The present invention is directed to a crystalline salt of 5-methyl-(6S)-tetrahydrofolic acid and L-isoleucine ethyl ester wherein the molar ratio of 5-methyl-(6S)-tetrahydrofolic acid to L-isoleucine ethyl ester is from 1:0.3 to 1:2.0 (in mol/mol) and/or hydrates and/or solvates thereof, as well as, a process of obtaining the same.
C07D 475/04 - Composés hétérocycliques contenant des systèmes cycliques ptéridine avec un atome d'oxygène lié directement en position 4 avec un atome d'azote lié directement en position 2
C07C 229/08 - Composés contenant des groupes amino et carboxyle liés au même squelette carboné ayant des groupes amino et carboxyle liés à des atomes de carbone acycliques du même squelette carboné le squelette carboné étant acyclique et saturé ayant un seul groupe amino et un seul groupe carboxyle liés au squelette carboné l'atome d'azote du groupe amino étant lié de plus à des atomes d'hydrogène
2.
Production of N-substituted aromatic hydroxylamine
with hydrogen, by catalytic hydration with possibly modified hydration catalysts in an aprotic solvent and in the presence of a halogen formic acid ester and in some cases in the presence of a base.
C07D 231/22 - Un atome d'oxygène lié en position 3 ou 5 avec des radicaux aryle liés aux atomes d'azote du cycle
C07C 269/00 - Préparation de dérivés d'acide carbamique, c.-à-d. de composés contenant l'un des groupes l'atome d'azote ne faisant pas partie de groupes nitro ou nitroso
C07D 257/06 - Cycles à cinq chaînons avec des atomes d'azote liés directement à l'atome de carbone du cycle
3.
PRODUCTION OF N-SUBSTITUTED AROMATIC HYDROXYLAMINE
The invention relates to an economical, single-stage method for producing n-substituted aromatic hydroxylamine of formula (I) R-N(OH)-C(=O)-(O) R1 (I), using hydrogen, by catalytic hydrogenation using optionally modified hydrogenation catalysts, in an aprotic solvent and in the presence of a halogenated formic acid ester and, optionally, in the presence of a base.
C07C 269/00 - Préparation de dérivés d'acide carbamique, c.-à-d. de composés contenant l'un des groupes l'atome d'azote ne faisant pas partie de groupes nitro ou nitroso
C07C 271/28 - Esters des acides carbamiques ayant des atomes d'oxygène de groupes carbamate liés à des atomes de carbone acycliques avec l'atome d'azote d'au moins un des groupes carbamate lié à un atome de carbone d'un cycle aromatique à six chaînons à un atome de carbone d'un cycle aromatique à six chaînons non condensé
C07D 231/22 - Un atome d'oxygène lié en position 3 ou 5 avec des radicaux aryle liés aux atomes d'azote du cycle
4.
PRODUCTION OF N-SUBSTITUTED AROMATIC HYDROXYLAMINE
The invention relates to an economical, single-stage method for producing n-substituted aromatic hydroxylamine of formula (I) R-N(OH)-C(=O)-(O) R1 (I), using hydrogen, by catalytic hydrogenation using optionally modified hydrogenation catalysts, in an aprotic solvent and in the presence of a halogenated formic acid ester and, optionally, in the presence of a base.
C07C 269/00 - Préparation de dérivés d'acide carbamique, c.-à-d. de composés contenant l'un des groupes l'atome d'azote ne faisant pas partie de groupes nitro ou nitroso
C07C 271/28 - Esters des acides carbamiques ayant des atomes d'oxygène de groupes carbamate liés à des atomes de carbone acycliques avec l'atome d'azote d'au moins un des groupes carbamate lié à un atome de carbone d'un cycle aromatique à six chaînons à un atome de carbone d'un cycle aromatique à six chaînons non condensé
C07D 231/22 - Un atome d'oxygène lié en position 3 ou 5 avec des radicaux aryle liés aux atomes d'azote du cycle
42 - Services scientifiques, technologiques et industriels, recherche et conception
Produits et services
Scientific research and development; chemical laboratory
services, particularly chemical syntheses; preparation of
scientific reports; services provided by consultants,
analysis, expert reports and studies, particularly in the
fields of chemistry, biochemistry, biology, biotechnology,
pharmacy and cosmetics; laboratory analyses in the fields of
medicine, cosmetics and medical products.
42 - Services scientifiques, technologiques et industriels, recherche et conception
Produits et services
(1) Scientific research and development, synthesis, consultancy, analysis, preparation of scientific reports as well as studies, in particular in the field of chemistry, biochemistry, biology, biotechnology, pharmacy and cosmetics, testing pharmaceutical products, medical products and cosmetics.
42 - Services scientifiques, technologiques et industriels, recherche et conception
Produits et services
(1) Scientific research and development, synthesis, consultancy, analysis, preparation of scientific reports as well as studies, in particular in the field of chemistry, biochemistry, biology, biotechnology, pharmacy and cosmetics, testing pharmaceutical products, medical products and cosmetics.
