Abstract: The present invention relates to a preparation method for and an application of a chiral spirocyclic phosphine-nitrogen-phosphine tridentate ligand SpiroPNP and an iridium catalyst Ir-SpiroPNP thereof. The chiral spirocyclic phosphine-nitrogen-phosphine tridentate ligand is a compound represented by formula I, or a racemate or optical isomer thereof, or a catalytically acceptable salt thereof, and the main structural feature is a phosphine ligand having a chiral spiro indene skeleton and a large sterically hindered substituent. The chiral spirocyclic phosphine-nitrogen-phosphine tridentate ligand can be synthesized into a chiral starting material from a 7-diaryl/alkylphosphino-7?-amino-1,1?-spirodihydroindenyl compound having a spiro ring skeleton. The iridium catalyst of the chiral spirocyclic phosphino-7?-amino-1,1?-spirodihydroindenyl compound having a sprio ring skeleton.

Abstract: A method for determining an optimal arrangement of circular pipe supports of a steel silo composite shear wall, including: designing a set of steel silo composite shear wall model including parameters of interval of the circular pipe supports, axial-load ratio, steel ratio and aspect ratio: establishing an ABAQUS finite element model including initial defect; performing force analysis by the finite element software ABAQUS and calculating a horizontal ultimate bearing capacity; fitting formulas of the horizontal ultimate bearing capacity of the steel silo composite shear wall by applying least square method; drawing a relationship curve between the interval of the circular pipe supports and the horizontal ultimate bearing capacity; determining the optimal arrangement of the circular pipe supports of the steel silo composite shear wall according to a critical point of the relationship curve between the interval of the circular pipe supports and the horizontal ultimate bearing capacity.

Abstract: The present invention relates to kinetic resolution of racemic ?-hydroxyl ester via asymmetric catalytic hydrogenation and an application thereof. In the presence of chiral spiro pyridyl phosphine ligand Iridium catalyst and base, racemic ?-hydroxyl esters were subjected to asymmetric catalytic hydrogenation to obtain extent optical purity chiral ?-hydroxyl esters and corresponding 1,5-diols. An optically active chiral ?-hydroxyl ester and 1,5-diols can be obtained at very high enantioselectivity and yield with relatively low usage of catalyst. The chiral ?-hydroxyl ester and 1,5-diols obtained by using the method can be used as a critical raw material for asymmetric synthesis of chiral drugs (R)-lisofylline and natural drugs (+)-civet, (?)-indolizidine 167B and (?)-coniine.

Abstract: The present invention relates to a chiral spiro phosphine-nitrogen-sulfur (P—N—S) tridentate ligand, preparation method and application thereof. The P—N—S tridentate ligand is a compound represented by Formula I or Formula II, their racemates, optical isomers, or catalytically acceptable salts thereof. The ligand has a primary structure skeleton characterized as a chiral spiro indan skeleton structure with a thio group. The chiral spiro phosphine-nitrogen-sulfur tridentate ligand can be synthesized by reacting racemic or optical active compound 7-diary/alkyl phosphine-7?-amino-1, 1?-spiro-dihydro-indene compound having a spiro-dihydro-indene skeleton as the starting material. The chiral spiro P—N—S tridentate ligand being complex with transition metal salt can be used in an asymmetric catalytic hydrogenation reaction for catalyzing carbonyl compound.

Abstract: The present invention relates to a chiral spiro phosphine-nitrogen-sulfur (P—N—S) tridentate ligand, preparation method and application thereof. The P—N—S tridentate ligand is a compound represented by Formula I or Formula II, their racemates, optical isomers, or catalytically acceptable salts thereof. The ligand has a primary structure skeleton characterized as a chiral spiro indan skeleton structure with a thio group. The chiral spiro phosphine-nitrogen-sulfur tridentate ligand can be synthesized by reacting racemic or optical active compound 7-diary/alkyl phosphine-7?-amino-1,1?-spiro-dihydro-indene compound having a spiro-dihydro-indene skeleton as the starting material. The chiral spiro P—N—S tridentate ligand being complex with transition metal salt can be used in an asymmetric catalytic hydrogenation reaction for catalyzing carbonyl compound.

