WO2020071818A1 - 탄소 이중결합 함유 화합물의 비대칭 수소첨가 반응용 촉매 - Google Patents
탄소 이중결합 함유 화합물의 비대칭 수소첨가 반응용 촉매Info
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- WO2020071818A1 WO2020071818A1 PCT/KR2019/012967 KR2019012967W WO2020071818A1 WO 2020071818 A1 WO2020071818 A1 WO 2020071818A1 KR 2019012967 W KR2019012967 W KR 2019012967W WO 2020071818 A1 WO2020071818 A1 WO 2020071818A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
Definitions
- the present invention is based on the filing date of Korean Patent Application No. 10-2018-0117777 filed with the Korean Patent Office on October 02, 2018 and Korean Patent Application No. 10-2019-0117657 filed with the Korean Patent Office on September 24, 2019. It claims to benefit, and all of its content is included in the present invention.
- the present invention relates to a catalyst for an asymmetric hydrogenation reaction of a compound containing a carbon double bond. Specifically, it relates to a catalyst for an asymmetric hydrogenation reaction that can be used to prepare an optical isomer from a carbon double bond-containing compound.
- X means OH, NH 2 , NRH, CO 2 H, CONH 2 , CONR 2, etc.
- Y means O, S, NH, etc., and contains the carbon double bond It is common for the compound to have a polar functional group that can be combined with a catalyst for an asymmetric hydrogenation reaction. Indeed, ruthenium metal or rhodium metal complex catalysts showed poor reactivity to asymmetric hydrogenation reactions for carbon double bond-containing compounds that do not contain polar functional groups.
- an iridium metal complex is mainly used instead of a ruthenium metal or rhodium metal complex.
- a typical iridium metal complex catalyst is a type of Crabtree's catalyst in which an N donor and a P donor are each bonded with a ligand, centering on an iridium metal.
- R 3 and R 4 are each independently a hydrogen atom; Hydroxy group; A substituted or unsubstituted, straight or branched C 1 -C 6 alkyl group; Halogen atom; Substituted or unsubstituted, straight or branched C 1 -C 6 alkoxy group; A substituted or unsubstituted, straight or branched C 1 -C 4 thioalkyl group; A substituted or unsubstituted allyloxy group; Or a substituted or unsubstituted aryloxy group;
- R 5 is a hydrogen atom or a C 1 -C 2 alkyl group or a C 1 -C 2 alkoxy group
- R 6 and R 6 ′ are each independently a hydrogen atom or a C 1 -C 6 alkyl group
- P is a substituted or unsubstituted, straight or branched C 1 -C 4 alkyl group; A substituted or unsubstituted benzyl group or allyl group; t-butyl dimethyl silyl group; t-butyl diphenyl silyl group; Methylphenylsilyl group; Trimethylphenylsilyl group; Or a protecting group of MeSO 2 , p-TsSO 2 ;
- n 1 to 3;
- the substituent is a halogen atom, a straight chain or branched chain C 1 -C 5 alkyl group, a straight chain or branched chain C 1 -C 5 alkoxy group or a straight chain or branched chain C 1- C 3 thioalkyl group.
- the (R) -optical isomer or (S) -optical isomer can be synthesized with an optical selectivity of 88% ee to 92% ee, and the recrystallization process is repeated using various organic solvents to obtain the opticality of the obtained compound. In some cases, the selectivity became rather low.
- the present invention is to provide a catalyst for an asymmetric hydrogenation reaction capable of separating optical isomers with excellent optical selectivity from a carbon double bond-containing compound.
- an iridium cation; And a ligand represented by Chemical Formula 1 bound to the iridium cation; to provide a catalyst for an asymmetric hydrogenation reaction of a carbon double bond-containing compound comprising:
- R 1 is a hydrogen atom; A substituted or unsubstituted, straight or branched C 1 -C 3 alkyl group; Or a substituted or unsubstituted, straight or branched C 1 -C 3 alkoxy group;
- R 2 and R 2 ′ are each independently a hydrogen atom; A substituted or unsubstituted, straight or branched C 1 -C 3 alkyl group; Or a substituted or unsubstituted, straight or branched C 1 -C 3 alkoxy group;
- the substituent is a halogen atom, a straight or branched chain C 1 -C 3 alkyl group, or a straight or branched chain C 1 -C 3 alkoxy group.
