32results about How to "Pure high enantiomeric excess" patented technology

The invention relates to a method for synthesizing chiral dihydro-5H-pyrrolo[2,1-c][1,4]-benzodiazepino-5-one by iridium-catalyzed asymmetric hydrogenation. The reaction conditions are as follows: the temperature is 20-50 DEG C; the solvent is a dichloromethane-toluene mixed solvent (V / V=1:2); the pressure is 13-50 atmospheric pressures; the ratio of the substrate to the catalyst is 50 / 1; the catalyst is a complex of (1,5-cyclooctadiene)iridium chloride dimer and diphosphine ligand; and the additive is morpholine trifluoroacetate or piperidine hydrochloride. Seven-element cyclic pyrrolo[2,1-c][1,4]-benzodiazepino-5-one is hydrogenated to obtain the corresponding chiral dihydro product, and the enantiomeric excess can reach 96%. The invention is simple and practical to operate, and has the advantages of accessible raw materials, favorable selectivity for antipode, high yield, atomic economical efficiency for reaction, and environment friendliness.

The invention provides a method for synthesizing chiral amine. Catalyzed pyrrole / indol [1,2-a] quinoxaline is prepared through asymmetric hydrogenation reaction, a catalyst is the complex of a metal precursor and chiral bisphosphine ligand of iridium, reaction activity and enantioselectivity are high, two kinds of hydrogenation products, i.e., an in situ protected hydrogenation product and a direct hydrogenation product, can be respectively or simultaneously obtained through regulating and controlling the added quantity and reaction time of acetic anhydride, a corresponding chiral tertiary amine compound is obtained, one or two kinds of high enantiomeric excess pure products can be obtained, and the enantiomeric excess of the pure products can be up to 97% at most. The method is simple, convenient, practical and easy in operation, high in yield and friendly to the environment, the catalyst can be commercially obtained, the reaction conditions are mild, and therefore, the method has a potential practical application value.

The invention discloses a method for synthesizing chiral tertiary amine by asymmetric hydrogenation of a 9-amide phenanthrene compound under catalysis of a ruthenium-diphosphine ligand. The method includes: adopting 2-5mol% of a ruthenium catalyst, and adding 4-10mol% of fluoboric acid for asymmetric hydrogenation of the 9-amide phenanthrene compound to obtain a corresponding chiral tertiary aminecompound, wherein the enantiomeric excess reaches 98%. The method is simple, convenient, practical and feasible in operation, high in yield, environmentally friendly and mild in reaction condition, the catalyst is commercially acquirable, and a potential practical application value is achieved.

Disclosed is a method for asymmetric hydrogenation of isoquinoline by activation of a halogen bond. A catalytic system used by the method is a chiral diphosphine complex of iridium, and an activator is halides. An reaction can be carried out under the following conditions: the temperature is 25-100 DEG C, a solvent is tetrahydrofuran, the pressure is 13-100 atmospheres, a ratio of a substrate to acatalyst is 50 / 1, and the catalyst is a complex of (1,5-cyclooctadiene) iridium chloride dimer and a bisphosphine ligand. The isoquinoline is hydrogenated to obtain corresponding chiral tetrahydroisoquinoline derivatives, and an enantiometric excess can reach 99%. The method has the advantages of simple and practical operation, easy availability of raw materials, high enantioselectivity and goodyield, and the reaction has the advantages of green atom economy, environmental friendliness and the like.

The invention discloses a method for synthesizing chiral fluoroamine by palladium catalytic asymmetric hydrogenation, wherein, the used catalysis system comprises a palladium chiral diphosphite complex. The reaction is carried out under the following conditions that: the temperature is 0-50 DEG C, the solvent is a 2,2,2-trifluoroethyl alcohol, the pressure is 1-42 atm, the ratio of the substrate to the catalyst is 50 : 1, the used metal precursor is palladium trifluoroacetate, the used chiral ligand is a chiral diphosphite ligand. The catalyst is prepared by stirring the palladium metal precursor and the chiral diphosphite ligand in acetone at room temperature, and then carrying out vacuum condensation. According to the invention, by the hydrogenation of imine containing trifluoromethyl, corresponding chiral amine containing trifluoromethyl is obtained, the enantiomeric excess can reach to 94 %; by the hydrogenation of imine containing perfluoroalkyl, corresponding chiral amine containing perfluoroalkyl is obtained, and the enantiomeric excess can reach to 86 %. The present invention has the advantages of simple and practical operation, high enantioselectivitiy, good yield, green atom economy of the reaction, and no environmental pollution.