Abstract: The present invention relates to kinetic resolution of racemic ?-hydroxyl ester via asymmetric catalytic hydrogenation and an application thereof. In the presence of chiral spiro pyridyl phosphine ligand Iridium catalyst and base, racemic ?-hydroxyl esters were subjected to asymmetric catalytic hydrogenation to obtain extent optical purity chiral ?-hydroxyl esters and corresponding 1,5-diols. The method is a new, efficient, highly selective, economical, desirably operable and environmentally friendly method suitable for industrial production. An optically active chiral ?-hydroxyl ester and 1,5-diols can be obtained at very high enantioselectivity and yield with relatively low usage of catalyst. The chiral ?-hydroxyl ester and 1,5-diols obtained by using the method can be used as a critical raw material for asymmetric synthesis of chiral drugs (R)-lisofylline and natural drugs (+)-civet, (?)-indolizidine 167B and (?)-coniine.

Abstract: The present invention relates to a spirobenzylamine-phosphine, preparation method therefor and use thereof. The compound has a structure represented by formula (I), wherein n=0 to 3; R1, R2, R3, R4, R5, R6, R7, R8 and R9 having a value as defined in claim 1. Starting from the substituted 7-trifluoromesyloxy-7?-diarylphosphino-1,1?-spiro-dihydroindene, the compound is synthesized in a two-step or three-step reactions. The new spirobenzylamine-phosphine is complexed with an iridium precursor and is subjected to ion exchange, to give an Iridium/spirobenzylamine-phosphine complex comprising various anions. The spiro benzyl amine-phosphine/Iridium complex according to the present invention may be used for catalyzing asymmetry hydrogenation of a variety of alpha-substituted acrylic acids, has high activity and enantio-selectivity, and has a good prospect of industrialization.

Abstract: The present invention relates to a chiral spiro-pyridylamidophosphine ligand compound, synthesis method therefor and application thereof. The chiral spiro-pyridylamidophosphine compound is a compound having a structure of Formula (I), a racemate or optical isomer thereof, or a catalytically acceptable salt thereof, and is mainly characterized by having a chiral spiro-dihydro-indene skeleton in its structure. The chiral spiro-pyridylamidophosphine compound may be synthesized with optical active 7-diaryl/alkylphosphino-7?-amino-1,1?-spiro-dihydro-indene or substituted 7-diaryl/alkylphosphino-7?-amino-1,1?-spiro-dihydro-indene having a spiro-skeleton as chiral starting material. The chiral spiro-pyridylamidophosphine compound may be used as a chiral ligand in asymmetric hydrogenation of a carbonyl compound catalyzed by iridium, in which the reaction activity is very high, the amount of the catalyst may be 0.0001 mol %, and the enantioselectivity of the reaction is up to 99.9% ee.

Abstract: The present invention relates to a spirobenzylamine-phosphine, preparation method therefor and use thereof. The compound has a structure represented by formula (I), wherein n=0 to 3; R1, R2, R3, R4, R5, R6, R7, R8 and R9 having a value as defined in claim 1. Starting from the substituted 7-trifluoromesyloxy-7?-diarylphosphino-1,1?-spiro-dihydroindene, the compound is synthesized in a two-step or three-step reactions. The new spirobenzylamine-phosphine is complexed with an iridium precursor and is subjected to ion exchange, to give an Iridium/spirobenzylamine-phosphine complex comprising various anions. The spiro benzyl amine-phosphine/Iridium complex according to the present invention may be used for catalyzing asymmetry hydrogenation of a variety of alpha-substituted acrylic acids, has high activity and enantio-selectivity, and has a good prospect of industrialization.