- the catalyst for an asymmetric hydrogenation reaction according to an embodiment of the present invention can prepare an optical isomer with high optical selectivity from a carbon double bond-containing compound.
- the dotted chain line means that the atomic group is placed at a position distant from the eye-viewing direction
- the thick and solid chains A steamer means that the atomic group is placed close to the eye.
- an iridium cation; And a ligand represented by Chemical Formula 1 bound to the iridium cation; to provide a catalyst for an asymmetric hydrogenation reaction of a carbon double bond-containing compound comprising:
- R 1 is a hydrogen atom; A substituted or unsubstituted, straight or branched C 1 -C 3 alkyl group; Or a substituted or unsubstituted, straight or branched C 1 -C 3 alkoxy group;
- R 2 and R 2 ′ are each independently a hydrogen atom; A substituted or unsubstituted, straight or branched C 1 -C 3 alkyl group; Or a substituted or unsubstituted, straight or branched C 1 -C 3 alkoxy group;
- the substituent is a halogen atom, a straight or branched chain C 1 -C 3 alkyl group, or a straight or branched chain C 1 -C 3 alkoxy group.
- the catalyst for an asymmetric hydrogenation reaction according to an embodiment of the present invention can prepare optical isomers from a carbon double bond-containing compound with excellent optical selectivity without a separate purification process.
- R 1 , R 2 , and R 2 ′ may each be hydrogen atoms.
- R 1 is a hydrogen atom
- R 2 , and R 2 ′ are each independently methyl, ethyl, n-propyl, isopropyl, 2-methylpropyl, or 2- It may be ethyl propyl.
- R 1 is a hydrogen atom
- R 2 , and R 2 ′ are each independently methoxy, ethoxy, n-propoxy, isopropoxy, 2-methylprop Foxy, or 2-ethylpropoxy.
- R 2 , and R 2 ′ are each a hydrogen atom, and R 1 may be methyl, ethyl, n-propyl, isopropyl, 2-methylpropyl, or 2-ethylpropyl.
- R 2 , and R 2 ′ are each a hydrogen atom, and R 1 is methoxy, ethoxy, n-propoxy, isopropoxy, 2-methylpropoxy, or 2-ethyl It can be propoxy.
- R 2 , and R 2 ′ are each a hydrogen atom, and R 1 is substituted with chlorine or fluorine, methyl, ethyl, n-propyl, isopropyl, 2-methylpropyl, or 2 -Ethylpropyl.
- the ligand of Formula 1 may be an optical isomer compound represented by Formula 2a or Formula 2b:
- R 1 , R 2 , and R 2 ′ may be the same as R 1 , R 2 , and R 2 ′ in Formula 1, respectively.
- the dotted chain line, the solid chain line and the bold line indicate the three-dimensional position of the atomic group constituting the compound as defined above.
- the optical isomer compound represented by Formula 2a may be any one of the following compounds.
- the catalyst for an asymmetric hydrogenation reaction comprising at least one of the ligands represented by the compounds 2a-1 to 2a-7, from a carbon double bond-containing compound, (R)-
- the optical isomers can be optically resolved with good optical selectivity.
- the catalyst for an asymmetric hydrogenation reaction can obtain (R) -optical isomers in high yield from a carbon double bond-containing compound even when a small amount of a catalyst is used as described later.
- the optical isomer compound represented by Formula 2b may be any one of the following compounds.
- the catalyst for an asymmetric hydrogenation reaction comprising at least one of the ligands represented by the compounds 2b-1 to 2b-7, from the carbon double bond-containing compound, (S)-
- the optical isomers can be optically resolved with good optical selectivity.
- the catalyst for the asymmetric hydrogenation reaction can obtain (S) -optical isomers in high yield from a carbon double bond-containing compound even when a small amount of catalyst is used as described later.
- the catalyst for the asymmetric hydrogenation reaction may further include, in addition to the ligand represented by Chemical Formula 1, an additional ligand capable of coordinating binding with the iridium cation.
- the additional ligand may be cycloocta-1,5-diene.
- the catalyst for the asymmetric hydrogenation reaction may include a complex of the following Chemical Formula 3:
- R 1 , R 2 , and R 2 ′ may be the same as R 1 , R 2 , and R 2 ′ in Chemical Formula 1, respectively.