A method for synthesizing chiral exocyclic amine by iridium-catalyzed asymmetric hydrogenation of quinoline-3-amine, the catalytic system used is chiral diphosphorus complex of iridium. The reaction can be carried out under the following conditions, temperature: 25-70°C; solvent: a mixed solvent of toluene / tetrahydrofuran (V / V=3:1); pressure: 2-14 atmospheres; the ratio of substrate to catalyst is 25 / l; The catalyst is a complex of (1,5-cyclooctadiene) iridium chloride dimer and a chiral bisphosphine ligand. For quinoline-3-amine, the corresponding chiral exocyclic amine derivative can be obtained, and its enantiomeric excess value can reach 94%. The invention has the advantages of simple and practical operation, readily available raw materials, high enantioselectivity and good yield, and the reaction has green atom economy and is environmentally friendly.

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.

The invention discloses a palladium-catalyzed asymmetric intramolecular reductive amination method for synthesizing chiral sulfonamides. The catalytic system used is palladium chiral bisphosphine complexes. Reductive amination of a simple and readily available ketoamine substrate yields the corresponding chiral sulfonamide with an enantiomeric excess of 99%. The invention is simple and practical in operation, easy to obtain raw materials, commercially available catalyst, and mild reaction conditions. In addition, chiral sulfonamides were synthesized by asymmetric reductive amination with high enantioselectivity, good yield and environmental friendliness.

The application of chiral organic bases in the preparation of chiral sulfur-containing indole compounds in the water-oil two-phase system is a small molecule of chiral organic bases in the water-oil two-phase system to catalyze the asymmetric vulcanization of mercaptans to indole, The catalyst used is a small molecule chiral organic base. The corresponding chiral indole sulfide can be obtained after sulfiding the vinylene imine intermediate generated by the racemic p-toluenesulfonyl indole under alkaline conditions, and the yield can reach 99%. The enantiomeric excess can reach 98%. The invention is simple, practical and easy to operate, the catalyst is commercially available, water is used as the solvent, the reaction condition is green and mild, the yield is high, the enantioselectivity is good, and the reaction is carried out in the water phase, which is environmentally friendly. In addition, the synthesis of chiral indole sulfide and derivatized indoline sulfide through asymmetric sulfidation have potential medical value.

The invention discloses a method for synthesizing chiral benzosultam via palladium-catalytic asymmetric hydrogenation, comprising the following reaction conditions that: the temperature is 25-70DEG C; a solvent is 2,2,2-trifluoroethanol; the pressure is 28-40atm; the proportion of a substrate to a catalyst is 50 / 1; the catalyst is a complex of palladium trifluoroacetate and diphosphine ligand; the benzo six-membered ring shaped sulfonyl enamine of the benzo is hydrogenated to obtain the corresponding chiral benzo six-membered sultam with an enantiomeric excess up to 98%; and the benzo five-membered ring shaped sulfonyl enamine is hydrogenated to obtain the corresponding chiral benzo five-membered sultam with an enantiomeric excess up to 94%. The method disclosed by the invention is simple, convenient and practical for operation, high in enantioselectivity, good in yield and environmentally friendly, and has green atom economy for the reaction.

