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Chiral center nitrogen heterocyclic carbine precursor salt with quadrol skeleton, synthetic method and application

A technology of nitrogen heterocyclic carbene and chiral center, applied in the field of chiral nitrogen heterocyclic carbene precursor salt, synthesis, can solve the problem of limited skeleton structure and the like, achieve simple synthesis method, high practical application value, enantioselectivity Good results

Active Publication Date: 2011-08-17
SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

But in general, the framework structure of nitrogen-heterocyclic carbene catalysts is limited. Looking for chiral nitrogen-heterocyclic carbene catalysts with new skeletons and making them suitable for some reactions or more reactions with good catalytic activity and enantioselectivity has been going on. It is one of the research hotspots of chemists

Method used

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  • Chiral center nitrogen heterocyclic carbine precursor salt with quadrol skeleton, synthetic method and application
  • Chiral center nitrogen heterocyclic carbine precursor salt with quadrol skeleton, synthetic method and application
  • Chiral center nitrogen heterocyclic carbine precursor salt with quadrol skeleton, synthetic method and application

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0024] (1) Synthesis of (5R, 6R)-5,6-diphenylpiperazin-2-one

[0025]

[0026] Among them, rt means room temperature; reflux means reflux.

[0027]Slowly add 1.65g (1.1mL, 10mmol) of ethyl bromoacetate in 20mL of absolute ethanol solution dropwise to (1R, 2R)-1,2-diphenyl-1,2-ethylenediamine (2.12g, 10mmol ) and NaOH 0.4g (10mmol) in 30mL absolute ethanol solution, it takes about three hours. React at room temperature for two days, and reflux at 80 degrees overnight. The solvent was removed under reduced pressure and separated by column chromatography (ethyl acetate / methanol=20 / 1) to obtain 1.4 g (5.55 mmol, yield 54%) of the product as a white solid.

[0028] P1(5R,6R)-5,6-Diphenylpiperazin-2-one

[0029] (and its enantiomers)

[0030] 1 H NMR (300MHz, CDCl 3 )δ7.11-6.86(m, 10H), 6.51(s, 1H), 4.40(d, J=9.0Hz, 2H), 3.63(m, 3H), 2.19(brs, 1H). 13 C NMR (75MHz, CDCl 3 )δ169.7, 138.5, 138.4, 128.26, 128.23, 128.17, 128.09, 127.7, 127.4, 65.8, 64.4, 50.0.

[0031] (2...

Embodiment 2

[0184] Application of Nitrogen Heterocyclic Carbenes in the Synthesis of Chiral Benzopyrone Compounds

[0185]

[0186] Among them, base means base, and solvent means organic solvent.

[0187] General experimental operation: Dissolve the catalyst precursor in xylene, add alkali, and stir at room temperature for 0.5 hours. Add 0.1 mmol of the substrate and react at room temperature. After TLC tracking the reaction is complete, add distilled water at 0°C to quench, extract with ethyl acetate, combine the organic phases, dry over anhydrous sodium sulfate, remove the solvent under reduced pressure, and purify by column chromatography (petroleum ether: ethyl acetate) to obtain the product, ee value Determined by chiral HPLC.

[0188]

[0189] Colorless oil, 95% yield, 93% ee [chiral column AD-H, n-hexane / isopropanol=97 / 3, v=0.7mL·min -1 , λ=254nm, t(major)=23.1min, t(minor)=34.9min]; [α] D 20 =-6.8 (c=1.0, CH 2 Cl 2 ). 1 H NMR (300MHz, CDCl 3 )δ7.89 (dd, J=1.8, 7.8Hz...

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Abstract

The invention provides a chiral center nitrogen heterocyclic carbine precursor salt with a quadrol skeleton, a synthetic method and application. The precursor salt has a structural formula shown in the specifications, and can be prepared from cheap and readily-available chiral substituted diamine as an initial raw material by three-step synthesis, well applied to a polarity inversion reaction of catalytic aldehyde compounds, and used for preparing chiral benzopyrone compounds.

Description

technical field [0001] The present invention relates to a class of chiral nitrogen heterocyclic carbene precursor salt, synthesis method and application, that is, a multi-chiral center nitrogen heterocyclic carbene precursor salt with ethylenediamine skeleton, synthesis method and application. Background technique [0002] In the past two decades, nitrogen heterocyclic carbene has been widely concerned by chemists as organic small molecule catalysts [(a) D.Enders and T.Balensiefer, Acc.Chem.Res.2004, 37, 534.(b)D .Enders, O.Niemeier and A.Henseler, Chem.Rev.2007, 107, 5606.(c) V.Nair, S.Vellalath, B.P.Babu Chem.Soc.Rev.2008, 37, 2691.(d)E.M. Phillips, A. Chan, K. A. Scheidt, Aldrichimica Acta 2009, 42, 55.]. In this field, we have recently developed a polychiral center nitrogen heterocyclic carbene precursor salt with an ethylenediamine skeleton, its synthesis method and use. Starting from commercially cheap and easy-to-obtain optically pure substituted ethylenediamine as ...

Claims

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Application Information

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IPC IPC(8): C07D311/22C07D307/83C07D487/04C07B53/00C07D335/06
Inventor 游书力贾敏强李毅
Owner SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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