42 - Services scientifiques, technologiques et industriels, recherche et conception
Produits et services
Scientific research and development; chemical laboratory services, namely, chemical engineering and chemical laboratories for the purposes of providing chemical syntheses; preparation of scientific reports, namely, providing research in the field of chemistry and providing scientific research and development services; services provided by consultants, analysis, expert reports and studies, namely, providing scientific feasibility studies and providing technical consulting services, particularly in the fields of chemistry, biochemistry, biology, biotechnology, pharmacy and cosmetics; laboratory analyses in the fields of medicine, cosmetics and medical products
9.
Bidentate chiral ligands for use in catalytic asymmetric addition reactions
C07D 333/26 - Composés hétérocycliques contenant des cycles à cinq chaînons comportant un atome de soufre comme unique hétéro-atome du cycle non condensés avec d'autres cycles non substitués sur l'atome de soufre du cycle avec des hétéro-atomes ou avec des atomes de carbone comportant trois liaisons à des hétéro-atomes, avec au plus une liaison à un halogène, p. ex. radicaux ester ou nitrile, liés directement aux atomes de carbone du cycle
Chiral compounds of the formula (1 ), which are optically pure or highly optically enriched in which R0 is C1-C12-alkyl which is unsubstituted or substituted by 1 to 2 C1-C4-alkoxy; cyclo- pentyl or cyclohexyl, which is unsubstituted or substituted by 1 to 3 C1-C4-alkyl or C1-C4-alkoxy; or benzyl, phenyl or naphtyl which is unsubstituted or substituted by 1 to 3 C1-C4-alkyl, C1-C4-alkoxy, C1-C4-fluoroalkyl or C1-C4-fluoroalkoxy, F or Cl, or R0 is -C R5 R6 OH or -C R5 R6 OSi(C1-C8-alkyl)3 wherein R5 and R6 are indedendently selected from the group consisting of H, unsubstituted C1 - C12 alkyl, substituted C1 - C12 alkyl, unsubstituted C4 - C8 cyclo alkyl, substituted C4 - C8 cyclo alkyl, unsubstituted aryl, substituted aryl or wherein R5 and R6 can form an unsubstituted 5-6 membered aliphatic carbocycle or a substituted 5-6 membered aliphatic carbocycle, each of R1 and R'1 independently is hydrogen or has the meaning of R0 whereby R1, R'1 and R0 can be same or different, R2 and R3 are independently a C-bonded hydrocarbon radical or a heterohydrocarbon radical, and each of both R4 is C1-C6-alkyl, cyclopentyl, cyclohexyl, phenyl, methylphenyl, methylbenzyl or benzyl, or both R4 together form an aliphatic C4-C6 carbocycle. Metal complexes of these ligands are homogeneous catalysts for asymmetric addition reaction, particularly hydrogenations.
Process for preparing ligands of the formula (1), in which R1 is C1-C8-alkyl, unsubstituted cyclopentyl, cyclohexyl, norbornyl or adamantyl, or cyclopentyl or cyclohexyl, substituted by 1 to 3 C1-C4-alkyl or C1-C4-alkoxy, or benzyl, phenyl, naphthyl and anthryl which are unsubstituted or substituted by 1 to 3 C1-C4-alkyl, C1-C4-alkoxy, C1-C4-fluoroalkyl or C1-C4-fluoroalkoxy, F and Cl, each of R2 and R3 is independently a C-bonded hydrocarbon radical or a heterohydrocarbon radical, and R4 is C1-C4-alkyl, cyclopentyl, cyclohexyl, phenyl, methylphenyl, methylbenzyl or benzyl, which comprises (a) stereoselective metallation in ortho position to the amine side-chain of a compound of formula (A) in which R4 is as defined above, reaction with a dihalide of formula R1-PX2 in which R1 is as defined above and X is Cl or Br, stereoselective hydrolysis to give a compound containing an SPO group, and reaction with a secondary phosphine of formula H-PR2R3 in which R2 and R3 are as defined above, to give the compounds of formula (1). New ligands obtained by that process and metal complexes thereof.
Process for preparing a compound according to formula (I) or (Ia) in a high enantiomeric excess, Formulae (I), (Ia), the process comprising reacting a nucleophile of formula R1NHR2 with a chiral compound of formula (II), in the form of a racemate, Formula (II), in the presence of a rhodium-based catalytic system which comprises a chiral diphosphine ligand, as well as compounds made by that process and the use of that process or those compounds for preparing active pharmaceutical ingredients (APIs).
C07D 217/04 - Composés hétérocycliques contenant les systèmes cycliques de l'isoquinoléine ou de l'isoquinoléine hydrogénée avec uniquement des atomes d'hydrogène ou des radicaux ne contenant que des atomes d'hydrogène et de carbone, liés directement aux atomes de carbone du cycle contenant l'azoteAlkylène-bis-isoquinoléines avec des radicaux hydrocarbonés ou des radicaux hydrocarbonés substitués liés à l'atome d'azote du cycle
C07D 295/04 - Composés hétérocycliques contenant des cycles polyméthylène imine d'au moins cinq chaînons, des cycles aza-3 bicyclo [3.2.2] nonane, piperazine, morpholine ou thiomorpholine, ne comportant que des atomes d'hydrogène liés directement aux atomes de carbone du cycle avec des radicaux hydrocarbonés substitués liés aux atomes d'azote du cycle
14.
Chiral ligands used in transition metal catalysts for asymmetric addition reactions especially hydrogenation
1 is a ferrocenyl radical with a planar chiral centre when Q is a ferrocenyl radical without a planar chiral centre. Metal complexes of these ligands are homogeneous catalysts for asymmetric addition reactions, particularly hydrogenations.