- the P atom and the N atom of the ligand represented by Chemical Formula 1 may form a coordination bond with an iridium cation.
- a double bond of cycloocta-1,5-diene may form a coordination bond with an iridium cation.
- the catalyst for an asymmetric hydrogenation reaction including the complex represented by Chemical Formula 3 can more stably perform an asymmetric hydrogenation reaction.
- the catalyst for the asymmetric hydrogenation reaction comprising the complex represented by the formula (3) is a carbon double bond-containing compound, (R) -optical isomer or (S) -optical isomer more stably and optically with excellent optical selectivity Can be divided.
- the complex represented by Chemical Formula 3 may be any one of the following compounds.
- the complex represented by Chemical Formula 3 may be any one of the following compounds.
- the catalyst for the asymmetric hydrogenation reaction may include a coordination anion.
- the catalyst for the asymmetric hydrogenation reaction may further include a coordination anion of the following Chemical Formula 4.
- the catalyst for the asymmetric hydrogenation reaction may include a compound represented by Formula 5 below.
- R 1 , R 2 , and R 2 ′ may be the same as R 1 , R 2 , and R 2 ′ in Chemical Formula 1, respectively.
- the compound represented by Formula 5 may be a compound represented by Formula 5a below.
- R 1 , R 2 , and R 2 ′ may be the same as R 1 , R 2 , and R 2 ′ in Formula 5, respectively.
- the compound represented by Chemical Formula 5a may be any one of the following compounds.
- (R) -optical isomers by using a catalyst for an asymmetric hydrogenation reaction comprising at least one of the compounds represented by the compounds 5a-1 to 5a-7, (R) -optical isomers with excellent optical selectivity It can be optically divided.
- the catalyst for an asymmetric hydrogenation reaction can obtain (R) -optical isomers in high yield from a carbon double bond-containing compound even when a small amount of a catalyst is used as described later.
- the compound represented by Chemical Formula 5 may be a compound represented by Chemical Formula 5b.
- R 1 , R 2 , and R 2 ′ may be the same as R 1 , R 2 , and R 2 ′ in Formula 5, respectively.
- the compound represented by Chemical Formula 5b may be any one of the following compounds.
- the catalyst for an asymmetric hydrogenation reaction comprising at least one of the compounds represented by the compounds 5b-1 to 5b-7, from the carbon double bond-containing compound, (S)-
- the optical isomers can be optically resolved with good optical selectivity.
- the catalyst for the asymmetric hydrogenation reaction can obtain (S) -optical isomers in high yield from a carbon double bond-containing compound even when a small amount of catalyst is used as described later.
- the compound of Formula 5a may be prepared through Reaction Formula 1a.
- Formula 5b may be prepared through the following Reaction Scheme 1b.
- the method for preparing the compounds of Formula 5a and Formula 5b is not limited, and the compounds of Formula 5a and Formula 5b may be prepared through methods used in the art.
- the carbon double bond-containing compound may be a compound having pro-chirality.
- the (R) -optical isomer and (S) -optical isomer are high from the carbon double bond-containing compound having pro-chirality, for example, an olefin-based compound having pro-chirality, using the catalyst for the asymmetric hydrogenation reaction.
- the catalyst for the asymmetric hydrogenation reaction can obtain (R) -optical isomers and (S) -optical isomers with high yields from olefinic compounds having prochirality even when a relatively small amount of catalyst is used.
- the carbon double bond-containing compound may be a compound represented by Formula 6 below.
