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WO2010021093A1 - Catalyseur organique asymétrique - Google Patents

Catalyseur organique asymétrique Download PDF

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Publication number
WO2010021093A1
WO2010021093A1 PCT/JP2009/003699 JP2009003699W WO2010021093A1 WO 2010021093 A1 WO2010021093 A1 WO 2010021093A1 JP 2009003699 W JP2009003699 W JP 2009003699W WO 2010021093 A1 WO2010021093 A1 WO 2010021093A1
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Prior art keywords
group
formula
asymmetric
added
compound
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Ceased
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PCT/JP2009/003699
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English (en)
Japanese (ja)
Inventor
敬司 中山
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Daiichi Sankyo Co Ltd
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Daiichi Sankyo Co Ltd
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Priority to JP2010525576A priority Critical patent/JP5548129B2/ja
Publication of WO2010021093A1 publication Critical patent/WO2010021093A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/01—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms
    • C07C311/02—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C311/09—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton the carbon skeleton being further substituted by at least two halogen atoms
    • 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
    • B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
    • 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
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/45—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by at least one doubly—bound oxygen atom, not being part of a —CHO group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C255/56—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and doubly-bound oxygen atoms bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
    • C07D319/06—1,3-Dioxanes; Hydrogenated 1,3-dioxanes not condensed with other rings
    • 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
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • 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
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
    • C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Definitions