C07F 9/53 - Oxydes des organo-phospinesSulfures des organo-phosphines
C07C 69/34 - Esters d'acides acycliques polycarboxyliques saturés dont un groupe carboxyle estérifié est lié à un atome de carbone acyclique
B01J 31/18 - Catalyseurs contenant des hydrures, des complexes de coordination ou des composés organiques contenant des complexes de coordination contenant de l'azote, du phosphore, de l'arsenic ou de l'antimoine
3 are independently selected from optionally substituted branched- and straight-chain alkyl, cycloalkyl, heterocycloalkyl, carbocyclic aryl, and heteroaryl.
Compounds of the formula I, in the form of mixtures comprising predominantly one enantiomer or in the form of pure enantiomers, secondary phosphine-Q-P*(=O)HR1 (I) in which secondary phosphine is a C-bonded, secondary phosphine group -P(R) 2; in which R is in each case independently hydrocarbon radicals or heterohydrocarbon radicals; Q is a bivalent, achiral, aromatic base skeleton, a bivalent, achiral ferrocene base skeleton, an optionally substituted bivalent cycloalkane or heterocycloalkane skeleton, or a C 1-C 4-alkylene skeleton, and in which base skeletons a secondary phosphine group is bonded directly to a carbon atom, or, in the case of cyclic base skeletons, directly to a carbon atom or via a C1-C 4-alkylene group, and in which base skeletons a P-chiral group -P*(O)HR1 is bonded to a carbon atom such that the phosphorus atoms are linked via 1 to 7 atoms of a carbon chain optionally interrupted by heteroatoms from the group of O, S, N, Fe or Si; P* is a chiral phosphorus atom; and R1 is a hydrocarbon radical, a C-bonded heterohydrocarbon radical or a ferrocenyl radical, with the proviso that R1 is an achiral ferrocenyl radical when Q is an achiral ferrocenyl base skeleton. Metal complexes of these ligands in a molarratio of ligand to metal of about 1.3:1 to 0.9:1are homogeneous catalysts for asymmetric addition reactions, particularly hydrogenations.
C07F 9/655 - Composés hétérocycliques, p. ex. contenant du phosphore comme hétéro-atome du cycle comportant des atomes d'oxygène, avec ou sans atomes de soufre, de sélénium ou de tellure, comme uniques hétéro-atomes du cycle
C07F 9/6553 - Composés hétérocycliques, p. ex. contenant du phosphore comme hétéro-atome du cycle comportant des atomes de soufre, avec ou sans atomes de sélénium ou de tellure, comme uniques hétéro-atomes du cycle
B01J 31/12 - Catalyseurs contenant des hydrures, des complexes de coordination ou des composés organiques contenant des composés organiques ou des hydrures métalliques contenant des composés organométalliques ou des hydrures métalliques
C07F 15/00 - Composés contenant des éléments des groupes 8, 9, 10 ou 18 du tableau périodique
C07C 213/02 - Préparation de composés contenant des groupes amino et hydroxy, amino et hydroxy éthérifiés ou amino et hydroxy estérifiés liés au même squelette carboné par des réactions impliquant la formation de groupes amino à partir de composés contenant des groupes hydroxy ou des groupes hydroxy éthérifiés ou estérifiés
C07C 231/12 - Préparation d'amides d'acides carboxyliques par des réactions n'impliquant pas la formation de groupes carboxamide
C07C 231/18 - Préparation d'isomères optiques par synthèse stéréospécifique
C07C 67/303 - Préparation d'esters d'acides carboxyliques par modification de la partie acide de l'ester sans introduction d'un groupe ester par hydrogénation de liaisons non saturées carbone-carbone
17.
BIDENTATE CHIRAL LIGANDS FOR USE IN CATALYTIC ASYMMETRIC ADDITION REACTIONS
Compounds of the formula (I), in the form of mixtures comprising predominantly one diastereomer or in the form of pure diastereomers, Z1-Q-P*R0R1 (I) in which Z1 is a C-bonded, secondary phosphine group -P(R)2; in which R is in each case independently hydrocarbon radicals or heterohydrocarbon radicals, or Z1 is the -P*R0R1 group; Q is a bivalent, achiral, aromatic base skeleton, a bivalent, achiral ferrocene base skeleton, an optionally substituted bivalent cycloalkane or heterocycloalkane skeleton, or a C1-C4-alkylene skeleton, and in which base skeletons a secondary phosphine group Z1 is bonded directly to a carbon atom, or, in the case of cyclic base skeletons, directly to a carbon atom or via a C1-C4-alkylene group, and in which base skeletons a P-chiral group -P*R0R1 is bonded directly to a carbon atom, or, in the case of cyclic base skeletons, directly to a carbon atom or via a C1-C4-alkylene group to a carbon atom such that the phosphorus atoms are linked via 1 to 7 atoms of a carbon chain optionally interrupted by heteroatoms from the group of O, S, N, Fe or Si; P* is a chiral phosphorus atom; R0 is methyl or hydroxyl, and R0 is methyl when Z1 is the -P*R0R1 group; and R1 is a C-bonded optically enriched or optically pure chiral, mono- or polycyclic, nonaromatic hydrocarbon or heterohydrocarbon radical which has 3 to 12 ring atoms and 1 to 4 rings and which has a stereogenic carbon atom at least in the α position to the P-C bond; Metal complexes of these ligands are homogeneous catalysts for asymmetric addition reactions, particularly hydrogenations.
