EP2061748A2 - Synthèse asymétrique catalytique d'amines primaires par réduction au borane d'éthers d'oxime au moyen d'esters de spiroborate - Google Patents

Synthèse asymétrique catalytique d'amines primaires par réduction au borane d'éthers d'oxime au moyen d'esters de spiroborate

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Publication number
EP2061748A2
EP2061748A2 EP07814214A EP07814214A EP2061748A2 EP 2061748 A2 EP2061748 A2 EP 2061748A2 EP 07814214 A EP07814214 A EP 07814214A EP 07814214 A EP07814214 A EP 07814214A EP 2061748 A2 EP2061748 A2 EP 2061748A2
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European Patent Office
Prior art keywords
chiral
oxime
reduction
prochiral
unsubstituted
Prior art date
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EP07814214A
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German (de)
English (en)
Inventor
Melvin De Jesus
Margarita Ortiz-Marciales
Viatcheslav Stepanenko
Xiaogen Huang
Kun Huang
Merced Francisco
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Office Of Intellectual Property And Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
    • C07C209/40—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of hydroxylamino or oxyimino groups
    • 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
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • B01J31/146—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of boron
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B53/00—Asymmetric syntheses
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C237/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups
    • C07C237/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C237/04—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C237/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups
    • C07C237/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C237/04—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C237/06—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated having the nitrogen atoms of the carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C237/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups
    • C07C237/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C237/04—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C237/08—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated having the nitrogen atom of at least one of the carboxamide groups bound to an acyclic carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/06—Esters of carbamic acids
    • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
    • C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C271/12—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/36—Radicals substituted by singly-bound nitrogen atoms
    • C07D213/40—Acylated substituent nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
    • C07D311/58—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4
    • C07D311/68—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4 with nitrogen atoms directly attached in position 4
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
    • C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D335/06—Benzothiopyrans; Hydrogenated benzothiopyrans
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
    • B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
    • B01J2231/643—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of R2C=O or R2C=NR (R= C, H)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/07—Optical isomers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
    • C07C2602/04—One of the condensed rings being a six-membered aromatic ring
    • C07C2602/08—One of the condensed rings being a six-membered aromatic ring the other ring being five-membered, e.g. indane
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
    • C07C2602/04—One of the condensed rings being a six-membered aromatic ring
    • C07C2602/10—One of the condensed rings being a six-membered aromatic ring the other ring being six-membered, e.g. tetraline