  • the present invention relates to an asymmetric organic catalyst for addition reaction or condensation reaction and a method for producing an optically active keto alcohol using the same.
  • a compound having an asymmetric carbon atom or the like includes a plurality of optically active substances having different steric configurations.
  • optically active substances there are compounds that are significantly different in physiological activity from other optically active substances, and it is extremely important to selectively produce such useful optically active substances.
  • optical resolution means in the selective production method of optically active substances a method of reacting with a compound having no asymmetric element and selectively synthesizing one enantiomer (enantioselective asymmetric) Synthesis) is useful without waste of raw materials.
  • metal complexes are widely known as such asymmetric catalysts.
  • metal complexes are generated as waste, and the metal at the center is often a rare metal (rare metal), which is problematic when considering earth resources and the like, and has environmental problems.
  • Non-Patent Documents 1 to 5 amino acids such as proline and diamines having a primary amino group, a secondary amino group, and a tertiary amino group have been reported (Non-Patent Documents 1 to 5).
  • these asymmetric organic catalysts have problems such as a large amount of use, an insufficient optical activity yield, and substrate specificity.
  • these catalysts are derived from the opposite optically active forms and require the opposite as an asymmetric source, and the induction is complicated.
  • An object of the present invention is to provide a new asymmetric organic catalyst capable of achieving a high optical activity yield with a small amount of use and an enantioselective asymmetric synthesis method using them.
  • the present inventor examined the asymmetric organic catalyst in the aldol reaction.
  • the aldol reaction was carried out using cyclohexanecarboxylic acids having the following primary amino group and secondary amino group, the enantiomer was obtained in a small amount and in a high yield.
  • the inventors have found that selective asymmetric synthesis is possible, and that the enantiomer of the resulting ketoalcohol compound can be selectively obtained by selecting an optically active form of the catalyst, and the present invention has been completed.
  • the present invention has the formula (1)
  • R 1 and R 2 represents a hydrogen atom and the other represents an acyl group
  • R 3 represents an alkoxy group, an aryloxy group, an aralkyloxy group, an amino group, an alkylamino group, or a dialkylamino group.
  • R 1 HN— and R 2 HN— have the same configuration on the asymmetric carbon atom.
  • An asymmetric organic catalyst for addition reaction or condensation reaction comprising an optically active diaminocyclohexanecarboxylic acid represented by the formula (1) or a Bronsted acid salt thereof is provided.
  • the asymmetric organic catalyst of the present invention is used, an enantiomer having high optical purity can be selectively obtained with a small amount of catalyst.
  • the enantioselectivity of the resulting keto alcohol is high, and the desired keto alcohol enantiomer can be selectively obtained by selecting the asymmetric organic catalyst to be used.
  • the asymmetric organic catalyst of the present invention comprises an optically active diaminocyclohexanecarboxylic acid ester and an amide represented by the formula (1).
  • one of R 1 and R 2 is a hydrogen atom and the other is an acyl group.
  • the acyl group is a group generated by removing one or more hydroxy groups of oxo acid, and examples thereof include a group generated by removing a hydroxy group from carboxylic acid or sulfonic acid.
  • the acyl group include an alkanoyl group, an aroyl group, an alkanesulfonyl group, a halogenoalkanesulfonyl group, and an arylsulfonyl group.
  • the alkanoyl group is preferably an alkanoyl group having 2 to 12 carbon atoms; more preferably an acetyl group, a propionyl group, or a butyryl group.
  • aroyl group a benzoyl group, a benzoyl group having a substituent, and the like are preferable.
  • the alkanesulfonyl group an alkanesulfonyl group having 1 to 6 carbon atoms is preferable; a methanesulfonyl group and an ethanesulfonyl group are more preferable.
  • the halogenoalkanesulfonyl group is preferably an alkanesulfonyl group having 1 to 6 carbon atoms substituted with 1 to 15 halogen atoms; a trifluoromethanesulfonyl group or a pentafluoroethanesulfonyl group is preferred.
  • a benzenesulfonyl group and a paratoluenesulfonyl group are preferable.
  • acyl groups represented by R 1 or R 2 an alkanesulfonyl group or a halogenoalkanesulfonyl group is particularly preferred.
  • R 1 and R 2 are hydrogen atom and the other is an acyl group in order for the compound of the formula (1) to function as an asymmetric organic catalyst. This is considered because the hydrogen atom acts as a Bronsted acid.
  • R 3 represents an alkoxy group, an aryloxy group, an aralkyloxy group, an amino group, an alkylamino group or a dialkylamino group.
  • alkoxy group include linear, branched or cyclic alkoxy groups having 1 to 12 carbon atoms, such as methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, isobutyloxy group, tert-butyloxy group. , Cyclopentyloxy group, cyclohexyloxy group and the like. Of these, alkoxy groups having 1 to 6 carbon atoms are particularly preferable.
  • aryloxy group examples include an aryloxy group having 6 to 14 carbon atoms, such as a phenoxy group, a naphthyloxy group, and an anthracenyloxy group.
  • aralkyloxy group examples include a group in which an alkoxy group having 1 to 6 carbon atoms is bonded to an aryl group having 6 to 14 carbon atoms, such as a phenyl C 1-6 alkoxy group, more specifically, a benzyloxy group, diphenyl A methyloxy group etc. are mentioned.
  • alkylamino group examples include alkylamino groups having 1 to 12 carbon atoms, such as a methylamino group, an ethylamino group, a propylamino group, and an isopropylamino group. Of these, an alkylamino group having 1 to 6 carbon atoms is particularly preferable.
  • dialkylamino group examples include a di (C 1-12 alkyl) amino group, such as a dimethylamino group, a diethylamino group, a dipropylamino group, and a dibutylamino group. Of these, a di (C 1-12 alkyl) amino group is particularly preferred.
  • an alkoxy group, an aralkyloxy group, an alkylamino group, and a dialkylamino group are particularly preferable.
  • asymmetric organic catalysts act as catalysts even in a salt form with Bronsted acid, and depending on the substrate, these salts may give better values.