C07F 9/655 - Composés hétérocycliques, p. ex. contenant du phosphore comme hétéro-atome du cycle comportant des atomes d'oxygène, avec ou sans atomes de soufre, de sélénium ou de tellure, comme uniques hétéro-atomes du cycle
C07F 9/6553 - Composés hétérocycliques, p. ex. contenant du phosphore comme hétéro-atome du cycle comportant des atomes de soufre, avec ou sans atomes de sélénium ou de tellure, comme uniques hétéro-atomes du cycle
B01J 31/12 - Catalyseurs contenant des hydrures, des complexes de coordination ou des composés organiques contenant des composés organiques ou des hydrures métalliques contenant des composés organométalliques ou des hydrures métalliques
C07C 67/303 - Préparation d'esters d'acides carboxyliques par modification de la partie acide de l'ester sans introduction d'un groupe ester par hydrogénation de liaisons non saturées carbone-carbone
C07C 213/02 - Préparation de composés contenant des groupes amino et hydroxy, amino et hydroxy éthérifiés ou amino et hydroxy estérifiés liés au même squelette carboné par des réactions impliquant la formation de groupes amino à partir de composés contenant des groupes hydroxy ou des groupes hydroxy éthérifiés ou estérifiés
C07C 231/12 - Préparation d'amides d'acides carboxyliques par des réactions n'impliquant pas la formation de groupes carboxamide
C07C 231/18 - Préparation d'isomères optiques par synthèse stéréospécifique
C07F 15/00 - Composés contenant des éléments des groupes 8, 9, 10 ou 18 du tableau périodique
C07F 17/02 - Metallocènes de métaux des groupes 8, 9 ou 10 du tableau périodique
18.
BIDENTATE CHIRAL LIGANDS FOR USE IN CATALYTIC ASYMMETRIC ADDITION REACTIONS
Compounds of the formula (I), in the form of mixtures comprising predominantly one diastereomer or in the form of pure diastereomers, Z1-Q-P*R0R1 (I) in which Z1 is a C-bonded, secondary phosphine group -P(R)2; in which R is in each case independently hydrocarbon radicals or heterohydrocarbon radicals, or Z1 is the -P*R0R1 group; Q is a bivalent, achiral, aromatic base skeleton, a bivalent, achiral ferrocene base skeleton, an optionally substituted bivalent cycloalkane or heterocycloalkane skeleton, or a C1-C4-alkylene skeleton, and in which base skeletons a secondary phosphine group Z1 is bonded directly to a carbon atom, or, in the case of cyclic base skeletons, directly to a carbon atom or via a C1-C4-alkylene group, and in which base skeletons a P-chiral group -P*R0R1 is bonded directly to a carbon atom, or, in the case of cyclic base skeletons, directly to a carbon atom or via a C1-C4-alkylene group to a carbon atom such that the phosphorus atoms are linked via 1 to 7 atoms of a carbon chain optionally interrupted by heteroatoms from the group of O, S, N, Fe or Si; P* is a chiral phosphorus atom; R0 is methyl or hydroxyl, and R0 is methyl when Z1 is the -P*R0R1 group; and R1 is a C-bonded optically enriched or optically pure chiral, mono- or polycyclic, nonaromatic hydrocarbon or heterohydrocarbon radical which has 3 to 12 ring atoms and 1 to 4 rings and which has a stereogenic carbon atom at least in the a position to the P-C bond; Metal complexes of these ligands are homogeneous catalysts for asymmetric addition reactions, particularly hydrogenations.
B01J 31/12 - Catalyseurs contenant des hydrures, des complexes de coordination ou des composés organiques contenant des composés organiques ou des hydrures métalliques contenant des composés organométalliques ou des hydrures métalliques
C07C 67/303 - Préparation d'esters d'acides carboxyliques par modification de la partie acide de l'ester sans introduction d'un groupe ester par hydrogénation de liaisons non saturées carbone-carbone
C07C 213/02 - Préparation de composés contenant des groupes amino et hydroxy, amino et hydroxy éthérifiés ou amino et hydroxy estérifiés liés au même squelette carboné par des réactions impliquant la formation de groupes amino à partir de composés contenant des groupes hydroxy ou des groupes hydroxy éthérifiés ou estérifiés
C07C 231/12 - Préparation d'amides d'acides carboxyliques par des réactions n'impliquant pas la formation de groupes carboxamide
C07C 231/18 - Préparation d'isomères optiques par synthèse stéréospécifique
C07F 9/655 - Composés hétérocycliques, p. ex. contenant du phosphore comme hétéro-atome du cycle comportant des atomes d'oxygène, avec ou sans atomes de soufre, de sélénium ou de tellure, comme uniques hétéro-atomes du cycle
C07F 9/6553 - Composés hétérocycliques, p. ex. contenant du phosphore comme hétéro-atome du cycle comportant des atomes de soufre, avec ou sans atomes de sélénium ou de tellure, comme uniques hétéro-atomes du cycle
C07F 15/00 - Composés contenant des éléments des groupes 8, 9, 10 ou 18 du tableau périodique
C07F 17/02 - Metallocènes de métaux des groupes 8, 9 ou 10 du tableau périodique
4-alkyl-substituted cyclopentadienyl; Y is a C-bonded chiral group which directs metals of metallation reagents into the ortho position; and Phos is a P-bonded P(III) substituent. The compounds are chiral ligands for complexes of transition metals which are used as homogeneous catalysts in asymmetric syntheses.
