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Catalyst for asymmetric synthesis, ligand used therefor and method for producing optically active compound by asymmetric synthetic reaction using the same

An optically active and compound technology, applied in asymmetric synthesis, catalytic reaction, organic chemical methods, etc., can solve the problems of poor selectivity and low yield of optically active aryl compounds

Inactive Publication Date: 2008-02-13
JAPAN SCI & TECH CORP
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

In 5), there are problems of low yield of optically active aryl compounds and poor selectivity

Method used

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  • Catalyst for asymmetric synthesis, ligand used therefor and method for producing optically active compound by asymmetric synthetic reaction using the same
  • Catalyst for asymmetric synthesis, ligand used therefor and method for producing optically active compound by asymmetric synthetic reaction using the same
  • Catalyst for asymmetric synthesis, ligand used therefor and method for producing optically active compound by asymmetric synthetic reaction using the same

Examples

Experimental program
Comparison scheme
Effect test

reference example 1

[0251] Synthesis of compounds 1-7

[0252] The synthetic schemes of compounds 1-7 are as described above.

[0253] Synthesis of compound 2

[0254] Into a 500ml round bottom flask was added NaH (60%, dispersed in mineral oil) (250mmol). The flask was filled with argon, then the compound was washed 2-3 times with THF. THF (100ml) was added and (R,R)-1,1'-binaphthol (50mmol) dissolved in THF (125ml) was added. After the mixture was stirred at 0°C for 1 hour, a solution of chloromethyl ether (125ml) in THF (30ml) was added dropwise. The mixture was then stirred at room temperature for 3 hours. Methanol and water were added, and the mixture was extracted 3 times with diethyl ether. The organic layer was washed with saturated aqueous sodium carbonate and saturated brine, and then dried over anhydrous sodium sulfate. After evaporation of the solvent, the residue was recrystallized from dichloromethane / pentane (92% yield).

[0255] Synthesis of compound 3

[0256] In a 2...

Embodiment 1

[0266] The synthetic method of compound 8, 9

[0267] Ammonium chloride (0.01 g) and compound 7 (1 mmol) were added to a 30 ml flask. The mixture was dissolved in toluene (10 ml), and hexamethylphosphoric triamide was added, followed by heating under reflux for 12 hours.

[0268] After cooling the mixture to room temperature, the solvent was distilled off. The residue was recrystallized from dichloromethane / pentane (75% yield, R=Me).

[0269] Structural formula and spectral data of R=Me (Compound 8)

[0270] Linked-pbosphoramidaite from(R)-BINOL C 46 h 38 N 2 o 5 P 2 Mol.Wt.: 761

[0271]

[0272] 1 H-NMR (CD 2 Cl 2 )δ=2.23-2.39(m, 12H), 4.82(d, J=13.3Hz, 2H), 5.02(d, J=13.3Hz, 2H), 7.07-7.39(m, 14H), 7.76-7.86(m , 6H), 8.15(s, 2H) 31 P-NMR (CD 2 Cl 2 )δ=150.8ppm MS (FAB), m / z (%): 43 (33), 266 (28), 282 (50), 329 (100), 373 (29), 388 (24), 716 (28) , 761 (M+H, 19) HRMS (FAB) calcd for C46H39N2O5P2 761.2334, found 761.2334

[0273] Structural formula and sp...

Embodiment 2

[0277] The synthetic method of compound 10

[0278] Add toluene (3ml), PCl 3 (2mmol), NEt 3 (4 mmol), the mixture was cooled to -60°C, a toluene solution of compound 7 was added dropwise, and the mixture was stirred for 2 hours. The mixture was warmed to room temperature, and the resulting salts were filtered off. The filtrate was cooled to -40°C, n-butyl lithium (2 mmol), diisopropylamine (3 mmol) were added, the mixture was warmed to room temperature and then stirred for 16 hours. After distilling off the solvent, the residue was recrystallized from dichloromethane / pentane to give compound 10.

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Abstract

Compounds of the following general formula (1a) or (1b). (1a) (1b) Further, there are provided a complex comprising a central metal of rhodium and any of compounds of the general formula (1a) or (1b) as a ligand; comprised of this complex, a catalyst for optically active ss-substituted carbonyl compound synthesis and catalyst for asymmetric 1,2 addition reaction; using these catalysts, a process for producing an optically active ss-aryl compound from an a,ss-unsaturated compound and an arylboronic acid derivative and process for producing an optically active aryl alcohol compound from an aldehyde compound and an aryl boronic acid derivative; a complex comprising a central metal of palladium and any of compounds of the general formula (1a) or (1b) as a ligand; comprised of this complex, a catalyst for asymmetric allyl-position substitution reaction; and using this catalyst, a process for producing an optically active dialkyl (1,3-disubstituted propenyl)malonate compound from a 1,3-disubstituted allyl acetate compound and a dialkyl malonate and process for producing an optically active allylamine compound from a 1,3-disubstituted allyl acetate compound and an amine compound. The compounds have not only the versatility of being usable in the synthesis of wide-ranging optically active aryl compounds but also the selectivity and reactivity permitting synthesis with high yield within a short period of time under industrially advantageous mild conditions.

Description

technical field [0001] The present invention relates to a catalyst for asymmetric synthesis, a ligand used therein, and a method for producing an optically active compound by an asymmetric synthesis reaction using the catalyst and the ligand. More specifically, the production method of an optically active compound relates to a production method of an optically active β-substituted carbonyl compound, a production method of an optically active alcohol compound, and an allylic substitution reaction. Background technique [0002] Optically active β-substituted carbonyl compounds are used as intermediates in the fields of medicine and food additives. Examples of known methods for producing optically active β-substituted carbonyl compounds are given below. [0003] 1) The following document reports a method for producing a linear or cyclic β-substituted carbonyl compound by reacting an arylboronic acid with an α,β-unsaturated ketene in the presence of a rhodium compound, a phosph...

Claims

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Application Information

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IPC IPC(8): C07F9/6574B01J31/22C07B53/00C07C29/44C07C33/34C07C33/44C07C45/70C07C47/228C07C49/213C07C49/563C07C49/657C07C49/76C07C67/24C07C67/343C07C69/612C07C69/618C07C209/16C07C211/28C07F15/00
CPCC07C29/38B01J2531/827C07C231/12C07F15/0073B01J31/186B01J2531/0266C07F15/0066B01J31/185B01J2231/344B01J2231/348C07C67/343C07B2200/07C07C45/69B01J2231/44C07F15/008C07C209/16C07F9/657154B01J2531/822C07B53/00B01J2531/821C07C69/618C07C211/28C07C233/11C07C33/34
Inventor 宫浦宪夫山本靖典
Owner JAPAN SCI & TECH CORP
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