The invention discloses a method using palladium to catalyze asymmetrical hydrogen to compound into chiral gamma-sultam, wherein, a catalytic system used by the invention is a chiral diphosphine complex of palladium. The reaction can be made within the following conditions: temperature: 25 to 75 DEG C; solvent: 2, 2, 2-trifluoroethanol; pressure: 35 to 40 atmospheric pressures; time: 10 to 12 hours. The proportion of substrate and catalyst is 50:1, a metal precursor of the catalyst is palladium trifluoroacetate; a chiral ligand is a chiral diphosphine ligand; the preparation method for the catalyst is that: the metal precursor of the palladium and the chiral diphosphine ligand are stirred in acetone at room temperature, and then are made a vacuum condensation to obtain the catalyst. To hydrogenise cyclic sulfimide can obtain corresponding chiral 3-substituted gamma-sultam, and enantiomeric excess thereof can reach 93 percent. The method has simple and practical operation, easy-obtaining raw materials, high enantioselectivity and good yield; the reaction has green atomic economy and is environment-friendly.

The invention discloses a method for synthesizing chiral tertiary amine by asymmetric hydrogenation of 9-amidophenanthrene compound catalyzed by ruthenium-bisphosphine ligand. Using 2-5mol% ruthenium catalyst, adding 4-10mol% fluoboric acid, asymmetric hydrogenation of 9-amide phenanthrene compound to obtain the corresponding chiral tertiary amine compound, and its enantiomeric excess can reach 98%. The invention has the advantages of simple and practical operation, high yield, environmental friendliness, commercially available catalyst, mild reaction conditions and potential practical application value.

The invention relates to a nitrogen-doped rhodium carbon catalyst as well as a preparation method and application thereof. The preparation method of the nitrogen-doped rhodium carbon catalyst comprises the following steps: mixing active carbon, a nitrogen-containing compound and a first solvent, and carrying out a reflux reaction to prepare nitrogen-doped active carbon; in the nitrogen-doped activated carbon, N atoms in the nitrogen-containing compound being connected with C atoms in the activated carbon in a chemical nitrogen form; mixing the nitrogen-doped activated carbon, rhodium salt and a second solvent, and carrying out dipping treatment to prepare a catalyst precursor; and carrying out reduction reaction and alkali treatment on the catalyst precursor to prepare the nitrogen-doped rhodium carbon catalyst. The nitrogen-doped rhodium-carbon catalyst prepared by the preparation method can catalyze hydrogenation reaction at high yield and high selectivity to prepare chiral compounds, and is suitable for industrial production and application.

A method for palladium-catalyzed asymmetric hydrogenation of quinoline-3-amine to synthesize chiral exocyclic amines is characterized in that Bronsted acid is used as an activator, and the catalytic system used is a chiral bisphosphine complex of palladium. Reaction can be carried out under following conditions, reaction temperature: 60-80 ℃; Reaction adopts solvent: methylene chloride; Hydrogen pressure: 20-70 atmospheric pressure; The molar ratio of substrate and catalyst is 20 / l; Used metal precursor : palladium trifluoroacetate (Pd(OCOCF3)2); chiral ligand used: chiral bisphosphine ligand; activator used: trifluoroacetic acid (CF3CO2H). For quinoline-3-amine, the corresponding chiral exocyclic amine derivative can be obtained, and its enantiomeric excess value can reach 90%. The invention has the advantages of simple and convenient operation, readily available raw materials, good enantioselectivity, high yield, and the reaction has green atom economy and is environmentally friendly.

The method for synthesizing chiral fluorine-containing propargylamine derivatives by biomimetic catalysis asymmetric hydrogenation uses ruthenium and chiral phosphoric acid as the catalytic system. Reaction can be carried out in following conditions, temperature: 25-100 ℃; Solvent: 1,2-ethylene dichloride; Pressure: 13-80 atmospheric pressure; The ratio of substrate and catalyst is 100 / l; Catalyst is (4- cymene) ruthenium iodide dimer and chiral phosphoric acid. The selective hydrogenation of fluorine-containing alkynyl-substituted imines affords the corresponding chiral fluorine-containing propylamine derivatives with an enantiomeric excess of up to 98%. The invention has the advantages of simple and practical operation, readily available raw materials, high enantioselectivity, good yield, and the reaction has the advantages of green atom economy and environmental friendliness.