Abstract Compounds of the formula (I) in the form of racemates, enantiomerically pure diastereomers or a mixture of diastereomers, where the radicals R1 are identical or different and are each C1-C4-alkyl; m is 0 or an integer from 1 to 4; n is 0 or an integer from 1 to 3; p is 0 or an integer from 1 to 5; R2 is an aromatic hydrocarbon radical or a C-bonded heterohydrocarbon radical and R3 is an aliphatic or C-bonded heteroaliphatic hydrocarbon radical; R2 and R3 are identical or different and are each an aliphatic or C-bonded heteroaliphatic hydrocarbon radical; R4 is an unsubstituted or C1-C6-alkyl-, C1-C6-alkoxy-or halogen-substituted hydrocarbon radical; and A is a secondary amino group, are ligands for metal complexes which are suitable as catalysts for homogeneous enantioselective hydrogenation.
B01J 31/18 - Catalyseurs contenant des hydrures, des complexes de coordination ou des composés organiques contenant des complexes de coordination contenant de l'azote, du phosphore, de l'arsenic ou de l'antimoine
C07C 51/36 - Préparation d'acides carboxyliques, de leurs sels, halogénures ou anhydrides par des réactions ne créant pas de groupes carboxyle par hydrogénation de liaisons non saturées carbone-carbone
C07F 17/02 - Metallocènes de métaux des groupes 8, 9 ou 10 du tableau périodique
21.
PREPARATION OF OPTICALLY PURE FERROCENEDIPHOSPHINES
[(RcRc)-, (SFc,SFc)-, (SP,SP)-1,1'-Bis(2-sec-aminoalkyl)-1-ferrocenyl]phosphino-ferrocene or the enantiomer [(Sc,Sc)-, (RFc,RFc)-, (RP,RP)-1,1'-bis (2-sec-aminoalkyl)-1-ferrocenyl]phosphinoferrocene are enriched by heating a mixture of optical isomers formed in the reaction of 1,1'-dilithioferrocene-amine complexes with at least 2 equivalents of a ferrocenylhalophosphine and are then separated off as optically pure compounds.
Compounds of the formulae (I) and (II), or a mixture of these enantiomers, where R'1 is C1-C4-alkyl and n is 0, 1 or 2; R1 is C1-C8-alkyl, C2-C8-alken-1-yl, -CH2-OR or - CH2-NR5R6; the two radicals R2 are identical or different and are each hydrogen or a monovalent radical of an electrophilic organic compound, or one R2 has this meaning and the other R2 is hydrogen; sec-phos is a secondary phosphino group; R is C1-C8- alkyl and R5 and R6 are each C1-C6-alkyl or R5 and R6 together form tetramethylene, pentamethylene or 3-oxa-1,5-pentylene, are ligands for metal complexes which can be used as valuable homogeneous catalysts for asymmetric syntheses. The compounds are obtained by a novel process in which 3,3'-metallated 1,1'-di-R1-2,2'- dibromoferrocenes are firstly reacted with sec-phos halide, the bromine atoms are then replaced by lithium and the substituent R2 is subsequently introduced by reaction with an electrophilic organic compound or with water.
Compounds of the formulae I and Ia in the form of mixtures of diastereomers or pure diastereomers, (I), (Ia), where R1 is a hydrogen atom or C1-C4-alkyl and R'1 is C1-C4-alkyl; X1 and X2 are each, independently of one another, a sec-phosphino group; T is C6-C20-arylene or C4-C18- heteroarylene having heteroatoms selected from the group consisting of O, S, -N= and N(C1-C4-alkyl); v is 0 or an integer from 1 to 4; X1 is bound in the ortho position relative to the T-C* bond; Q is vinyl, methyl, ethyl, -CH2-OR, -CH2-N(C1-C4-alkyl)2 or a C- or S-bonded chiral group which directs metals of metallation reagents into the ortho position; R is hydrogen, a silyl radical or an aliphatic, cycloaliphatic, aromatic or aromatic-aliphatic hydrocarbon radical which has from 1 to 18 carbon atoms and is unsubstituted or substituted by C1-C4-alkyl, C1-C4-alkoxy, F or CF3; are ligands for metal complexes as homogeneous catalyst in asymmetric syntheses.
The invention provides a compound of the formula l having at least two chiral centres in the form of mixtures of diastereomers or pure diastereomers, wherein formula l is: secondary phosphine-Q-P*(=O)HR1 in which secondary phosphine is a secondary phosphine group with hydrocarbon radicals or heterohydrocarbon radicals as substituents. The compound of formula l may be used in preparing a metal complex with a transition metal, and the metal complex may be used as a catalyst in preparing a chiral organic compound by asymmetric addition of hydrogen to a carbon or carbon-heteroatom double bond in a prochiral organic compound.
