A kind of fluorine nitrogen type amination reagent, its preparation method and application

A fluorine-nitrogen, amination technology, used in the preparation of sulfonic acid amides, chemical instruments and methods, preparation of organic compounds, etc.

Active Publication Date: 2018-12-18
SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

In the document J.Am.Chem.Soc.2015,137,999, it is reported that starting from a diaryl enamine, a rhodium-catalyzed asymmetric hydrogenation reaction can be achieved to directly obtain a chiral 2,2-diaryl amino acid with high enantioselectivity derivatives, but the reaction requires highly functionalized diarylenamines as substrates

Method used

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  • A kind of fluorine nitrogen type amination reagent, its preparation method and application
  • A kind of fluorine nitrogen type amination reagent, its preparation method and application
  • A kind of fluorine nitrogen type amination reagent, its preparation method and application

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Experimental program
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Effect test

Embodiment 1

[0076]

[0077] In a 500mL three-necked flask, N-methylbenzenesulfonamide (13.5g, 78.9mmol) was dissolved in FCCl 3 / HCl 3 (200mL, v / v 1:1) mixed solvent, after cooling to -78°C, F 2 / N 2 (2:8) The gas is slowly passed into the reaction solution (1-2 bubbles / minute). After 3 hours of reaction, TLC showed that most of the starting material had been consumed. Access to N 2 Half an hour later, after the reaction returned to room temperature, the reaction solution was passed through a short column of silica gel, CH 2 Cl 2 Rinse, concentrate the filtrate, and separate by flash column chromatography (petroleum ether / ethyl acetate=20:1) to obtain 6.7 g (45% yield) of a colorless liquid. R f =0.5 (petroleum ether / ethyl acetate=10:1). 1 H NMR (400MHz, CDCl 3 )δ7.97(d, J=8.0Hz, 2H), 7.77(t, J=8.0Hz, 1H), 7.64(t, J=8.0Hz, 2H), 3.17(d, J=31.6Hz, 3H) . 13 C NMR (100MHz, CDCl 3 )δ135.0, 131.0, 130.1, 129.3, 40.8 (d, J=12.2Hz). 19 F NMR (376MHz, CDCl 3 )δ-37.46(q,J=31.6Hz).H...

Embodiment 2

[0079]

[0080]Weigh NaH (3.6g, 60mmol, 60wt% in mineral oil) into a 500mL round bottom bottle, add anhydrous CH 2 Cl 2 (250mL), stirred into a paste. Under the protection of Ar gas, a dichloromethane solution (50 mL) of N-alkylbenzenesulfonamide (30 mmol) was added dropwise, and a large amount of gas was generated during the dropwise addition. After the dropwise addition was completed, stirring was continued at room temperature for 30 minutes. N-fluorobisbenzenesulfonimide (NFSI, 56 g, 180 mmol) was added into the reaction system, and stirred at room temperature for 6 hours. The reaction solution was slowly poured into ice water to quench unreacted NaH. Separate the organic phase with a separatory funnel and the aqueous phase with CH 2 Cl 2 (200mL×3) extraction, anhydrous MgSO 4 The organic phase is dried and filtered. After the filtrate was concentrated, it was separated by flash column chromatography (PE / EA=20:1) to obtain the target product.

[0081]

[0082]...

Embodiment 3

[0095]

[0096] Step 1: In a 100mL sealed tube, ligand L* (82.0mg, 0.20mmol) and Cu(CH 3 EN) 4 PF 6 (37.0mg, 0.10mmol) was dissolved in DMA / CH under the protection of argon 2 Cl 2 (1:4, 20 mL), after stirring for 0.5 h, the resulting colorless solution was ready for use.

[0097]Step 2: In a sealed 10 mL tube, add the compound represented by formula III (0.40 mmol, 2.0 equiv) and anhydrous LiOtBu (8.0 mg, 0.10 mmol, 0.5 equiv). Under the protection of argon, in the reaction tube cooled to -20°C, add the above copper catalyst solution (2.0mL), the compound (0.20mmol, 1.0equiv) shown in formula II, and the fluorine nitrogen shown in formula I Type amination reagent (0.4mmol, 2.0equiv), the reaction solution turned blue. The reaction was stirred at -10°C. After the specified time, the reaction solution was diluted with 20 mL of ethyl acetate and washed with water (10 mL×3). The organic phase was washed with anhydrous MgSO 4 Drying, filtration, after the filtrate is conc...

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Abstract

The invention discloses a fluorine-nitrogen type animation reagent as well as a preparation method and application thereof. The application comprises the following steps: carrying out reaction described in the specification on a fluorine-nitrogen type animation reagent shown in a formula I, a compound shown in a formula II and a compound shown in a formula III under the actions of a copper catalyst, a dinitrogen ligand and alkali in an organic solvent under the gas protection condition, so that a compound shown in a formula IV is obtained. The fluorine-nitrogen type animation reagent disclosed by the invention can obtain an optically active 2,2-diaryl ethylamine compound with good yield and excellent corresponding selectivity by taking alkene as substrate and carrying out asymmetric amine arylation reaction of the alkene under the actions of the copper catalyst and the dinitrogen ligand. (A reaction formula is described in the specification.).

Description

technical field [0001] The invention relates to a fluorine nitrogen type amination reagent, its preparation method and application. Background technique [0002] N-fluoro-N-alkylsulfonamide is usually used as an electrophilic fluorinating reagent, which can efficiently realize the fluorination of carbanions (J.Am.Chem.Soc.1984,106,454; US Patent 4479901), and its amine group Part of it is in the form of N-alkylsulfonamide as a by-product, and the atom economy is not high. N-fluoro-N-alkylsulfonamide has never been reported as an aminating reagent. [0003] Optically active 2,2-diarylethanamine compounds widely exist in drugs, active molecules and natural products. It is of great significance to develop asymmetric synthesis methods for such compounds, but there are relatively few studies in this field. [0004] In the document J.Am.Chem.Soc.2004,126,1954, it was reported that the asymmetric addition reaction of aryllithium reagents to β-nitrovinyl compounds was realized by...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C303/40C07C311/48C07C311/16C07C311/17C07C311/19C07J41/00C07D209/08C07D333/20C07D333/58C07C213/02C07C217/60
CPCY02P20/55
Inventor 刘国生王定海陈品红
Owner SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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