  • the counter acid include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid, organic carboxylic acids such as acetic acid, benzoic acid and tartaric acid, and organic sulfonic acids such as mesylic acid and paratoluenesulfonic acid. Of these, organic sulfonic acids such as mesylic acid are particularly preferred.
  • the compound of the formula (1) can be produced, for example, according to the following reaction formula.
  • the configuration of the following reaction formula is the case of Formula (1a), the compound of another configuration can be manufactured similarly.
  • R 3a represents an alkyl group, an aryl group or an aralkyl group
  • Boc represents a t-butoxycarbonyl group
  • Z represents a benzyloxycarbonyl group
  • R 1 is the same as above
  • a compound (B) is obtained by an iodolactone reaction using iodination of a readily available cyclohexene carboxylic acid (A).
  • This iodolactonization reaction can be performed by reacting compound (A) with iodine and potassium iodide in the presence of an alkali such as sodium bicarbonate.
  • Compound (C) is obtained by reacting compound (B) with an alkali such as sodium hydroxide to cause lactone ring opening and epoxidation.
  • Compound (D) is obtained by azidating compound (C) with sodium azide or the like.
  • Compound (E) is then obtained by reducing compound (D) in the presence of di-tert-butyl dicarbonate.
  • the reduction reaction is preferably catalytic reduction using palladium carbon or the like as a catalyst.
  • Compound (F) is obtained by azidating the hydroxy group of compound (E).
  • the compound (F) is then reduced, preferably catalytically reduced, to give the compound (G).
  • compound (H) is obtained.
  • Boc is eliminated by hydrolysis to obtain compound (I), which is reacted with acylating agent (R 1 ) to obtain compound (J), and then protecting group ( If Z) is eliminated by hydrogenation, compound (1a) is obtained.
  • the compound (H) is hydrogenated to remove the protecting group (Z) to obtain a compound (K), which is reacted with an acylating agent (R 2 ) to obtain a compound (L), and then protected. If the group (Boc) is eliminated by hydrolysis, the compound (1b) is obtained.
  • Boc and Z which are protecting groups for amino groups
  • the protective group include a combination of a hydrolytic leaving group such as a benzoyl group or 3,4,5-trimethoxyphenylmethyl group and a hydrogenation leaving group such as a benzyl group or a phenylethyl group.
  • a compound in which R 3 is an amino group, an alkylamino group or a dialkylamino group can be obtained by amidating an ester (—COOR 3a ) at any stage of the above reaction step.
  • the amidation reaction can be performed using, for example, ammonia, ammonium salt, alkylamine, or dialkylamine.
  • the compound (1) thus obtained is useful as an asymmetric organic catalyst for addition reaction or condensation reaction. That is, if an addition reaction or a condensation reaction is performed in the presence of the compound (1), an enantiomer can be obtained with high yield and high optical purity, and enantioselective asymmetric synthesis is possible.
  • examples of the addition reaction or condensation reaction include aldol reaction, Mannich reaction, Michael reaction, amination reaction, halogenation reaction and the like.
  • the catalyst of the present invention is particularly preferably applied to the aldol reaction.
  • the aldol reaction using the asymmetric organic catalyst of the present invention is represented by the following reaction formula.
  • R 4 and R 5 represent a hydrogen atom or an organic group
  • R 6 represents an organic group
  • * represents an asymmetric carbon atom, and has a specific configuration
  • the organic group represented by R 4, R 5 and R 6, are not limited to, hydrocarbon group, heterocyclic group, an alcohol, ether and the like.
  • hydrocarbon group both an aromatic hydrocarbon group and an aliphatic hydrocarbon group are included.
  • These hydrocarbon groups and heterocyclic groups, alcohols, ethers and the like may have a substituent such as a halogen atom, a nitro group, an amino group, a cyano group, a carboxyl group, an alkoxycarbonyl group, or a silyl group.
  • R 4 and R 5 may be combined to form a cycloalkane structure.
  • the catalyst of the formula (1) to be used may be used in an amount of 0.5 to 10 mol%, more preferably 1 to 10 mol%, relative to the raw material compound of the formula (2) or the formula (3).
  • the amount of catalyst used is small compared to the amount of conventional asymmetric organic catalysts used.
  • the reaction may be carried out in accordance with a normal aldol reaction, for example, at 0 to 20 ° C. for about 0.5 to 72 hours in the presence or absence of a solvent.
  • the configuration of the enantiomer of the target keto alcohol can be controlled by changing the configuration of the asymmetric organic catalyst of the formula (1) used. That is, the configuration of the enantiomer of the keto alcohol obtained is determined depending on whether the catalyst of the formula (1a) or the catalyst of the formula (1b) is used, so that two catalysts are synthesized from a common asymmetric source. By doing so, the target enantiomer can be selectively obtained.
  • the catalyst of the present invention can be recovered from the reaction mixture and reused.
  • Example 5 0.9 mL cyclohexanone and 45.3 mg p-nitrobenzaldehyde were added to a mixture of 0.9 mL tetrahydrofuran and 0.9 mL water. To this was added 5 mol% of compound (1a-1) or compound (1b-1) with respect to 1 mol of p-nitrobenzaldehyde, and the mixture was stirred at room temperature (25 ° C.) for 3 to 4 days. The reaction mixture was extracted with 3 mL of ethyl acetate, and after liquid separation, the organic layer was concentrated. The residue was purified by silica gel column chromatography to obtain 74.9 mg (yield 99%, diastereo ratio: 7/93 (syn / anti), 97% ee) of an aldol adduct.
  • Table 1 shows the results of the aldol reaction as in Example 5.
  • Example 6 0.9 mL of cyclopentanone and 45.3 mg of p-nitrobenzaldehyde were added to a mixture of 0.9 mL of tetrahydrofuran and 0.9 mL of water. To this was added 5 mol% of compound (1a-1) or compound (1b-1) with respect to 1 mol of p-nitrobenzaldehyde, and the mixture was stirred at room temperature (25 ° C.) for 16 to 22 hours. Thereafter, the same treatment as in Example 5 was performed to obtain 69.9 mg (yield 99%, diastereo ratio 92/8 (syn / anti), 93% ee) of an aldol adduct.
  • Table 2 shows the results of the aldol reaction performed in the same manner as in Example 6.
  • Example 7 The reaction was performed in substantially the same manner as in Example 5 except that 2,2-dimethyl-1,3-dioxa-5-one was used instead of cyclohexanone. The results are shown in Table 3.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
  • Catalysts (AREA)