C07C 51/36 - Préparation d'acides carboxyliques, de leurs sels, halogénures ou anhydrides par des réactions ne créant pas de groupes carboxyle par hydrogénation de liaisons non saturées carbone-carbone
C07C 67/28 - Préparation d'esters d'acides carboxyliques par modification de la partie hydroxyle de l'ester sans introduction d'un groupe ester
C07C 67/283 - Préparation d'esters d'acides carboxyliques par modification de la partie hydroxyle de l'ester sans introduction d'un groupe ester par hydrogénation de liaisons non saturées carbone-carbone
C07C 213/02 - Préparation de composés contenant des groupes amino et hydroxy, amino et hydroxy éthérifiés ou amino et hydroxy estérifiés liés au même squelette carboné par des réactions impliquant la formation de groupes amino à partir de composés contenant des groupes hydroxy ou des groupes hydroxy éthérifiés ou estérifiés
C07C 221/00 - Préparation de composés contenant des groupes amino et des atomes d'oxygène, liés par des liaisons doubles, liés au même squelette carboné
C07F 15/00 - Composés contenant des éléments des groupes 8, 9, 10 ou 18 du tableau périodique
C07F 17/02 - Metallocènes de métaux des groupes 8, 9 ou 10 du tableau périodique
25.
CHIRAL LIGANDS USED IN TRANSITION METAL CATALYSTS FOR ASYMMETRIC ADDITION REACTIONS ESPECIALLY HYDROGENATION
Ligands of the formula (I) secondary phosphine-Q-P(=O)HR1 (I) in the form of mixtures of diastereomers or pure diastereomers, in which secondary phosphine is a secondary phosphine group with hydrocarbon radicals or heterohydrocarbon radicals as substituents; Q is a bivalent bisaryl or bisheteroaryl radical with an axial chiral centre to which the two phosphorus atoms are bonded in the ortho positions to the bisaryl or bisheteroaryl bridge bond, or Q is a bivalent ferrocenyl radical with a planar chiral centre or without a planar chiral centre, to which the phosphorus atom of the secondary phosphine is bonded directly or via a C1-C4-carbon chain to a cyclopentadienyl ring, the -P*(=O)HR1 group is bonded either on the same cyclopentadienyl ring in ortho position to the bonded secondary phosphine or on the other cyclopentadienyl ring; P* is a chiral phosphorus atom, and R1 is a hydrocarbon radical, a heterohydrocarbon radical or a ferrocenyl radical, where R1 is a ferrocenyl radical with a planar chiral centre when Q is a ferrocenyl radical without a planar chiral centre. Metal complexes of these ligands are homogeneous catalysts for asymmetric addition reactions, particularly hydrogenations.
C07C 51/36 - Préparation d'acides carboxyliques, de leurs sels, halogénures ou anhydrides par des réactions ne créant pas de groupes carboxyle par hydrogénation de liaisons non saturées carbone-carbone
C07C 67/28 - Préparation d'esters d'acides carboxyliques par modification de la partie hydroxyle de l'ester sans introduction d'un groupe ester
C07C 67/283 - Préparation d'esters d'acides carboxyliques par modification de la partie hydroxyle de l'ester sans introduction d'un groupe ester par hydrogénation de liaisons non saturées carbone-carbone
C07C 213/02 - Préparation de composés contenant des groupes amino et hydroxy, amino et hydroxy éthérifiés ou amino et hydroxy estérifiés liés au même squelette carboné par des réactions impliquant la formation de groupes amino à partir de composés contenant des groupes hydroxy ou des groupes hydroxy éthérifiés ou estérifiés
C07C 221/00 - Préparation de composés contenant des groupes amino et des atomes d'oxygène, liés par des liaisons doubles, liés au même squelette carboné
C07F 15/00 - Composés contenant des éléments des groupes 8, 9, 10 ou 18 du tableau périodique
C07F 17/02 - Metallocènes de métaux des groupes 8, 9 ou 10 du tableau périodique
Compounds of the formula I in the form of enantiomerically pure diastereomers or a mixture of diastereomers, (I), where the radicals R1 are identical or different and are each C1-C4-alkyl; m is 0 or an integer from 1 to 3; n is 0 or an integer from 1 to 4; R2 is a hydrocarbon radical or a C-bonded heterohydrocarbon radical; Cp is unsubstituted or C1-C4-alkyl-substituted cyclopentadienyl; Y is a C-bonded chiral group which directs metals of metallation reagents into the ortho position; and Phos is a P-bonded P(III) substituent. The compounds are chiral ligands for complexes of transition metals which are used as homogeneous catalysts in asymmetric syntheses.
Compounds of the formula I in the form of enantiomerically pure diastereomers or a mixture of diastereomers, (I), where the radicals R1 are identical or different and are each C1-C4-alkyl; m is 0 or an integer from 1 to 3; n is 0 or an integer from 1 to 4; R2 is a hydrocarbon radical or a C-bonded heterohydrocarbon radical; Cp is unsubstituted or C1-C4-alkyl-substituted cyclopentadienyl; Y is a C-bonded chiral group which directs metals of metallation reagents into the ortho position; and Phos is a P-bonded P(III) substituent. The compounds are chiral ligands for complexes of transition metals which are used as homogeneous catalysts in asymmetric syntheses.