Definitions

  • the claimed invention was made with U.S. Government support under grant numbers MBRS GM 08216 and NIH-IMBRE NC P20 RR-016470 awarded by the National Institutes of Health (NIH). The government has certain rights in this invention.
  • the present invention relates to a method for the reduction of oxime ethers using stable spiroborate esters to prepare enantiopure primary amines in a truly catalytic process with excellent enantioselectivity.
  • O-benzyloxy amine 2a can also, be obtained due to incomplete reduction.
  • O-methylarylalkyl oxime ethers have been reduced with spiroborate esters derived from (S) proline and [R)- or (S)-1 ,1 '-bi-2-naphthol.
  • Reduction of acetophenone O-methyloxime, as a model compound, with 2 equiv of borane and 10% of catalyst produced only 58% yield and 42% ee. Therefore, one equiv of catalyst was required to increase the yield and enantioselectivity of the reaction.
  • This invention relates to a method for the reduction of oxime ethers using these stable spiroborate esters to prepare enantiopure primary arylalkyl amines in a truly catalytic process with excellent enantioselectivity. More specifically, we developed and synthesized stable chiral spiroborate esters derived from enantiopure 1 ,2-aminoalcohols, 5 - 10, shown in Figure 2, as a new type of catalysts for asymmetric reduction of ketones.
  • catalyst 5 derived from (S)-diphenylvalinol
  • Fig. 1 is a schematic diagram showing a catalytic reduction according to the prior art.
  • Fig. 2 is a schematic diagram showing spiroborate esters derived from chiral aminoalcohols according to an embodiment of the invention.
  • Fig. 3 is a schematic diagram showing the enantioselective reduction of oxime ethers according to an embodiment of the invention.
  • Fig. 4 is a schematic diagram showing the enantioselective reduction of O-benzyl acetophenone oxime with the catalysts according to one embodiment of the invention.
  • Fig. 5 is a schematic diagram showing the synthesis of oximes and corresponding O- benzylated arylketoximes according to an embodiment of the invention.
  • Fig. 6 is a schematic diagram showing the synthesis and enantioselective reduction of O-benzyl pyridyl ketoximes 13 with a catalyst according to a preferred embodiment of the invention.
  • oxazaborolidines for the enantioselective reduction of ketones, oximes and imino derivatives in the preparation of pharmaceutical intermediaries are widely known.
  • the present invention is industrially advantageous since it offers a new process for a more efficient and facile preparation of enantiopure amines by reduction with borane in the presence of our recent developed spiroborate esters, which are highly efficient chiral transfer catalysts, analogous to the well-known oxazaborolidines catalysts.
  • This process can be used to carry out the preparation of enantiopure drugs with equal or better stereoselectivity in a practical catalytic way.
  • the disclosed invention can be applied to the synthesis of (S)-dolaphenine (as disclosed in U.S. Patent No. 6,020,495), a precursor for the preparation of the antineoplastic peptide chain Dolastatin 10, by the borane reduction of 4-CF 3 Bn oxime ether using as reagent the spiroborate ester derived from valinol and ethylene glycol.
  • (S)-dolaphenine as disclosed in U.S. Patent No. 6,020,495
  • the above-mentioned patent mentions other examples of important chiral amines with pharmaceutical properties that can be prepared by the proposed process using the discovered catalysts, such as the 3-phenyl-1 -indanamines that have antidepressant activity (as disclosed by Bogeso, K. P.
  • catalysts 5 - 10 provided quantitatively primary amine 3, which by GC analysis of the ethoxycarbonyl derivative 4 on a chiral column exhibited moderate to high enantioselectivity, catalyst 5 being the most efficient, since it provided 93% ee of ⁇ -methylbenzylamine 3, as illustrated in Table 1.
  • the reaction was performed at room temperature in THF using different equivalents of catalyst 5 and borane, and different borane sources like, borane-DMS and borane-THF, with NaBH 4 or ⁇ /-isopropyl ⁇ /-methyl te/t-butyl amine, as additives.
  • borane sources like, borane-DMS and borane-THF, with NaBH 4 or ⁇ /-isopropyl ⁇ /-methyl te/t-butyl amine, as additives.
  • the ratio of products was determined by GC analysis.
  • the ee of compound 3 was determined by chiral GC analysis of the ethoxy carbamide derivative.
  • oxime in THF was added in 10 hours, then 24 hours stirring at room temperature.
  • the borane reagent was stabilized with ⁇ 0.005 M ⁇ /-isopropyl ⁇ /-methyl te/t-butyl amine.
  • the yield in parenthesis was obtained after purification of ethoxy carbamide.
  • BH 3 -THF reagent is stabilized with 0.005 M ⁇ /-isopropyl N- methyl te/t-butylamine.
  • the amount of borane was 4 equiv to 1 equiv of oxime ether and the reactions were made at room temperature for 36 hours.
  • the oxime in the chosen solvent was added during the 1 1 th hour.
  • the oxime in the chosen solvent was added during 1 st hour.
  • BH 3 -THF reagent is stabilized with 0.005 M ⁇ /-isopropyl ⁇ /-methyl tert- butyl amine.
  • BH 3 -THF reagent is stabilized with 0.005 M NaBH 4 .
  • a further aspect of the invention involves the effect of aromatic substitution of acetophenone oximes 1 b-e in the enantioselectivity of the reduction shown in Fig. 5. As indicated in Table 6, steric and electronic factors did not change significantly the ee, except for 4-CF 3 benzyl oxime that readily afforded 99% ee.
  • the optimized synthetic method was extended to other substrates using unsubstituted O-benzyl oxime ethers since the benzyl bromide not only is less expensive, but also affords pure (£)-benzylated products.
  • Representative aromatic benzyl oximes 11 were prepared by the general method, shown in Fig 5, and reduced using 0.1 equiv of catalyst 5 in dioxane at room temperature and 0 0 C. The results are indicated in Table 7. After an acidic work up, the corresponding crude (S) primary amines were acetylated with acetic anhydride in the presence of triethylamine and DMAP in dichloromethane.
  • 2-, 3- or 4-pyridyl alkyl oxime ethers were prepared and reduced in the presence of catalyst 5 at different reaction conditions, as indicated in Fig 6 and Table 8.
  • the 4-acetylpyridine O-benzyloxime, 13a afforded the N-(1 -pyridyl-4yl-ethyl)-acetamides, 14a, in 99% ee at 0 Q C in dioxane with 5 equiv of BH 3 -THF, but the chemical yield was low, as indicated in entries 4.
  • TLC indicated remaining starting material.
  • PROCEDURE (F?)-2-amino-1 ,1 ,2-triphenylethanol 1 , (S)-2-amino-1 ,1 ,2-triphenylethanol 1 , (S)-2-amino-3- methyl-1 ,1 -diphenylbutan-1 -ol 2 were synthesized according to literature procedures. These include: (1 ) Bach, J.; Berenger, R.; Garcia, J.; Loscertales, T.; Vilarrasa, J. J. Org. Chem. 1996, 61, 9021 -9025; and (2) Itsuno, S.; Ito, K. J. Org. Chem. 1984, 49, 555-557.
  • 1 H, 13 C and 11 B spectra were recorded on a Bruker Avance 400 MHz spectrometer with standard pulse sequences operating at 400.152 MHz, 100.627 MHz, and 128.384 MHz for 1 H, 13 C and 11 B respectively.
  • Chiral gas chromatography analysis was processed on a Hewlett Packard GC 5890 equipped with a Chrompack Chiralsil-Dex-CB column (30 m x 0.25 mm ⁇ .25 ⁇ m).
  • GC-MS analysis was processed on a Finnigan Trace GC/Polaris Q Mass detector using a Restek RTX-5MS column.
  • reaction was quenched with 6N HCI and then 6 N NaOH until the solution was strongly basic.
  • the aqueous solution was extracted with diethylether to obtain the primary amine and the combined organic phase was washed with saturated NaCI solution and dried over anhydrous Na 2 SO 4 .
  • the solvent was removed under vacuum and the residue acetylated to prepare the amide derivative.
  • the reaction mixture was quenched with methanol (5 ml_) and then refluxed for 6 h. The solvent was evaporated under vacuum and the residue was directly acetylated.
  • the conversion ratio was determined by GC analysis (Hewlett Packard GC 5890); for compound 1 a: 13.3 min, compound 2a: 12.6 min, and compound 3: 3.9 min. The ratio was calculated from the area accumulation.
  • acetic anhydride (0.11 ml_, 1.0 mmol, 2.0 equiv) was added to a solution of the crude amine in anhydrous CH 2 CI 2 (1 OmL) with DMAP (13mg, 10%), Et 3 N (0.2 ml_, 1 mmol, 2.0 equiv). The resulting mixture was stirred for 3 h. The solvent was removed under vacuum. The residue was purified directly by column chromatography on silica gel, eluted with PE/EA (1v/1v) giving the corresponding amides.
  • the pyridyl compounds (15a-15h) were purified by column chromatography by elution first with ether, and then with CH 2 CI 2 /CH 3 OH (10v/1 v). The pure amides were analyzed by GC using the chiral column.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Pyridine Compounds (AREA)
  • Heterocyclic Compounds Containing Sulfur Atoms (AREA)
  • Pyrane Compounds (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne une réduction asymétrique d'éther de cétoxime d'arylalkyle et de pyridylalkyle avec du borane catalysé par plusieurs spiroborates chiraux dérivés de 1,2-amino alcools non racémiques. Une conversion complète d'oxime en amine primaire est extrêmement dépendante du catalyseur, de la source et de la quantité de borane et de la température. La conversion et l'énantiosélectivité sont déterminées par la substitution benzylique de l'oxime. Après optimisation, un catalyseur dérivé du diphényl valinol pourrait avec succès permettre d'obtenir des amines primaires avec un bon rendement et une énantiosélectivité s'élevant jusqu'à 99% ee. Au moyen de la méthodologie développée, d'autres pyridyl alkyl méthanamines primaires non racémiques ont également été préparées pour déboucher sur un rendement chimique élevé et une excellente énantiosélectivité.
EP07814214A 2006-08-29 2007-08-17 Synthèse asymétrique catalytique d'amines primaires par réduction au borane d'éthers d'oxime au moyen d'esters de spiroborate Withdrawn EP2061748A2 (fr)

