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Method for catalyzing indole silylation and proton transfer hydrogenation

A proton transfer, indole silane technology, applied in chemical instruments and methods, physical/chemical process catalysts, organic compound/hydride/coordination complex catalysts, etc. Due to the large amount of catalyst and other problems, it can achieve the effects of efficient and fast proton transfer hydrogenation, mild reaction conditions, and wide applicability of substrates.

Active Publication Date: 2019-08-13
JILIN UNIV
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AI Technical Summary

Problems solved by technology

The current technical status is that the reaction conditions are harsh, such as the reaction requires heating, the amount of catalyst used is large, and the use of precious metals is used for catalysis, etc., often accompanied by side reactions of hydrosilation, and the conversion rate of products is not high.
The synthesis of indoline compounds is mainly catalyzed by metals and Lewis acids. The hydrogen source is mainly provided by silane or hydrogen. The reaction conditions have disadvantages such as high temperature, high pressure, and long reaction time.

Method used

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  • Method for catalyzing indole silylation and proton transfer hydrogenation
  • Method for catalyzing indole silylation and proton transfer hydrogenation
  • Method for catalyzing indole silylation and proton transfer hydrogenation

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0033] Embodiment 1 in situ nuclear magnetic generation C 9 h 11 N PhSiH 2 ·B(C 6 f 5 ) 3 (3e)

[0034]

[0035] Add B(C) to the J.Young-type NMR tube 6 f 5 ) 3 (12.8mg, 0.025mmol) and 0.3mL of CD 2 Cl 2 , add 0.1mL Ph 2 SiH 2 (4.6mg, 0.025mmol) and the CD of 0.2ml 1-methylindoline (3.3mg, 0.025mmol) 2 Cl 2 Solution, mix evenly, the solution is colorless after reacting for ten minutes, carry out NMR test, it can be clearly seen from the H NMR spectrum that the main product generated is C 9 h 11 N PhSiH 2 ·B(C 6 f 5 ) 3 (3e). ( 1 H / 19 See attached for F NMR chart figure 1 and 2 ) 1 H NMR (500MHz, CD 2 Cl 2 )δ7.78–7.71 (m,3H,H Ar ),7.71–7.67(m,2H,H Ar ),7.60–7.54(m,6H,H Ar ),7.42–7.33(m,4H,H Ar ),7.27(t,J=8.5Hz,1H,H Ar ),7.13(t,J=8.0Hz 1H,H Ar ),6.92(d,J=8.0Hz,1H,H Ar ),6.45(d,J=8.5Hz,1H,H Ar ), 4.92 (ddd, J=11.6, 9.4, 4.0Hz, 1H, NCH 2 ),3.92(s,3H,NCH 3 ),3.90–3.84(m,1H,NCH 2 ),3.66(br q,1H,BH),3.58(s,3H,NCH 3 ),3.21–3.12(m,1H,NCH 2 ), 2....

Embodiment 2

[0036] Embodiment 2 in situ nuclear magnetic generation C 9 h 11 N·C 21 h 18 NSiH·B(C 6 f 5 ) 3 (3f)

[0037]

[0038] Add B(C) to the J.Young-type NMR tube 6 f 5 ) 3 (12.8mg, 0.025mmol) and 0.3mL of CD 2 Cl 2 , add 0.1mL C into it with a syringe 21 h 18 CD of NSiH(4aa) (7.8mg, 0.025mmol) and 0.2ml 1-methylindoline (3.3mg, 0.025mmol) 2 Cl 2 Solution, mixed evenly, the solution was colorless after ten minutes of reaction, nuclear magnetic test was carried out, it can be clearly seen from the hydrogen nuclear magnetic spectrum that the main product generated is C 9 h 11 N·C 21 h 18 NSiH·B(C 6 f 5 ) 3 (3f). ( 1 H / 19 See attached for F NMR chart image 3 and 4 ) 1 H NMR (500MHz, CD 2 Cl 2 )δ7.78–7.71 (m,3H,H Ar ),7.71–7.67(m,2H,H Ar ),7.60–7.54(m,6H,H Ar ),7.42–7.33(m,4H,H Ar ),7.27(t,J=8.5Hz,1H,H Ar ),7.13(t,J=8.0Hz1H,H Ar ),6.92(d,J=8.0Hz,1H,H Ar ),6.45(d,J=8.5Hz,1H,H Ar ), 4.92 (ddd, J=11.6, 9.4, 4.0Hz, 1H, NCH 2 ),3.92(s,3H,NCH 3 ),3.9...

Embodiment 3

[0040] Preparation of 3-(diphenylsilyl)-1-methylindole and 1-methylindoline under the conditions of embodiment 3 without solvent

[0041]

[0042] In the glove box, weigh 1-methylindole (13.1g 0.1mol), B(C 6 f 5 ) 3 (0.01mmol, 5.6mg) was fully stirred in a 30mL reaction flask, when B(C 6 f 5 ) 3 After complete dissolution, add Ph 2 SiH 2 (9.2g0.05mol), stirring at room temperature for 24h, taking 0.2mL reaction solution with a pipette gun and dissolving it in deuterated benzene, calculating the conversion rate of the reaction by the integrated area of ​​the raw material and the product nitrogen methyl group on the proton nuclear magnetic spectrum to be 96.9%, The yields of 3-(diphenylsilyl)-1-methylindole and 1-methylindoline were 46.1% and 45.2%, respectively. Post-processing method: Pour the reaction mixture into 300 mL of hexane, stir for 30 minutes, filter to obtain a white solid, wash with (3×30 mL) hexane and dry it, and obtain a white solid 3-(diphenylsilyl)- ...

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Abstract

The invention discloses a catalytic system for efficiently catalyzing indole silanization and proton transfer hydrogenation, and belongs to the technical field of organic synthesis. According to the catalytic system, indole and silane serve as raw materials, tris(pentafluorophenyl) boron (B (C6F5)3) serves as a catalyst, reaction is performed for 10 minutes at the indoor temperature to simultaneously achieve 3-position selective indole silanization and proton transfer hydrogenation or reaction is performed for 10-1440 minutes at the temperature ranging from 100 DEG C to 140 DEG C to achieve 3-position efficient and specific catalytic indole silanization. The catalytic system has the advantages that the catalytic system is convenient to operate, mild in reaction condition, rapid in reaction, high in conversion rate, less in catalyst consumption and applicable to various solvent systems or body systems without any solvents, raw materials are easily acquired, precious metal is omitted, a catalytic intermediate is high in stability and the like.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, and in particular relates to a highly efficient catalytic system for catalyzing indole silylation and proton transfer hydrogenation. Background technique [0002] In recent years, indole silylation products have been widely used in various fields, especially in organic electronics and photonics, pharmaceuticals and molecular material synthesis. (J.Org.Chem.2007,72,6241 2008, 86, 230. Drug Discovery Today 2003, 8, 551. J. Med. Chem. 2013, 56, 388. Chem. Rev. 1995, 95, 1375. Chem. Soc. Rev. Science 2012, 337, 1644). Indoline compounds are mainly used to synthesize indole derivatives, such as indoline dyes and sensitizers for solar cells, which have good photoelectric conversion properties. It is also an intermediate of medicine and plant growth regulator. Therefore, indole silylation products and indoline compounds have always been research hotspots in related fields such as chemistry a...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07F7/08B01J31/14
CPCB01J31/146C07F7/0814C07F7/0829
Inventor 张越涛何江华韩玉玺张苏韬
Owner JILIN UNIV
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