An iridium-catalyzed two-way enantioselective synthesis method of chiral tetrahydroisoquinoline, the catalyst system used is a chiral bisphosphine complex of iridium. Using a single chiral source, the asymmetric hydrogenation of simple and easy-to-obtain 3,4-dihydroisoquinoline substrates was realized by adjusting the amount of achiral additive N-bromosuccinimide in the reaction system . The method utilizes a single chiral source to obtain two enantiomers of the corresponding chiral tetrahydroisoquinoline respectively, and the enantiomeric excess can reach 89% (S) and 98% (R), respectively. The invention is simple and practical in operation, simple and easy to obtain raw materials, commercially available catalyst, mild reaction conditions, high yield and high enantioselectivity. In addition, the two enantiomers of tetrahydroisoquinoline can be obtained only through the conditions of achiral additives, successfully avoiding the synthesis of two different configuration ligands.

The invention provides a method for synthesizing chiral amine. Catalyzed pyrrole / indol [1,2-a] quinoxaline is prepared through asymmetric hydrogenation reaction, a catalyst is the complex of a metal precursor and chiral bisphosphine ligand of iridium, reaction activity and enantioselectivity are high, two kinds of hydrogenation products, i.e., an in situ protected hydrogenation product and a direct hydrogenation product, can be respectively or simultaneously obtained through regulating and controlling the added quantity and reaction time of acetic anhydride, a corresponding chiral tertiary amine compound is obtained, one or two kinds of high enantiomeric excess pure products can be obtained, and the enantiomeric excess of the pure products can be up to 97% at most. The method is simple, convenient, practical and easy in operation, high in yield and friendly to the environment, the catalyst can be commercially obtained, the reaction conditions are mild, and therefore, the method has a potential practical application value.

A method for synthesizing chiral 3-trifluoromethyl-3,4-dihydroquinoxalinone by palladium-catalyzed asymmetric hydrogenation, the catalytic system is a chiral bisphosphorus complex of palladium, and the reaction conditions are: temperature: 0- 80°C; solvent: 2,2,2-trifluoroethanol or hexafluoroisopropanol; pressure: 100-1000psi; ratio of substrate to catalyst is 33 / l; metal precursor used: palladium trifluoroacetate; The chiral ligand used: chiral diphosphorus ligand; the preparation method of the catalyst is: stirring the metal precursor of palladium and the chiral diphosphorus ligand in acetone at room temperature, and then vacuum concentrating to obtain the catalyst. The hydrogenation of trifluoromethyl-containing quinoxalinone can give the corresponding chiral trifluoromethyl-containing dihydroquinoxalinone, and its enantiomeric excess can reach 99%. 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.

The invention discloses a palladium-catalyzed asymmetric hydrogenolysis and racemization-substituted oxaziridine method for synthesizing chiral sulfonamides. The catalytic system used in the method is palladium chiral bisphosphine complexes. Hydrogenolysis of racemic substituted oxaziridines can afford the corresponding chiral sulfonamides with an enantiomeric excess of 99%. The invention is simple and practical to operate, the catalyst is commercially available, and the reaction conditions are mild. In addition, the synthesis of chiral sulfonamides by asymmetric hydrogenolysis has high enantioselectivity and good yield, and the reaction is environmentally friendly with green atom economy.

A method for synthesis of chiral piperidine derivatives through iridium-catalyzed asymmetric hydrogenation of pyridine employs a catalytic system of chiral diphosphine complex of iridium. The reaction can be carried out under the following conditions: temperature of 25-60 DEG C; a mixed solvent of toluene / dichloromethane (V / V=1:1); pressure of 13-50 barometric pressure; a ratio of substrate and catalyst of 50 / 1; and a catalyst of a complex of (1,5-cyclo-octadiene) iridium chloride dimer and diphosphine ligand. Hydrogenation of pyridine salt can obtain a corresponding chiral 2-substituted piperidine derivative, whose enantiomeric excess can reach 93%. The invention has advantages of simple and practical operation, easily available raw materials, high enantioselectivity, and good yield; in addition, the reaction has green atom economy and is friendly to environment.