- X is oxygen (O) or carbon (C);
- R a1 and R a2 are each independently a hydrogen atom, a substituted or unsubstituted carbon atom having 1 to 3 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms, an alkoxy group, or a substituted or unsubstituted aryloxy group having 6 to 15 carbon atoms. Or an aralkyloxy group,
- R a1 and R a2 together form a substituted or unsubstituted, cyclic or heterocyclic group having 4 to 10 carbon atoms;
- R 5 is a hydrogen atom or a C 1 -C 2 alkyl group or a C 1 -C 2 alkoxy group
- Y 1 and Y 2 are different from each other, and each independently a hydrogen atom, a substituted alkyl group having 1 to 3 carbon atoms, a substituted alkoxy group having 1 to 3 carbon atoms, or Ki,
- R 3 and R 4 are each independently a hydrogen atom; Hydroxy group; A substituted or unsubstituted, straight or branched C 1 -C 6 alkyl group; Halogen atom; Substituted or unsubstituted, straight or branched C 1 -C 6 alkoxy group; A substituted or unsubstituted, straight or branched C 1 -C 4 thioalkyl group; A substituted or unsubstituted allyloxy group; Or a substituted or unsubstituted aryloxy group,
- P is a substituted or unsubstituted, straight or branched C 1 -C 4 alkyl group; A substituted or unsubstituted benzyl group or allyl group; t-butyl dimethyl silyl group; t-butyl diphenyl silyl group; Methylphenylsilyl group; Trimethylphenylsilyl group; Or a protective group of MeSO 2 and p-TsSO 2 ,
- n 1 to 3
- the substituent is a halogen atom, straight chain or branched chain C 1 -C 5 It is an alkyl group, a straight chain or branched chain C 1 -C 5 alkoxy group, or a straight chain or branched chain C 1 -C 3 thioalkyl group.
- X is O
- R a1 and R a2 together form a substituted or unsubstituted, heterocyclic group having 4 to 10 carbon atoms;
- Y 1 is a hydrogen atom and Y 2 is It can be a flag.
- R 3 , R 4 , P and n are as defined above.
- the carbon double bond-containing compound may be a compound represented by Formula 7 below:
- R 3 and R 4 are each independently a hydrogen atom; Hydroxy group; A substituted or unsubstituted, straight or branched C 1 -C 6 alkyl group; Halogen atom; Substituted or unsubstituted, straight or branched C 1 -C 6 alkoxy group; A substituted or unsubstituted, straight or branched C 1 -C 4 thioalkyl group; A substituted or unsubstituted allyloxy group; Or a substituted or unsubstituted aryloxy group;
- R 5 is a hydrogen atom or a C 1 -C 2 alkyl group or a C 1 -C 2 alkoxy group
- R 6 and R 6 ′ are each independently a hydrogen atom or a C 1 -C 6 alkyl group
- P is a substituted or unsubstituted, straight or branched C 1 -C 4 alkyl group; A substituted or unsubstituted benzyl group or allyl group; t-butyl dimethyl silyl group; t-butyl diphenyl silyl group; Methylphenylsilyl group; Trimethylphenylsilyl group; Or a protecting group of MeSO 2 , p-TsSO 2 ;
- n 1 to 3;
- the substituent is a halogen atom, a straight chain or branched chain C 1 -C 5 alkyl group, a straight chain or branched chain C 1 -C 5 alkoxy group or a straight chain or branched chain C 1- C 3 thioalkyl group.
- the catalyst for the asymmetric hydrogenation reaction of the carbon double bond-containing compound is effective from the compound represented by the formula (7) (R) -optical isomer and (S) -optical isomer with high optical selectivity It can be optically divided.
- the catalyst for the asymmetric hydrogenation reaction can obtain (R) -optical isomers and (S) -optical isomers with high yields from the compound represented by Chemical Formula 7 even when a relatively small amount of catalyst is used.
- NaBArF sodium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate
- Example 1 [(2-((S) -4,5-dihydro-2-phenyloxazol-4-yl) -1,3-diphenylpropan-2-yl) ((((S) -1,1'-binaphthalene)- 2,2'-diyl) phosphite )] (1,5-COD) iridium (I) Synthesis of tetrakis (3,5-bis (trifluoromethyl) phenyl) borate catalyst (Compound 5a-1)
- Example 2 [(2-((R) -4,5-dihydro-2-phenyloxazol-4-yl) -1,3-diphenylpropan-2-yl) (((R) -1,1'-binaphthalene)- 2,2'-diyl) phosphite )] (1,5-COD) iridium (I) Synthesis of tetrakis (3,5-bis (trifluoromethyl) phenyl) borate catalyst (Compound 5b-1)
- Example 1-1 except that (R) -methyl 4,5-dihydro-2-phenyloxazole-4-carboxylate is used instead of (S) -methyl 4,5-dihydro-2-phenyloxazole-4-carboxylate.
- 2-((R) -4,5-dihydro-2-phenyloxazol-4-yl) -1,3-diphenylpropan-2-ol was obtained.