Abstract: The present invention relates to a preparation method of carboxylic acids with optical activity, particularly, publishes that very useful chiral carboxylic acids can be obtained by the asymmetric catalytic hydrogenation of tri-substituted ?,?-unsaturated carboxylic acids, with the complexes of the chiral phosphor nitrogen ligands and iridium used as the catalysts which show high activity and enantioselectivity (up to 99.8% ee), thus provides a more efficient method with higher enantioselectivity for asymmetric catalytic hydrogenation of chiral carboxylic acid-like compounds, and has important application value to asymmetric hydrogenation of chiral carboxylic acids.

Abstract: The present invention relates to a chiral spiro-pyridylamidophosphine ligand compound, synthesis method therefor and application thereof. The chiral spiro-pyridylamidophosphine compound is a compound having a structure of Formula (I), a racemate or optical isomer thereof, or a catalytically acceptable salt thereof, and is mainly characterized by having a chiral spiro-dihydro-indene skeleton in its structure. The chiral spiro-pyridylamidophosphine compound may be synthesized with optical active 7-diaryl/alkylphosphino-7?-amino-1,1?-spiro-dihydro-indene or substituted 7-diaryl/alkylphosphino-7?-amino-1,1?-spiro-dihydro-indene having a spiro-skeleton as chiral starting material. The chiral spiro-pyridylamidophosphine compound may be used as a chiral ligand in asymmetric hydrogenation of a carbonyl compound catalyzed by iridium, in which the reaction activity is very high, the amount of the catalyst may be 0.0001 mol %, and the enantioselectivity of the reaction is up to 99.9% ee.

Abstract: The present invention belongs to a spiro phosphine-oxazoline and preparation method and application thereof, particularly, publishes a novel spiro phosphine-oxazoline and the preparation method of its iridium complex. The substituted 7-diaryl phosphino-7?-carboxy-1,1?-Lo-dihydro-indene is used as the starting raw material to synthesize the novel spiro phosphine-oxazoline of the present invention through a two-step reaction. The novel spiro phosphine-oxazoline and the iridium precursor are complexed to become a complex, and then through ion exchange, an iridium/phosphine spiro-oxazoline complex with different anions can be obtained. The present invention overcomes the shortcomings of the existing technology. The cheap readily available amino alcohol is used as the raw material to synthesize the novel spiro phosphine-oxazoline, on the fourth position of the oxazoline ring of which there is no substitutent.

Abstract: The present invention belongs to a spiro phosphine-oxazoline and preparation method and application thereof, particularly, publishes a novel spiro phosphine-oxazoline and the preparation method of its iridium complex. The substituted 7-diaryl phosphino-7?-carboxy-1,1?-Lo-dihydro-indene is used as the starting raw material to synthesize the novel spiro phosphine-oxazoline of the present invention through a two-step reaction. The novel spiro phosphine-oxazoline and the iridium precursor are complexed to become a complex, and then through ion exchange, an iridium/phosphine spiro-oxazoline complex with different anions can be obtained. The present invention overcomes the shortcomings of the existing technology. The cheap readily available amino alcohol is used as the raw material to synthesize the novel spiro phosphine-oxazoline, on the fourth position of the oxazoline ring of which there is no substitutent.

Abstract: The present invention relates to a preparation method of carboxylic acids with optical activity, particularly, publishes that very useful chiral carboxylic acids can be obtained by the asymmetric catalytic hydrogenation of tri-substituted ?,?-unsaturated carboxylic acids, with the complexes of the chiral phosphor nitrogen ligands and iridium used as the catalysts which show high activity and enantioselectivity (up to 99.8% ee), thus provides a more efficient method with higher enantioselectivity for asymmetric catalytic hydrogenation of chiral carboxylic acid-like compounds, and has important application value to asymmetric hydrogenation of chiral carboxylic acids.