-400 mesh chromatography silica gel) (petroleum ether-ethyl acetate=19:1) yielded 41.9 mg of product P01 with a yield of 91%.

[0067] 1 H NMR (400MHz, CDCl 3 )δ (ppm): 8.09-8.01 (m, 2H), 7.59-7.50 (m, 1H), 7.43 (dd, J = 8.4, 7.0Hz, 2H), 5.42 (tt, J = 7.2, 1.3Hz, 1H ), 4.84(d, J=7.2Hz, 2H), 2.32-2.24(m, 2H), 2.20-2.12(m, 2H), 1.58(p, J=2.3Hz, 6H);

[0068] 13 C NMR (101MHz, CDCl 3 )δ (ppm): 166.81, 147.21, 132.88, 130.73, 129.72, 128.41, 115.36, 61.28, 37.14, 29.27, 28.50, 27.93, 26.75;

[0069] HRMS-ESI(m / z): 231.1378[M...

Embodiment 2

[0071]

[0072] Weigh K first 2 CO 3 (27.6mg, 0.20mmol) and compound A01 (82.4mg, 0.20mmol) were added to the reaction tube, and the gas was purged three times through the vacuum line. Under nitrogen atmosphere, DCM (2.0mL) and compound M02 (14.4mg, 0.24mmol) were added , Reaction at room temperature for 24h. After the reaction was completed, the solvent was removed by rotary evaporation, and the sample was applied by dry method. Column chromatography (300-400 mesh chromatography silica gel) (petroleum ether-ethyl acetate=19:1) yielded 21.6 mg of product P02 with a yield of 64%.

[0073] 1 H NMR (400MHz, CDCl 3 )δ(ppm): 5.28(tt, J=7.3, 1.2Hz, 1H), 4.58(d, J=7.3Hz, 2H), 2.22-2.17(m, 2H), 2.11(d, J=5.6Hz, 2H), 2.05(s, 3H), 1.56(tt, J=6.9, 4.5Hz, 6H);

[0074] 13 C NMR (100MHz, CDCl 3 )δ (ppm): 171.29, 147.07, 115.26, 60.81, 37.14, 29.14, 28.46, 27.86, 26.74, 21.25;

[0075] HRMS-ESI(m / z): 169.1225[M+H] + .

Embodiment 3

[0077]

[0078] Weigh K first 2 CO 3 (27.6mg, 0.20mmol) and compound A01 (82.4mg, 0.20mmol) were added to the reaction tube, and the gas was purged three times through the vacuum line. Under nitrogen atmosphere, DCM (2.0mL) and compound M03 (11.0mg, 0.24mmol) were added , Reaction at room temperature for 24h. After the reaction was completed, the solvent was removed by rotary evaporation, and the sample was applied by dry method. Column chromatography (300-400 mesh chromatography silica gel) (petroleum ether-ethyl acetate=19:1) yielded 22.8 mg of product P03 with a yield of 74%.

[0079] 1 H NMR (400MHz, CDCl 3 )δ(ppm): 8.06(s, 1H), 5.31(tt, J=7.4, 1.3Hz, 1H), 4.68(d, J=7.4Hz, 2H), 2.21(t, J=5.5Hz, 2H) , 2.16-2.09(m, 2H), 1.56(h, J=4.2Hz, 7H);

[0080] 13 C NMR (100MHz, CDCl 3 )δ (ppm): 161.26, 147.99, 114.64, 60.17, 37.12, 29.15, 28.44, 27.84, 26.69;

[0081] HRMS-ESI(m / z): 155.1066[M+H] + .

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Abstract

The invention discloses a novel allylation coupling reaction method. The method comprises the following steps: with alkenyl thianthrene salt as an allylation reagent, respectively with a carboxylic acid compound and organic amine as substrates, in the presence of alkali, or directly with a carboxylate compound and aromatic hydrocarbon / heterocyclic hydrocarbon as substrates, reacting in an organic solvent at room temperature to obtain an allylation coupling product. The preparation method has the advantages of mild conditions and no transition metal participation, can efficiently realize the preparation of various allyl esters, allyl substituted amines and allyl substituted aromatic hydrocarbon / heterocyclic hydrocarbon compounds, and has ideal application prospects in the fields of fine chemical engineering, material science and pharmacy.

Description

technical field [0001] The invention belongs to the technical field of chemical synthesis methods, and in particular relates to a metal-free catalyzed allylation coupling reaction method and its application. Background technique [0002] Allylamines, esters are ubiquitous compounds in bioactive molecules and organic materials and can be used as versatile starting materials for a variety of chemical transformations. So far, Pd-catalyzed allyl CH activation is a dominant method for the synthesis of allylamines, and only monosubstituted terminal alkenes are suitable substrates (Chem.Sci.DOI: 10.1039 / d0sc05952h). The allylation reaction of acids and amines is an important reaction in organic synthesis, and the catalytic reaction involving transition metals is currently the main way to construct allyl functional groups. According to reports, the Ritter research group used primary amines as raw materials and oxythianthymine as a substrate to achieve allylic amination of terminal ...

Claims

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Application Information

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IPC IPC(8): C07C67/04
CPCC07C67/04C07D215/48C07D333/38C07D209/42C07D307/68C07D207/34C07J9/005C07D263/32C07C303/40C07D495/04C07D499/04C07D499/46C07C209/60C07C41/30C07D295/023C07D295/03C07K5/06078C07C2601/14C07C2601/16C07C2603/74C07C69/78C07C69/145C07C69/07C07C69/24C07C69/75C07C69/612C07C69/618C07C69/738C07C69/94C07C311/16C07C69/734C07C211/48C07C211/27C07C211/38C07C211/25C07C43/215Y02P20/55
Inventor 舒伟刘明上
Owner SOUTH UNIVERSITY OF SCIENCE AND TECHNOLOGY OF CHINA
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