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Organic phosphoric acid catalyst and its preparation method and application

An organophosphoric acid, organolithium technology, applied in organic chemistry methods, organic compound/hydride/coordination complex catalysts, organic chemistry and other directions, can solve the problem of large amount of catalyst used, achieve excellent catalytic performance, easy preparation, The effect of mild reaction conditions

Inactive Publication Date: 2008-03-26
PEKING UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, to the best of our knowledge, previously reported chiral organophosphate catalysts are based on only a few limited frameworks, such as 3,3′-substituted BINOL, 3,3′-substituted H 8 -BINOL (Liu, H.; Cun, L.-F.; Mi, A.-Q.; Jing, Y.-Z. and Gong, L.-Z. Org. Lett. 2006, 8, 6023.) , TADDOL (Akiyama, T.; Saitoh, Y.; Morita, H.; Fuchibe, K. Adv. Synth. Catal. 2006, 347, 1523.), VANOL and VAPOL (Rowland, G.B.; Zhang, H.; Rowland , E.B.; Chennamadhavuni, S.; Wang, Y. and Antilla, J.C.J.Am.Chem.Soc.2005, 127, 15696.)
In addition, the organic reactions that organophosphoric acid catalysts can catalyze have certain limitations, and the amount of catalyst used in some reactions is still relatively large

Method used

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  • Organic phosphoric acid catalyst and its preparation method and application
  • Organic phosphoric acid catalyst and its preparation method and application
  • Organic phosphoric acid catalyst and its preparation method and application

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0030] Example 1: Preparation of (R)-2'-cyclohexyloxy-(1,1'-binaphthyl)-2-ol

[0031]

[0032](R)-Binaphthol (BINOL) (8.58 g, 30 mmol), triphenylphosphine (7.86 g, 30 mmol) and cyclohexanol (9.0 g, 90 mmol) were dissolved in 60 mL of tetrahydrofuran. Under stirring at room temperature, a solution of diethyl azodicarboxylate (DEAD) (5.22 g, 30 mmol) in 40 mL of tetrahydrofuran was added dropwise to the above mixture over 4 hours. After stirring at room temperature for 20 hours, the mixture was evaporated to remove the solvent under reduced pressure. The residue was separated by silica gel column chromatography (petroleum ether-dichloromethane-ethyl acetate 40:10:1) to obtain oily (R)-2'-cyclohexyloxy-(1,1'-binaphthyl)-2- Phenol 4.3g, yield 39%. [α] D 20 =-55.0 (c1.0, CHCl 3 ); 1 H NMR (300MHz, CDCl 3 ): δ0.93-1.64(m, 10H), 4.06-4.15(m, 1H), 5.14(s, 1H), 7.05-7.34(m, 8H), 7.74-7.81(m, 4H); 13 C NMR (75MHz, CDCl 3 ): δ22.9, 23.0, 25.2, 31.6, 76.9, 115.4, 117.2, 117.5,...

Embodiment 2

[0033] Example 2: Preparation of (R)-2-cyclohexyloxy-2'-methoxymethyl-1,1'-binaphthalene

[0034]

[0035] Dissolve (R)-2′-cyclohexyloxy-(1,1′-binaphthyl)-2-ol (9.74g, 26.47mmol) in 60mL tetrahydrofuran (THF), add 1.27g NaH under stirring at 0°C . The reaction mixture was stirred for an additional 1 h at 0°C and chloromethyl methyl ether (3.0 mL, 37 mmol) was added. As detected by TLC, the reaction was complete 6 hours after the addition of chloromethyl methyl ether. The reaction mixture was added to 100 ml of water, the aqueous phase was separated and extracted three times with ethyl acetate. The organic layer was washed with brine and water, followed by Na 2 SO 4 Dry and concentrate under reduced pressure. The crude product was separated by silica gel column chromatography, and the eluent was petroleum ether-dichloromethane-ethyl acetate (40:10:1) to obtain (R)-2-cyclohexyloxy-2'-methoxy 10.6 g of methyl-1,1'-binaphthalene, yield 97%. [α] D 20 =+64.1(c1.0, CHCl ...

Embodiment 3

[0036] Example 3: Preparation of (R)-2-methoxy-2'-methoxymethyl-3'-iodo-1,1'-binaphthalene

[0037]

[0038] Dissolve (R)-2-methoxy-2'-methoxymethyl-1,1'-binaphthyl (4.6g, 13.4mmol) in anhydrous tetrahydrofuran (100mL), and then add n- Butyllithium (16mmol, 7.0mL 2.3M hexane solution) was removed from the cooling bath and naturally raised to room temperature and stirred for 2 hours. A solution of iodine (4.57 g, 36 mmol) in tetrahydrofuran (20 mL) was added dropwise to the reaction mixture at -78°C, stirring was continued for 1 hour, and saturated Na 2 S 2 o 3 solution (30ml), then warmed to room temperature and stirred for 1 hour. The organic phase was separated and the aqueous phase was extracted with ethyl acetate (3 x 40 mL). The combined organic phases were washed with anhydrous NaSO 4 dry. Concentration under reduced pressure, the residue was separated by silica gel column chromatography, the eluent was petroleum ether-ethyl acetate (10:1), to obtain (R)-2-metho...

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Abstract

The present invention provides one new kind of chiral organic phosphoric acid catalyst characterizing biaxial chirality and its preparation process. The chiral organic phosphoric acid catalyst is prepared with chiral binaphthol or its derivative, and through protection with methoxymethyl group, alkylation, iodination, coupling with boric acid intermediate to obtain binaphthol derivative, the deprotection of the binaphthol derivative and reaction with phosphorus oxychloride to obtain the organic phosphoric acid compound. The chiral catalyst preparing process is simple, and the chiral catalyst is applied in catalyzing asymmetric hydrogenation reaction of quinoline compounds and has high efficiency, and high selectivity.

Description

technical field [0001] The invention belongs to the technical field of organic compounds and asymmetric organocatalytic synthesis, and in particular relates to a novel biaxial chiral organic phosphoric acid compound catalyst, a preparation method and an application thereof. Background technique [0002] With the development of medicine, pesticide and materials science research and industrial application, the demand for chiral compounds is increasing day by day, and the development of important chiral catalysts and asymmetric catalytic methods with high enantioselectivity has very important application value. The key to catalytic asymmetric synthesis of chiral compounds is chiral catalyst technology. The design and synthesis of new chiral catalysts and the research on asymmetric catalysis have aroused great interest of many scientists (Comprehensive Asymmetric Synthesis; Jacobsen, E.N.; Pfaltz, A.; Yamamoto, H., Eds.; Vols.I, II, III, Springer: Berlin, 1999.). In recent yea...

Claims

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Application Information

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IPC IPC(8): C07F9/09B01J31/24C07B53/00
Inventor 杜大明郭群胜许家喜
Owner PEKING UNIV
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