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Method for application of enamine in palladium catalytic asymmetry allyl group alkylated reaction

An allyl alkylation and asymmetric technology, applied in asymmetric synthesis, organic chemical methods, chemical instruments and methods, etc., can solve the problems of expensive and dangerous reagents, harsh reaction conditions, troublesome operation, etc., and achieve high reaction Active, easy and safe operation, good application effect

Inactive Publication Date: 2008-03-12
SHANGHAI JIAO TONG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Its disadvantages are: harsh reaction conditions, expensive and dangerous reagents, troublesome operation

Method used

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  • Method for application of enamine in palladium catalytic asymmetry allyl group alkylated reaction

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0019] 1. Preparation of enamine

[0020] Cyclohexanone (20 g, 0.20 mol) was dissolved in cyclohexane (250 mL), then anhydrous magnesium sulfate (120 g) was added in one portion under nitrogen. The system was cooled down to 0° C., and pyrrolidine (84 mL, 1.0 mol, 5 equiv) was added thereto through a syringe for about 0.5 h. Continue to keep warm for 0.5h, and then stir the mixed system at room temperature overnight. Magnesium sulfate was removed by filtration and washed with ring-dried cyclohexane (3 x 50 mL). The combined filtrates were evaporated to remove the solvent under reduced pressure, and the residue was distilled under reduced pressure (69°C / 1mmHg) to obtain the product N-cyclohexenylpyrrolidine as a colorless liquid. Sealed under nitrogen and stored in refrigerator.

[0021] 1 H NMR (CDCl 3 , 400Hz): δ1.49-1.55(m, 2H), 1.62-1.68(m, 2H), 1.78-1.82(m, 4H), 2.05-2.09(m, 2H), 2.14-2.17(m, 2H) , 2.95-2.98(m, 4H), 4.24-4.26(m, 1H).

[0022] 2. Application in asymme...

Embodiment 2

[0025] 1. Preparation of enamine

[0026] Cyclohexanone (20 g, 0.20 mol) was dissolved in cyclohexane (250 mL), then anhydrous magnesium sulfate (120 g) was added in one portion under nitrogen. The system was cooled down to 0° C., and pyrrolidine (84 mL, 1.0 mol, 5 equiv) was added thereto through a syringe for about 0.5 h. Continue to keep warm for 0.5h, and then stir the mixed system at room temperature overnight. Magnesium sulfate was removed by filtration and washed with ring-dried cyclohexane (3 x 50 mL). The combined filtrates were evaporated to remove the solvent under reduced pressure, and the residue was distilled under reduced pressure (69°C / 1mmHg) to obtain the product N-cyclohexenylpyrrolidine as a colorless liquid. Sealed under nitrogen and stored in refrigerator.

[0027] 1 H NMR (CDCl 3 , 400Hz): δ1.49-1.55(m, 2H), 1.62-1.68(m, 2H), 1.78-1.82(m, 4H), 2.05-2.09(m, 2H), 2.14-2.17(m, 2H) , 2.95-2.98(m, 4H), 4.24-4.26(m, 1H).

[0028] 2. Application in asymme...

Embodiment 3

[0031] 1. Preparation of enamine

[0032] Cyclohexanone (20 g, 0.20 mol) was dissolved in cyclohexane (250 mL), then anhydrous magnesium sulfate (120 g) was added in one portion under nitrogen. The system was cooled down to 0° C., and pyrrolidine (84 mL, 1.0 mol, 5 equiv) was added thereto through a syringe for about 0.5 h. Continue to keep warm for 0.5h, and then stir the mixed system at room temperature overnight. Magnesium sulfate was removed by filtration and washed with ring-dried cyclohexane (3 x 50 mL). The combined filtrates were evaporated to remove the solvent under reduced pressure, and the residue was distilled under reduced pressure (69°C / 1mmHg) to obtain the product N-cyclohexenylpyrrolidine as a colorless liquid. Sealed under nitrogen and stored in refrigerator.

[0033] 1 H NMR (CDCl 3 , 400Hz): δ1.49-1.55(m, 2H), 1.62-1.68(m, 2H), 1.78-1.82(m, 4H), 2.05-2.09(m, 2H), 2.14-2.17(m, 2H) , 2.95-2.98(m, 4H), 4.24-4.26(m, 1H).

[0034] 2. Application in asymme...

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Abstract

The present invention relates to a method in the chemical technological field wherein the enamine is used in the palladium-catalyzed asymmetric allyl alkylation; the chiral ligand and the palladium catalyst are dissolved in the solvent first and react at the room temperature; the substituted allyl acetate is added; the mixture is stirred; then the enamine category compounds are added in the reaction; the cold saturated ammonium chloride solution is used for hydrolysis after the reaction is finished; thus, the product can be made. The enamine is a quite convenient and quite promising pro-nuclear reagent and overcomes the trouble of the unstable enol ether caused by the replacement of the alkali with the simple ketone; the operation is simple and safe; and the catalytic reaction has the high activity and selectivity of the reaction.

Description

technical field [0001] The invention relates to an asymmetric synthesis method in the technical field of chemical industry, in particular to a method for using enamine in a palladium-catalyzed asymmetric allyl alkylation reaction. Background technique [0002] In the current literature, asymmetric allyl substitution reactions using simple ketones as nucleophiles always form unstable enol structures. This just needs the condition of following several aspects: 1) needs to use the very strong base of basicity, such as butyllithium or LDA etc., not only the price of reagent is comparatively expensive, danger is also big; 2) preparation enol formula reactive intermediate The conditions required during this process are very harsh, otherwise it will either cause reaction failure or may cause experimental accidents. Sometimes additives need to be added to make negative ions form relatively stable enol ethers; 3) enol ethers must be prepared and used before each reaction. , making t...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C49/796C07C45/00C07B53/00
Inventor 张万斌谢芳刘德龙
Owner SHANGHAI JIAO TONG UNIV
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