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A kind of method for synthesizing chiral amine by asymmetric hydrogenolysis of palladium-catalyzed amino alcohol

A technology that catalyzes aminoalcohols and asymmetries. It is applied in the preparation of amino compounds, chemical instruments and methods, and the preparation of organic compounds. It achieves the effects of mild conditions, high reactivity and enantioselectivity, and chiral value-added.

Active Publication Date: 2017-01-18
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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Problems solved by technology

But in the actual process, the products obtained by hydrogenolysis are often racemic, and few asymmetric hydrogenolysis reactions have been reported (Reference 3: (a) Chan, A.S.C.; Coleman, J.P.J. Chem. Soc., Chem. Commun.1991,535.(b)Bakos,J.;Orosz,A.;Cserépi,S.;Tóth,I.;Sinou,D.J.Mol.Catal.A:Chem.1997,116,85.(c)( a) Kündig, E.P.; Chaudhuri, P.D.; House, D.; Bernardinelli, G. Angew. Chem. Int. Ed. 2006, 45, 1092. (d) Mercier, A.; Yeo, W.C.; Y.; Chaudhuri, P.D.; Bernardinelli, G.; Kündig, E.P. Chem. Commun. 2009, 5227. (e) Mercier, A.; Urbaneja, X.; Yeo, W.C.; D.; Bernardinelli, G.; Kündig, E.P. Chem. Eur. J. 2010, 16, 6285. (f) Mercier, A.; Yeo, W.C.; Urbaneja, X.; g) Chen, M.-W.; Chen, Q.-A.; Duan, Y.; Ye, Z.-S.; Zhou, Y.-G. Chem.Commun.2012, 1698.)

Method used

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  • A kind of method for synthesizing chiral amine by asymmetric hydrogenolysis of palladium-catalyzed amino alcohol
  • A kind of method for synthesizing chiral amine by asymmetric hydrogenolysis of palladium-catalyzed amino alcohol
  • A kind of method for synthesizing chiral amine by asymmetric hydrogenolysis of palladium-catalyzed amino alcohol

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Experimental program
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Effect test

Embodiment 1

[0027] Embodiment 1: optimization of conditions

[0028] Put palladium trifluoroacetate (0.0025 mmol, 0.9 mg) and chiral ligand (0.003 mmol) into the reaction bottle, add 1 ml of acetone after nitrogen replacement, and stir at room temperature for 1 hour. Then concentrate in vacuo, add 2.5 ml 2,2,2-trifluoroethanol under nitrogen, transfer this solution to the reaction kettle with substrate 1a (45 mg, 0.125 mmol) in advance, and pass hydrogen gas for 28 or 40 Atmospheric pressure, reaction at 70°C for 15 hours. Slowly release hydrogen, remove the solvent, and directly separate the pure product by column chromatography. The reaction formula and ligand structure are as follows:

[0029]

[0030] The conversion rate was determined by proton nuclear magnetic resonance spectroscopy, and the enantiomeric excess of the product was determined by chiral liquid chromatography, as shown in Table 1.

[0031] Table 1. Asymmetric hydrogenolysis of N-sulfonylamino alcohols 1a

[0032] ...

Embodiment 2

[0034] Example 2: Synthesis of various chiral benzamines by palladium-catalyzed asymmetric hydrogenolysis 2

[0035] Palladium trifluoroacetate (0.9 mg, 0.0025 mmol) and (R)-DifluorPhos (2.1 mg, 0.003 mmol) or (1R,1′R,2S,2′S)-DuanPhos (1.1 mg , 0.003 mmol), and after nitrogen replacement, 1 ml of acetone was added, and stirred at room temperature for 0.75-1.5 hours. Then concentrate in vacuo, add 3.0 ml of a mixed solvent of 2,2,2-trifluoroethanol and dichloromethane (3:1) under nitrogen, and transfer this solution to a reaction kettle with substrate (0.125 mmol) in advance , feed hydrogen to 28 atmospheres, react at 60 degrees for 15-70 hours, and release hydrogen slowly. After removing solvent, direct column chromatography separates and obtains pure product, and reaction formula is as follows:

[0036]

[0037] The enantiomeric excess of the product was determined by chiral liquid chromatography, see Table 2.

[0038] Table 2. Palladium-catalyzed asymmetric hydrogenati...

Embodiment 3

[0041] Example 3: Palladium-catalyzed asymmetric hydrogenolysis of benzo six-membered ring N-sulfonylamino alcohol 1j.

[0042] Palladium trifluoroacetate (0.9 mg, 0.0025 mmol) and (R)-DifluorPhos (2.1 mg, 0.003 mmol) or (1R,1′R,2S,2′S)-DuanPhos (1.1 mg , 0.003 mmol), and after nitrogen replacement, 1 ml of acetone was added, and stirred at room temperature for 0.75-1.5 hours. Then concentrate in vacuo, add 3.0 ml of a mixed solvent of 2,2,2-trifluoroethanol and dichloromethane (3:1) under nitrogen, and transfer this solution to a reaction kettle with substrate (0.125 mmol) in advance , feed hydrogen to 28 atmospheres, react at 60 degrees for about 60 hours, and release hydrogen slowly. After removing solvent, direct column chromatography separates and obtains pure product, and reaction formula is as follows:

[0043]

[0044] The enantiomeric excess of the product was determined by chiral liquid chromatography.

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Abstract

A method for palladium-catalyzed asymmetric hydrogenolysis of N-sulfonyl amino alcohol compounds, the reaction conditions are as follows, temperature: 25-70 degrees; solvent: 2,2,2-trifluoroethanol / dichloromethane; pressure: 28-40 Atmospheric pressure; The ratio of substrate and catalyst is 50 / l; The catalyst is the complex of palladium trifluoroacetate and bisphosphorus ligand; The hydrogenolysis of the five-membered ring N-sulfonyl amino alcohol of p-benzo obtains the corresponding chiral The enantiomeric excess of benzopenta-membered N-sulfonyl amino compounds can reach 94%. The invention has the advantages of simple and practical operation, high enantioselectivity and good yield, and the reaction has green atom economy and is friendly to the environment.

Description

technical field [0001] The invention relates to cyclic sulfonamide compounds, in particular to a palladium-catalyzed asymmetric hydrogenolysis method for N-sulfonylaminoalcohol compounds with high enantioselectivity and stereoconvergence in a palladium homogeneous system. Background technique [0002] In organic synthesis, hydrogenolysis reaction is an important synthetic method, and has been widely used in industrial processes (document 1: (a) Speight, J.G. The Desulfurization of Heavy Oil and Residua, 2nd ed.; Marcel Dekker: New York, 2000. (b) Chianelli, R.R. Catal. Rev. 1984, 26, 361. (c) Poutsma, M. L. Energy Fuels 1990, 4, 113. (d) Startsev, A. N. Russ. Chem. Rev. 1992, 61, 175. (e) Ichimura, K. ; Inoue, Y.; Yasmumori, I.Catal.Rev.1992,34,301.), in the synthesis of natural products (document 2: (a) Clive, D.L.J.; Wang, J.J.Org.Chem.2004, 69, 2773.(b ) Crich, D.; Cai, F. Org. Lett. 2007, 9, 1613. (c) Tamaki, M.; Han, G.-X.; Hruby, V. J. J. Org. Chem. 2001, 66, 3593.) ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C303/40C07C311/20C07C211/42C07C209/62
Inventor 周永贵余长斌时磊
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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