Applications Claiming Priority (2)

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US84114706P 2006-08-29 2006-08-29
PCT/US2007/076195 WO2008027740A2 (fr) 2006-08-29 2007-08-17 Synthèse asymétrique catalytique d'amines primaires par réduction au borane d'éthers d'oxime au moyen d'esters de spiroborate

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EP (1) EP2061748A2 (fr)
JP (1) JP2010502632A (fr)
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AU2011329233A1 (en) 2010-11-15 2013-05-23 Abbvie Deutschland Gmbh & Co Kg NAMPT and ROCK inhibitors
CN102584876A (zh) * 2012-01-18 2012-07-18 广西壮族自治区化工研究院 高活性手性催化剂螺硼酸酯的制备方法
CN105693595B (zh) * 2016-04-28 2018-09-28 上海亚兴生物医药科技有限公司 一种(r)-3-氨基-1,2,3,4-四氢咔唑的合成方法
KR102323561B1 (ko) * 2020-01-06 2021-11-09 (주)분자와물질 아미노알콜-보론-바이놀 복합체 및 이를 이용한 광학활성 아미노알콜 유도체의 제조방법

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JP2679248B2 (ja) * 1989-05-26 1997-11-19 住友化学工業株式会社 光学活性アミン類の製造方法
EP0485069B1 (fr) * 1990-10-08 1995-02-15 Sumitomo Chemical Company Limited Procédé pour la préparation d'amines optiquement actifs
JPH08337556A (ja) * 1995-04-13 1996-12-24 Sumitomo Chem Co Ltd 光学活性アミン類の製造法
CN1243757C (zh) * 2003-02-27 2006-03-01 武汉大学 螯合手性硼酸酯及其制备方法和用途

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CN101547890A (zh) 2009-09-30
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JP2010502632A (ja) 2010-01-28
WO2008027740A2 (fr) 2008-03-06

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