- Example 3 [(2-((R) -4,5-dihydro-2-phenyloxazol-4-yl) -1,3-dip-tolylpropan-2-yl) ((((R) -1,1'-binaphthalene ) -2,2'-diyl) phosphite ] (1,5-COD) iridium (I) Synthesis of tetrakis (3,5-bis (trifluoromethyl) phenyl) borate catalyst (Compound 5b-2)
- Example 4 [(2-((S) -4,5-dihydro-2-phenyloxazol-4-yl) -1,3-bis (4-methoxyphenyl) propan-2-yl) (((S) -1, One'- binaphthalene ) -2,2'- diyl ) phosphite ] (1,5-COD) iridium (I) Synthesis of tetrakis (3,5-bis (trifluoromethyl) phenyl) borate catalyst (Compound 5a-4)
- Example 5 [(2-((R) -4,5-dihydro-2-phenyloxazol-4-yl) -1,3-bis (3,5-dimethylphenyl) propan-2-yl) (((R)- 1,1'- binaphthalene ) -2,2'- diyl ) phosphite ] (1,5-COD) iridium (I) Synthesis of tetrakis (3,5-bis (trifluoromethyl) phenyl) borate catalyst (Compound 5b-3)
- Example 6 [ (2-((S) -4,5-dihydro-2- (4-methoxyphenyl) oxazol-4-yl) -1,3-diphenylpropan-2-yl) ((((S) -1,1'-binaphthalene ) -2,2'-diyl) phosphite ] (1,5-COD) iridium (I) Synthesis of tetrakis (3,5-bis (trifluoromethyl) phenyl) borate catalyst (Compound 5a-5)
- Example 7 [(2-((S) -4,5-dihydro-2-p-tolyloxazol-4-yl) -1,3-diphenylpropan-2-yl) ((((S) -1,1'-binaphthalene ) -2,2'-diyl) phosphite ] (1,5-COD) iridium (I) Synthesis of tetrakis (3,5-bis (trifluoromethyl) phenyl) borate catalyst (Compound 5a-6)
- Example 1 except that (S) -methyl 4,5-dihydro-2-p-tolyloxazole-4-carboxylate was used instead of (S) -methyl 4,5-dihydro-2-phenyloxazole-4-carboxylate.
- the same method as -1 was performed to obtain 2-((S) -4,5-dihydro-2-p-tolyloxazol-4-yl) -1,3-diphenylpropan-2-ol.
- Example 8 [(2-((S) -2- (4- (trifluoromethyl) phenyl) -4,5-dihydrooxazol-4-yl) -1,3-diphenylpropan-2-yl) (((S) -1 ,One'- binaphthalene ) -2,2'- diyl ) phosphite ] (1,5-COD) iridium (I) tetrakis (3,5- bis (trifluoromethyl) phenyl ) borate Synthesis of catalyst (Compound 5a-7)
- the following comparative compound 3 was purchased from Solvias AG (Cas no. 583844-38-6).
- % ee (number of moles of one optical isomer -number of moles of another optical isomer) / number of moles of two optical isomers X 100
- S means compounds a-1 to a-3
- C means a catalyst for an asymmetric hydrogenation reaction. It means the weight ratio of the compound a and the catalyst for an asymmetric hydrogenation reaction when the compound a does not exist because all of the compound a is asymmetric hydrogenated.
- R is as defined in the above experimental scheme.
- catalysts for asymmetric hydrogenation reactions of Examples 1 to 2 and Examples 4 to 7 of the present invention are asymmetric hydrogens of Comparative Examples 1 and 3 It was confirmed that all compounds a could be asymmetrically hydrogenated by using a smaller amount than the catalyst for the addition reaction.
- the compound b-1 which is an intermediate in which only one of the two carbon double bonds reacted, was produced up to 29%, and the compound a-1 was at least 47% Since the degree remained, the optical selectivity of the optical isomers could not be confirmed.
- the catalyst for an asymmetric hydrogenation reaction easily separates (R) -optical isomers and (S) -optical isomers with excellent optical selectivity and high yield even when a small amount is used. You can see that you can.
