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Chiral phosphoric acid with 5,5'-bitetralone skeleton and preparation method thereof

A technology of tetralone and phosphoric acid, which is applied in the field of intermediates involved in the preparation process, can solve the problems of low activity of organic chiral phosphoric acid catalysts, and achieve the effects of short steps, high yield and mild reaction conditions

Inactive Publication Date: 2015-12-02
NANJING UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0006] In order to solve the shortcomings of the low activity of traditional organic chiral phosphoric acid catalysts, the invention discloses the structure and preparation method of a newly designed mobile phone phosphoric acid catalyst

Method used

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  • Chiral phosphoric acid with 5,5'-bitetralone skeleton and preparation method thereof
  • Chiral phosphoric acid with 5,5'-bitetralone skeleton and preparation method thereof
  • Chiral phosphoric acid with 5,5'-bitetralone skeleton and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0050] Embodiment 1, the preparation of (R)-5,5'-tetralone-6,6'-diol (2)

[0051]

[0052] The reaction equation is shown in the above formula, wherein, DDQ is 2,3-dichloro-5,6-dicyano-1,4-benzoquinone;

[0053] Weigh (R)-H into a 500mL single-necked bottle 8 -BINOL (4.42g, 15.0mmol), add 100mL 1,4-dioxane and 5mLH 2 O stirred to dissolve. DDQ (13.62 g, 60.0 mmol) was added under ice cooling. After reacting at 25°C for 4 hours, filter with suction, and wash the filter residue with 50 mL of 1,4-dioxane. Concentrate the filtrate, add 200mL ethyl acetate, saturated Na 2 SO 3 The solution was washed three times. Anhydrous Na 2 SO 4 The organic phase was dried, filtered with suction, concentrated, and directly cast into the next step. It can also be purified by silica gel column chromatography (petroleum ether: ethyl acetate, volume ratio 2:1 ~ 1:2) to obtain a white solid. Melting point 263~264℃; [α] D 20 =+129.2 (c0.48, MeOH); IR (film) 3164, 2945, 1648, 1571, 1274...

Embodiment 2

[0054] Example 2, the preparation of (R)-7,7'-dibromo-5,5'-tetralone-6,6'-diol (3)

[0055]

[0056] In a water bath at 25°C, add 100 mL of 1,4-dioxane to a 250 mL single-necked bottle, add HBr (48% aq) (7.5 mL, 66.0 mmol) under stirring, and then add H 2 o 2 (35% aq) (3.7 mL, 42.9 mmol), and the product from the previous step was added. After reacting for 1 hour, add 0.95g Na 2 SO 3 Dissolve the solution in 25 mL of water, stir for half an hour, adjust the pH to 8-9 with 10% NaOH aqueous solution, and wash with ethyl acetate three times. Use 6mol / L dilute hydrochloric acid to acidify the aqueous phase to pH 1~2, extract with ethyl acetate, anhydrous Na 2 SO 4 Drying, suction filtration, concentration, and silica gel column chromatography (petroleum ether:ethyl acetate, volume ratio 3:1-3:2) yielded 4.90 g of a light yellow solid product, and the total yield of the two steps was 68%. Melting point 280~281℃; [α] D 20 =+83.0(c0.42, MeOH); IR(film) 3281, 2947, 1662, 15...

Embodiment 3

[0057] Example 3, the preparation of (R)-7,7'-diphenyl-5,5'-bitetralone-6,6'-diol (4)

[0058]

[0059] The reaction equation is shown in the above formula, wherein Ac is acetyl; Ph is phenyl; n Bu is n-butyl; Ad is adamantyl; DME is ethylene glycol dimethyl ether;

[0060] Under argon protection, compound (R)-3 (5.0g, 10.46mmol), phenylboronic acid (4.46g, 36.61mmol), palladium acetate (0.0472g, 0.21mmol), bis(adamantyl ) n-butylphosphine (0.094g, 0.262mmol), 90mL ethylene glycol dimethyl ether and 45mL 1.0mol / L potassium carbonate solution. The reactor was placed in a 95°C oil bath and stirred. Stop heating after 11 hours, cool to room temperature, add 50 mL of saturated ammonium chloride solution, acidify to pH 3-4 with 1.6 mol / L dilute hydrochloric acid in ice bath, let stand for 2 hours, and suction filter (obtain filtrate 1). The filter cake was dissolved in dichloromethane / methanol, anhydrous Na 2 SO 4 Dry, filter with suction, concentrate to quick dryness, filt...

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Abstract

The invention belongs to the technical field of organic chemical synthesis, and discloses a 5,5'-bitetralone chiral skeleton, a chiral phosphoric acid with the 5,5'-bitetralone skeleton, and a method for preparing the chiral phosphoric acid on the basis of 5,5'-bitetralone-6,6'-diphenol and substitutes thereof. The phosphoric acid maintains the advantages of favorable enantioselectivity in the chiral phosphoric acid based on BINOL and H8-BINOL in tradition, and also has excellent enantioselectivity in some organic reactions. The chiral phosphoric acid with the 5,5'-bitetralone skeleton overcomes the defect of lower catalytic activity, and has higher reaction activity than the traditional phosphoric acid. The preparation method has the advantages of cheap and accessible raw materials and catalyst, shorter synthesis route, simple technique and mild conditions, and has industrialization potential.

Description

technical field [0001] The invention belongs to the technical field of organic chemical synthesis, in particular to a chiral phosphoric acid with a 5,5'-tetralone skeleton, and a 5,5'-tetralone-6,6'-diphenol-based A method for preparing the chiral phosphoric acid and its substitutes, as well as intermediates involved in the preparation process. Background technique [0002] The development of novel chiral catalysts is an active field in asymmetric synthesis. In 2004, two groups of Akiyama and Terada independently discovered the BINOL-based chiral binaphthylphosphoric acid catalyst (phosphoricacid, Angew.Chem.Int.Ed.2004,43,1566; J.Am.Chem.Soc.2004,126,5356 ), which have been widely used in many organic transformations. The reaction catalyzed by chiral phosphoric acid has a variety of activation modes (Chem.Rev.2014, 114, 9047), and has achieved excellent enantioselectivity, but most of the reaction time is long and the amount of catalyst is large (5%-20% ), which to some ...

Claims

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Application Information

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IPC IPC(8): C07F7/08C07F9/6574C07C49/747C07C49/755
Inventor 史一安王亚洲刘伟任文龙
Owner NANJING UNIV
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