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Chiral allylamine compounds and synthesis method and applications thereof

A technology of allyl amines and compounds, which is applied in the field of chiral allyl amine compounds, can solve the problems of difficult product conversion, derivatization application, and single product type, and achieve easy conversion and derivatization, reaction operation and product The effect of simple post-processing and high ee value

Inactive Publication Date: 2011-07-20
SHANGHAI INST OF ORGANIC CHEMISTRY - CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In this type of work reported in the current literature, there is a drawback that the product type is relatively single; the obtained product is difficult to transform, derivatize and be applied in synthesis

Method used

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  • Chiral allylamine compounds and synthesis method and applications thereof
  • Chiral allylamine compounds and synthesis method and applications thereof
  • Chiral allylamine compounds and synthesis method and applications thereof

Examples

Experimental program
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Effect test

Embodiment 1

[0036] Embodiment 1: the synthesis of chiral allylamine compound

[0037]

[0038] Wherein, naphthyl represents naphthyl;

[0039] Add [Pd(C 3 h 5 )Cl] 2 (5.0umol), ligand L1 (10.0umol) and dichloromethane (1.0mL), stirred at room temperature for 15min, then added 2 (0.3mmol), 1 (0.2mmol), potassium phosphate (0.3mmol) and di Chloromethane (1.0 mL). Stir the reaction at room temperature, follow the reaction by TLC until the raw materials disappear completely, react for 8-48 hours, filter with diatomaceous earth, and concentrate to obtain a crude product, which is purified by silica gel column chromatography (petroleum ether / ethyl acetate / triethylamine=30 / 1 / 1 ) to obtain product 3, the absolute configuration of the product is R.

[0040] Product 3a: Yield: 93%; ee: 98%; [α] D 20 =+1.5° (c 1.16, CHCl 3 ); 1 H NMR (400MHz, CDCl 3 )δ1.45(s, 9H), 3.49(s, 3H), 5.29(ddt, J=1.2, 17.2, 26.4Hz, 2H), 5.54(d, J=7.0Hz, 1H), 6.23(ddd, J =7.0, 10.4, 17.3Hz, 1H), 7.24-7.42(m, 5H...

Embodiment 2

[0052] Embodiment 2: the synthetic side of chiral allylamine compound.

[0053]

[0054] Add [Pd(C 3 h 5 )Cl] 2 (5.0umol), ligand L1 (10.0umol) and Chinese name (DCM) (1.0mL), stirred at room temperature for 15min, then added 2 (0.3mmol), 5 (0.2mmol), potassium carbonate (0.3mmol) and dichloromethane (1.0 mL). The reaction was stirred at room temperature, and the reaction was tracked by TLC until the raw materials disappeared completely. The crude product was obtained by filtration with diatomaceous earth, and purified by silica gel column chromatography (petroleum ether / ethyl acetate / triethylamine=30 / 1 / 1) to obtain the product 3, the product The absolute configuration of is R.

[0055] Product 3a: Yield: 89%; ee: 96%; [α] D 20 =+1.5° (c 1.16, CHCl 3 ); 1 H NMR (400MHz, CDCl 3 )δ1.45(s, 9H), 3.49(s, 3H), 5.29(ddt, J=1.2, 17.2, 26.4Hz, 2H), 5.54(d, J=7.0Hz, 1H), 6.23(ddd, J =7.0, 10.4, 17.3Hz, 1H), 7.24-7.42(m, 5H); 13 CNMR (101MHz, CDCl 3 )δ28.2, 63.8, 65.7, 81....

Embodiment 3

[0056] Embodiment 3: the synthesis of chiral allylamine compound

[0057]

[0058] Add [Pd(C 3 h 5 )Cl] 2 (5.0umol), ligand L2 (10.0umol) and dichloromethane (1.0mL), stirred at room temperature for 15min, then added 2 (0.3mmol), 1 (0.2mmol), potassium phosphate (0.3mmol) and di Chloromethane (1.0 mL). Stir the reaction at room temperature, follow the reaction by TLC until the raw materials disappear completely, react for 8-48 hours, filter with diatomaceous earth, and concentrate to obtain a crude product, which is purified by silica gel column chromatography (petroleum ether / ethyl acetate / triethylamine=30 / 1 / 1 ) to obtain the product 3, the absolute configuration of the product is S.

[0059] Product 3a: Yield: 90%; ee: 98%; [α] D 20 = -1.5° (c 1.16, CHCl 3 ); 1 H NMR (400MHz, CDCl 3 )δ1.45(s, 9H), 3.49(s, 3H), 5.29(ddt, J=1.2, 17.2, 26.4Hz, 2H), 5.54(d, J=7.0Hz, 1H), 6.23(ddd, J =7.0, 10.4, 17.3Hz, 1H), 7.24-7.42(m, 5H); 13 CNMR (101MHz, CDCl 3)δ28.2, 63.8, 65...

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Abstract

The invention provides chiral allylamine compounds and a synthesis method and applications thereof. By utilizing the allyl amination reaction which is performed under the asymmetric catalysis of palladium, a kind of allylamine compounds which are easy to convert, derive and apply can be synthetized highly selectively. The allylamine compounds can be used in the syntheses of (-)-Cytoxazone, (+)-CP-99,994, (+)-CP-122,721 and (-)-Lasubine. The structures of the chiral allylamine compounds are shown as below.

Description

technical field [0001] The invention provides a chiral allyl amine compound, a synthesis method and an application thereof. The invention utilizes the allyl amination reaction catalyzed by asymmetric palladium to synthesize a class of allylamine compounds which are easy to transform, derivatize and apply with high selectivity. Background technique [0002] Chiral allylamine compounds are a very useful class of compounds in organic synthesis. Many types of natural products and pharmaceutical intermediates contain allylamine fragments, or can be prepared from such compounds (Some examples: Chem .Rev.1998, 98, 1689-1708; J.Org.Chem.2004, 69, 5595-5607; J.Am.Chem.Soc.2006, 128, 6054-6055; Tetrahedron Lett.2007, 48, 7094- 7098; Tetrahedron: Asymmetry 2006, 17, 860-866; Tetrahedron Lett. 2009, 50, 5686-5688). Allyl substitution reaction is the most direct, economical and effective method for the synthesis of allylamine compounds. Wherein the reaction system with palladium as th...

Claims

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Application Information

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IPC IPC(8): C07C239/20C07C271/18C07C271/12C07C269/06C07C215/28C07C213/00C07D263/24C07D211/56C07D455/02
CPCY02P20/55
Inventor 侯雪龙郑宝会
Owner SHANGHAI INST OF ORGANIC CHEMISTRY - CHINESE ACAD OF SCI