Process for stereoselective hydrogenation by reacting racemic aldehydes or ketones having a stereogenic carbon atom in the position relative to the C(O) group and containing the structural element -(O)C-C-CH- by means of hydrogen in the presence of a base and a ruthenium complex containing a bidentate ligand having coordinating P and N atoms, a monophosphine ligand and anionic and/or uncharged ligands as homogeneous catalyst, with the charge being balanced by one or two monovalent acid anions or a divalent acid anion when uncharged ligands are present.
C07C 29/141 - Préparation de composés comportant des groupes hydroxyle ou O-métal liés à un atome de carbone ne faisant pas partie d'un cycle aromatique à six chaînons par réduction d'un groupe fonctionnel contenant de l'oxygène de groupes contenant C=O, p. ex. —COOH d'un groupe —CHO avec de l'hydrogène ou des gaz contenant de l'hydrogène
C07C 29/145 - Préparation de composés comportant des groupes hydroxyle ou O-métal liés à un atome de carbone ne faisant pas partie d'un cycle aromatique à six chaînons par réduction d'un groupe fonctionnel contenant de l'oxygène de groupes contenant C=O, p. ex. —COOH de cétones avec de l'hydrogène ou des gaz contenant de l'hydrogène
C07C 31/135 - Alcools monohydroxyliques contenant des cycles saturés monocycliques à cycles à cinq ou six chaînonsAlcools naphténiques
There is provided a process for the preparation of 5,15-bis-⏧4-(3- trrmethylarnmonio-propyloxy)-phenyl]-porphyrin dihalide, wherein the process comprises step (a) of providing 4-(3-bromopropyloxy)benzaldehyde, step (b) of providing dipyrrolmethane, step (c) of reacting the 4-(3-bromopropyloxy)- benzaldehyde with the dipyrrol-methane, together with trifluoro acetic acid, in the presence of an oxidation reagent to produce 5,15-bis-⏧4-(3-bromo- propyloxy)-phenyl] -porphyrin which is purified by Soxhlet extraction from the adsorbed state on a bed of alumina under highly controlled conditions; and step (d) of reacting the 5,15-bis-⏧4-(3-bromo-propyloxy)-phenyl]-porphyrin with trimethylamine in the presence of dry dimethylformamide to produce 5,15-bis- ⏧4-(3-trrmethylarnmonio-propyl-oxy)-phenyl] -porphyrin dibromide. In a preferred embodiment, the process further comprises step (e) of passing the 5, 15-bis-⏧4-(3 -1rimemylammonio-propyloxy)-phenyl]-porphyrin di-bromide produced in step (d) through an anion exchanger to produce 5,15-bis-⏧4-(3- trimethylammonio-propyloxy)-phenyl]-porphyrin dichloride. There is provided a process for the preparation of 5,15-bis-(4-3-⏧(3-dimemylamino-propyl)- dimethyl-ammonio]-propyloxy} -phenyl] -porphyrin dihalide.
C07D 487/22 - Composés hétérocycliques contenant des atomes d'azote comme uniques hétéro-atomes dans le système condensé, non prévus par les groupes dans lesquels le système condensé contient au moins quatre hétérocycles
A61K 31/409 - Composés hétérocycliques ayant l'azote comme hétéro-atome d'un cycle, p. ex. guanéthidine ou rifamycines ayant des cycles à cinq chaînons avec un azote comme seul hétéro-atome d'un cycle, p. ex. sulpiride, succinimide, tolmétine, buflomédil ayant quatre de ces cycles, p. ex. dérivés de la porphine, bilirubine, biliverdine
A probe for simultaneously measuring the absorption and the scattered light at one wavelength or at two different wavelengths in the range of from 800 to 3000 nm in fuels containing suspended water is used to detect critical proportions of free water or pure water. The probe may be equipped with a sensor head and thus be used to monitor continuously for quality assurance and safety.
G01N 21/85 - Analyse des fluides ou solides granulés en mouvement
G01N 21/31 - CouleurPropriétés spectrales, c.-à-d. comparaison de l'effet du matériau sur la lumière pour plusieurs longueurs d'ondes ou plusieurs bandes de longueurs d'ondes différentes en recherchant l'effet relatif du matériau pour les longueurs d'ondes caractéristiques d'éléments ou de molécules spécifiques, p. ex. spectrométrie d'absorption atomique
Compounds of the formulae (I) and (V) in the form of racemates, mixtures of stereoisomers or optically pure stereoisomers, where R is unsubstituted or F-, Cl-, OH-, C1-C4-alkyl- or C1-C4-alkoxy-subsituted C1-C8-alkyl, C3-C8-cycloalkyl-C1-C4-alkyl or C7-C11 i-aralkyl; X1 is a secondary phosphino group; Ri is C1-C4-alkyl or phenyl; and n is 0 or from 1 to 5. The compounds are ligands for the formation of catalytically active metal complexes as asymmetric, homogeneous catalysts.