Abstract

La présente invention concerne un catalyseur organique asymétrique avec lequel il est possible de réaliser un rendement optiquement actif élevé lorsque ledit catalyseur est utilisé en une petite quantité, ainsi qu'un procédé permettant de produire un composé à l'aide dudit catalyseur. Le catalyseur organique asymétrique est utilisé pour une réaction d'addition ou une réaction de condensation et est formé à partir d'un acide diaminocyclohexanecarboxylique optiquement actif ou un sel d'acide de Brønsted de celui-ci représenté par la formule (1), dans laquelle : un parmi R1 et R2 est un atome d'hydrogène et l'autre est un groupe acyle, et R3 est un groupe alcoxy, aryloxy, aralkyloxy, amino, alkylamino, ou dialkylamino. * est un atome de carbone asymétrique, et R1HN- et R2HN-  ont la même configuration sur l'atome de carbone asymétrique.
PCT/JP2009/003699 2008-08-18 2009-08-04 Catalyseur organique asymétrique Ceased WO2010021093A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012002538A1 (fr) * 2010-07-02 2012-01-05 第一三共株式会社 Procédé pour la préparation de sel dérivé de diamine optiquement actif
US8541443B2 (en) 2010-03-19 2013-09-24 Daiichi Sankyo Company, Limited Crystal of diamine derivative and method of producing same
CN104781244A (zh) * 2012-11-23 2015-07-15 第一三共株式会社 用于制备(1s,4s,5s)-4-溴-6-氧杂二环[3.2.1]辛烷-7-酮的方法
CN104936961A (zh) * 2013-03-29 2015-09-23 第一三共株式会社 (1s,4s,5s)-4-溴-6-氧杂二环[3.2.1]辛-7-酮的制备方法
CN105017121A (zh) * 2015-06-09 2015-11-04 哈尔滨工程大学 带有Fmoc-L-羟脯氨酸的光学活性苯乙炔衍生物及制备和应用方法

Citations (1)

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Publication number Priority date Publication date Assignee Title
JP2002275118A (ja) * 2001-03-15 2002-09-25 Central Glass Co Ltd アルドール反応生成物の製造方法

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JP2002275118A (ja) * 2001-03-15 2002-09-25 Central Glass Co Ltd アルドール反応生成物の製造方法

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
GUIZZETTI STEFANIA ET AL.: "Enantioselective Direct Aldol Reaction "on Water" Promoted by Chiral Organic Catalysts", ORG. LETT., vol. 9, no. 7, 29 March 2007 (2007-03-29), pages 1247 - 1250 *
LUO SANZHONG ET AL.: "Highly Enantioselective Direct syn- and anti-Aldol Reactions of Dihydroxyacetones Catalyzed by Chiral Primary Amine Catalysts", ORG. LETT., vol. 10, no. 4, 21 February 2008 (2008-02-21), pages 653 - 656 *
NAKADAI MASAKAZU ET AL.: "Diversity-based strategy for discovery of environmentally benign organocatalyst:diamine-protonic acid catalysts for asymmetric direct aldol reaction", TETRAHEDRON, vol. 58, no. 41, 7 October 2002 (2002-10-07), pages 8167 - 8177 *
NAKAYAMA KEIJI ET AL.: "Complete Switch of Procuct Selectivity in Asymmetric Direct Aldol Reaction with Two Different Chiral Orgnocatalysts from a Common Chiral Source", J. AM. CHEM. SOC., vol. 130, no. 52, 31 December 2008 (2008-12-31), pages 17666 - 17667 *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8541443B2 (en) 2010-03-19 2013-09-24 Daiichi Sankyo Company, Limited Crystal of diamine derivative and method of producing same
WO2012002538A1 (fr) * 2010-07-02 2012-01-05 第一三共株式会社 Procédé pour la préparation de sel dérivé de diamine optiquement actif
CN103080078A (zh) * 2010-07-02 2013-05-01 第一三共株式会社 光学活性二胺衍生物盐的制备方法
US20130165657A1 (en) * 2010-07-02 2013-06-27 Daiichi Sankyo Company, Limited Process for preparation of optically active diamine derivative salt
US8901345B2 (en) 2010-07-02 2014-12-02 Daiichi Sankyo Company, Limited Process for preparation of optically active diamine derivative salt
CN103080078B (zh) * 2010-07-02 2015-02-11 第一三共株式会社 光学活性二胺衍生物盐的制备方法
JP5780657B2 (ja) * 2010-07-02 2015-09-16 第一三共株式会社 光学活性ジアミン誘導体の塩の製造方法
CN104781244A (zh) * 2012-11-23 2015-07-15 第一三共株式会社 用于制备(1s,4s,5s)-4-溴-6-氧杂二环[3.2.1]辛烷-7-酮的方法
CN104936961A (zh) * 2013-03-29 2015-09-23 第一三共株式会社 (1s,4s,5s)-4-溴-6-氧杂二环[3.2.1]辛-7-酮的制备方法
CN105017121A (zh) * 2015-06-09 2015-11-04 哈尔滨工程大学 带有Fmoc-L-羟脯氨酸的光学活性苯乙炔衍生物及制备和应用方法

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