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Abstract
Description
실험예 번호(사용한 비대칭 수소첨가 반응용 촉매) | 시작 화합물/최종 화합물 | 100% 변환율에서의 S/C 비(%) | (R)-광학이성질체의 함량(%) | (S)-광학이성질체의 함량(%) | %ee |
실험예 1-1(실시예 1의 화합물 5a-1) | 화합물 a-1/화합물 c-1 | 70 | 99.2% | 0.8% | (R)-광학이성질체 98.4 |
실험예 1-2(실시예 1의 화합물 5a-1) | 화합물 a-2/화합물 c-2 | 40 | 97.7% | 2.3% | (R)-광학이성질체95.4 |
실험예 1-3(실시예 1의 화합물 5a-1) | 화합물 a-3/화합물 c-3 | 40 | 99.4% | 0.6% | (R)-광학이성질체98.8 |
실험예 2-1(실시예 2화합물 5b-1) | 화합물 a-1/화합물 c-1 | 50 | 0.5% | 99.5% | (S)-광학이성질체99 |
실험예 2-2(실시예 2의 화합물 5b-1) | 화합물 a-2/화합물 c-2 | 70 | 1.0% | 99.0% | (S)-광학이성질체98.0 |
실험예 2-3(실시예 2의 화합물 5b-1) | 화합물 a-3/화합물 c-3 | 40 | 0.8% | 99.2% | (S)-광학이성질체98.4 |
실험예 3(실시예 4의 화합물 5a-4) | 화합물 a-1/화합물 c-1 | 50 | 98.9% | 1.1% | (R)-광학이성질체97.8 |
실험예 4 (실시예 5의 화합물 5b-3) | 화합물 a-1/화합물 c-1 | 40 | 1.5% | 98.5% | (R)-광학이성질체97.0 |
실험예 5(실시예 6의 화합물 5a-5) | 화합물 a-1/화합물 c-1 | 40 | 97.7% | 2.2% | (R)-광학이성질체95.5 |
실험예 6(실시예 7의 화합물 5a-6) | 화합물 a-1/화합물 c-1 | 40 | 97.3% | 2.7% | (R)-광학이성질체94.6 |
비교실험예 1(비교예 1의 비교 화합물 1) | 화합물 a-1/화합물 c-1 | 28 | 95.4% | 4.6% | (R)-광학이성질체90.8 |
비교실험예 2(비교2의 비교 화합물 2) | 화합물 a-1/ | N.A. | N.A. | N.A. | N.A. |
비교실험예 3(비교예 3의 비교 화합물 3) | 화합물 a-1/화합물 c-1 | 25 | 96.4% | 3.6% | (R)-광학이성질체92.8 |
실험예 번호(사용한 비대칭 수소첨가 반응용 촉매) | 시작 화합물 | 최종 화합물 | 100% 변환율에서의 S/C 중량비(%) | (R)-광학이성질체 수율 | (S)-광학이성질체 수율 | %ee |
실험예 7(화합물 5a-1) | 25 | 98.2% | 1.8% | (R)-광학이성질체96.4 | ||
실험예 8(화합물 5a-1) | 10 | 99.1% | 0.9% | (R)-광학이성질체98.2 |
Claims (7)
- 이리듐 양이온; 및상기 이리듐 양이온에 결합되는 하기 화학식 1의 리간드;를 포함하는 탄소 이중결합 함유 화합물의 비대칭 수소첨가 반응용 촉매:[화학식 1]상기 화학식 1에서,R 1은 수소 원자; 치환 또는 비치환, 직쇄 또는 분지쇄 C 1-C 3 알킬기; 또는 치환 또는 비치환, 직쇄 또는 분지쇄 C 1-C 3 알콕시기이고;R 2 및 R 2 '는 각각 독립적으로 수소 원자; 치환 또는 비치환, 직쇄 또는 분지쇄 C 1-C 3 알킬기; 또는 치환 또는 비치환, 직쇄 또는 분지쇄 C 1-C 3 알콕시기이고;상기 치환 알킬기, 및 치환 알콕시기의 경우, 상기 치환기는 할로겐 원자, 직쇄 또는 분지쇄 C 1-C 3 알킬기, 또는 직쇄 또는 분지쇄 C 1-C 3 알콕시기이다.