C07C 67/303 - Préparation d'esters d'acides carboxyliques par modification de la partie acide de l'ester sans introduction d'un groupe ester par hydrogénation de liaisons non saturées carbone-carbone
C07F 17/02 - Metallocènes de métaux des groupes 8, 9 ou 10 du tableau périodique
C07F 15/00 - Composés contenant des éléments des groupes 8, 9, 10 ou 18 du tableau périodique
Compounds of the formula (I) in the form of racemates, mixtures of stereoisomers or optically pure stereoisomers, formula (I), where X1 and X2 are each, independently of one another, a secondary phosphino group; R1 is a halogen atom or a substituent bound via a C atom, N atom, S atom, Si atom, a P(O) group or a P(S) group to the cyclopentadienyl ring; R2 is C1-C4-alkyl or phenyl; m is from 1 to 3 and n is 0 or from 1 to 5, are ligands for complexes of transition metals as enantioselective and homogeneous catalysts. As a result of the substitution, the conversion, the stereoselectivity and/or the configuration of the adduct formed can be influenced and optimization of catalysts can be made possible in this way.
The invention relates to the compounds of formula (I) in the form of enantiomer-pure diastereomers or a mixture of diastereomers, wherein R'1 represents C1-C4 alkyl, C6-C10 aryl, C7-C10 aralkyl or C7-C12 alkaralkyl and n is 0 or an integer of from 1 to 5; R1 represents a hydrogen atom, halogen, a hydrocarbon group with 1 to 20 C atoms that is either unsubstituted or substituted with -SC1-C4 alkyl, -OC1-C4 alkyl, -OC6-C10 aryl or -Si(C1C4 alkyl)3, or a silyl group with 3 C1-C12 hydrocarbon groups; Y represents vinyl, methyl, ethyl, -CH2-OR, -CH2-N(C1-C4 alkyl)2, a C-bound chiral group that directs metals of metalation reagents to the ortho position X1, or Y is a group -CHR2-OR'2; R2 represents C1-C8 alkyl, C5-C8 cycloalkyl, C6-C10 aryl, C7-C12 aralkyl or C7-C12 alkaralkyl; R'2 represents hydrogen or C1-C18 acyl; X1 and X2 independently represent a P-bound P(III) substituent, -SH or an S-bound group of mercaptan; and R represents hydrogen, a silyl group or an aliphatic, cycloaliphatic, aromatic or aromatic-aliphatic hydrocarbon group with 1 to 18 C atoms which is unsubstituted or substituted with C1-C4 alkyl, C1-C4 alkoxy, F or CF3. The inventive compounds are ligands for metal complexes of transition metals such as Ru, Rh or Ir which are catalysts for especially the enantioselective hydration of prochiral unsaturated compounds. Use of these compounds allows to achieve high catalyst activities and an excellent stereoselectivity.
Disclosed are compounds of formulas (I) and (II) in the form of enantiomer-pure diastereomers o diastereomer mixtures. In said formulas (I) and (II), R'1 represents C1-C4 alkyl while n represents 0 or an integer from 1 to 5; R1 represents a hydrogen atom, a hydrocarbon radical with 1 to 20 C atoms, secondary phosphino, a mercaptan radical with 1 to 20 C atoms in the hydrocarbon radical, or a silyl radical with 3 C1-C12 hydrocarbon radicals; R2 is the monovalent radical of an electrophilic organic compound; X1 represents F, Cl, Br, or I; and Y represents vinyl, methyl, ethyl, -CH2-N(C1-C4-alkyl)2, -CH2-OR wherein R is a hydrocarbon radical, or a C-bonded, S-bonded, or P-bonded chiral group that directs metals of metallization reagents into the ortho position X1. The inventive compounds are coordinating ligands for metal complexes of transition metals as homogeneous catalysts for coupling reactions and intermediate products for producing bidentate ligands.
Preparation of cyclic esters by hydrogenation of a carbonyl group in at least one anhydride radical -C(O)-O-C(O)- of a cyclic dicarboxylic or polycarboxylic anhydride by means of hydrogen in the presence of a homogeneous noble metal catalyst, characterized in that the hydrogenation is carried out in a homogeneous reaction mixture using an iridium catalyst. The cyclic esters are obtained in good chemical and optical yields when prochiral anhydrides are used together with chiral iridium catalysts.
C07D 307/77 - Composés hétérocycliques contenant des cycles à cinq chaînons comportant un atome d'oxygène comme unique hétéro-atome du cycle condensés en ortho ou en péri avec des carbocycles ou avec des systèmes carbocycliques
C07D 307/88 - Benzo [c] furannesBenzo [c] furannes hydrogénés avec un atome d'oxygène lié directement en position 1 ou 3
C07D 309/30 - Atomes d'oxygène, p. ex. delta-lactones
The present invention concerns a metallocene-based phosphine ligand for use in enantioselective catalysis, the ligand having the Formula (I): Wherein M is a metal; Z is P or As; L is a suitable linker; R1 is selected from alkyl, alkoxy, alkylamino, cycloalkyl, cycloalkoxy, cycloalkylamino carbocyclic aryl, substituted and unsubstituted carbocyclic aryloxy, heteroaryl, heteroaryloxy, carbocyclic arylamino and heteroarylamino; X* is selected from (II): Wherein R, R2 and R3 are independently selected from optionally substituted branched- and straight-chain alkyl, cycloalkyl, heterocycloalkyl, carbocyclic aryl, and heteroaryl.
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Scientific research and development, syntheses, advice,
analyses, expert opinions and studies, especially in the
fields of chemistry, biochemistry, biology and
biotechnology.
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