- 제1항에 있어서,상기 화학식 1의 리간드는 하기 화학식 2a 또는 화학식 2b로 표시되는 광학 이성질체 화합물인 탄소 이중결합 함유 화합물의 비대칭 수소첨가 반응용 촉매:[화학식 2a][화학식 2b]상기 화학식에서,R 1은 수소 원자; 치환 또는 비치환, 직쇄 또는 분지쇄 C 1-C 3 알킬기; 또는 치환 또는 비치환, 직쇄 또는 분지쇄 C 1-C 3 알콕시기이고;R 2 및 R 2 '는 각각 독립적으로 수소 원자; 치환 또는 비치환, 직쇄 또는 분지쇄 C 1-C 3 알킬기; 또는 치환 또는 비치환, 직쇄 또는 분지쇄 C 1-C 3 알콕시기이고;상기 치환 알킬기, 및 치환 알콕시기의 경우, 상기 치환기는 할로겐 원자, 직쇄 또는 분지쇄 C 1-C 3 알킬기, 또는 직쇄 또는 분지쇄 C 1-C 3 알콕시기이다.
- 제1항에 있어서,상기 촉매는 하기 화학식 3의 착물을 포함하는 탄소 이중결합 함유 화합물의 비대칭 수소첨가 반응용 촉매:[화학식 3]상기 화학식 3에서,R 1은 수소 원자; 치환 또는 비치환, 직쇄 또는 분지쇄 C 1-C 3 알킬기; 또는 치환 또는 비치환, 직쇄 또는 분지쇄 C 1-C 3 알콕시기이고;R 2 및 R 2 '는 각각 독립적으로 수소 원자; 치환 또는 비치환, 직쇄 또는 분지쇄 C 1-C 3 알킬기; 또는 치환 또는 비치환, 직쇄 또는 분지쇄 C 1-C 3 알콕시기이고;상기 치환 알킬기, 및 치환 알콕시기의 경우, 상기 치환기는 할로겐 원자, 직쇄 또는 분지쇄 C 1-C 3 알킬기, 또는 직쇄 또는 분지쇄 C 1-C 3 알콕시기이다.
- 제1항에 있어서,상기 탄소 이중결합 함유 화합물은 하기 화학식 6으로 표시되는 화합물인 탄소 이중결합 함유 화합물의 비대칭 수소첨가 반응용 촉매:[화학식 6]상기 화학식 6에서,X는 산소(O) 또는 탄소(C)이고;R a1과 R a2는 각각 독립적으로 수소 원자, 탄소수 1 내지 3의 치환 또는 비치환, 알킬기, 탄소수 1 내지 3의 치환 또는 비치환, 알콕시기, 또는 탄소수 6 내지 15의 치환 또는 비치환 아릴옥시기 또는 아랄킬옥시기이거나,R a1과 R a2는 함께 탄소수 4 내지 10의 치환 또는 비치환, 시클릭기 또는 헤테로시클릭기를 형성하고;R 5는 수소 원자 또는 C 1-C 2 알킬기 또는 C 1-C 2 알콕시기이고;여기서R 3 및 R 4는 각각 독립적으로 수소 원자; 히드록시기; 치환 또는 비치환, 직쇄 또는 분지쇄 C 1-C 6 알킬기; 할로겐 원자; 치환 또는 비치환, 직쇄 또는 분지쇄 C 1-C 6 알콕시기; 치환 또는 비치환, 직쇄 또는 분지쇄 C 1-C 4 티오알킬기; 치환 또는 비치환 알릴옥시기; 또는 치환 또는 비치환 아릴옥시기이고,P는 치환 또는 비치환, 직쇄 또는 분지쇄 C 1-C 4 알킬기; 치환 또는 비치환된 벤질기, 알릴기; t-부틸다이메틸실릴기; t-부틸다이페닐실릴기; 메틸페닐실릴기; 트리메틸페닐실릴기; 또는 MeSO 2, p-TsSO 2의 보호기를 의미하며,n은 1 내지 3이고,OP가 복수개일 때는 동일 또는 상이하고; 및상기 치환 알킬기, 치환 알콕시기, 치환 티오알킬기, 치환 아릴옥시기, 치환 아랄킬옥시기, 치환 시클릭기 및 치환 헤테로시클릭기의 경우, 상기 치환기는 할로겐 원자, 직쇄 또는 분지쇄 C 1-C 5 알킬기, 직쇄 또는 분지쇄 C 1-C 5 알콕시기 또는 직쇄 또는 분지쇄 C 1-C 3 티오알킬기이다.
- 제6항에 있어서,상기 탄소 이중결합 함유 화합물은 하기 화학식 7로 표시되는 화합물인 탄소 이중결합 함유 화합물의 비대칭 수소첨가 반응용 촉매:[화학식 7]상기 화학식 7에서,R 3 및 R 4는 각각 독립적으로 수소 원자; 히드록시기; 치환 또는 비치환, 직쇄 또는 분지쇄 C 1-C 6 알킬기; 할로겐 원자; 치환 또는 비치환, 직쇄 또는 분지쇄 C 1-C 6 알콕시기; 치환 또는 비치환, 직쇄 또는 분지쇄 C 1-C 4 티오알킬기; 치환 또는 비치환 알릴옥시기; 또는 치환 또는 비치환 아릴옥시기이고;R 5는 수소 원자 또는 C 1-C 2 알킬기 또는 C 1-C 2 알콕시기이고;R 6 및 R 6'는 각각 독립적으로 수소 원자 또는 C 1-C 6 알킬기이고;P는 치환 또는 비치환, 직쇄 또는 분지쇄 C 1-C 4 알킬기; 치환 또는 비치환된 벤질기, 알릴기; t-부틸다이메틸실릴기; t-부틸다이페닐실릴기; 메틸페닐실릴기; 트리메틸페닐실릴기; 또는 MeSO 2, p-TsSO 2의 보호기를 의미하며;n은 1 내지 3이고;OP가 복수개일 때는 동일 또는 상이하고; 및상기 치환 알킬기, 치환 알콕시기 및 치환 티오알킬기의 경우, 상기 치환기는 할로겐 원자, 직쇄 또는 분지쇄 C 1-C 5 알킬기, 직쇄 또는 분지쇄 C 1-C 5 알콕시기 또는 직쇄 또는 분지쇄 C 1-C 3 티오알킬기이다.
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CA3114162A CA3114162A1 (en) | 2018-10-02 | 2019-10-02 | Catalyst for asymmetric hydrogenation of compound containing carbon double bond |
DK19869816.9T DK3862083T3 (da) | 2018-10-02 | 2019-10-02 | Katalysator til asymmetrisk hydrogenering af forbindelse indeholdende carbon-dobbeltbinding |
EP19869816.9A EP3862083B1 (en) | 2018-10-02 | 2019-10-02 | Catalyst for asymmetric hydrogenation of compound containing carbon double bond |
IL281947A IL281947B2 (en) | 2018-10-02 | 2019-10-02 | A catalyst for the asymmetric hydrogenation of a compound containing a carbon double bond |
CN201980064463.5A CN112789108B (zh) | 2018-10-02 | 2019-10-02 | 用于含有碳双键的化合物的不对称氢化的催化剂 |
ES19869816T ES2942569T3 (es) | 2018-10-02 | 2019-10-02 | Catalizador para la hidrogenación asimétrica de un compuesto que contiene doble enlace de carbono |
PL19869816.9T PL3862083T3 (pl) | 2018-10-02 | 2019-10-02 | Katalizator do uwodorniania asymetrycznego związku zawierającego podwójne wiązanie węglowe |
AU2019352450A AU2019352450A1 (en) | 2018-10-02 | 2019-10-02 | Catalyst for asymmetric hydrogenation of compound containing carbon double bond |
US17/281,652 US11420988B2 (en) | 2018-10-02 | 2019-10-02 | Catalyst for asymmetric hydrogenation of compound containing carbon double bond |
JP2021517652A JP7442511B2 (ja) | 2018-10-02 | 2019-10-02 | 炭素二重結合含有化合物の不斉水素添加反応用触媒 |
MX2021003787A MX2021003787A (es) | 2018-10-02 | 2019-10-02 | Catalizador para la hidrogenación asimetrica de compuestos que contienen doble enlace de carbono. |
SG11202103311PA SG11202103311PA (en) | 2018-10-02 | 2019-10-02 | Catalyst for asymmetric hydrogenation of carbon-carbon double bond-containing compound |
BR112021005672-6A BR112021005672B1 (pt) | 2018-10-02 | 2019-10-02 | Catalisador para a hidrogenação assimétrica de composto contendo ligação dupla de carbono |
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