JPH0597735A - Production of optically active secondary alcohol - Google Patents
Production of optically active secondary alcoholInfo
- Publication number
- JPH0597735A JPH0597735A JP3263702A JP26370291A JPH0597735A JP H0597735 A JPH0597735 A JP H0597735A JP 3263702 A JP3263702 A JP 3263702A JP 26370291 A JP26370291 A JP 26370291A JP H0597735 A JPH0597735 A JP H0597735A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- hydrogen atom
- optically active
- mgc2h5
- substituted
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Pyrrole Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明はピロリジンメタノ−ル誘
導体を用いる光学活性二級アルコ−ルの製造方法に関す
るものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an optically active secondary alcohol using a pyrrolidine methanol derivative.
【0002】[0002]
【従来の技術】光学活性な二級アルコ−ルは、医薬品や
液晶等の原料として有用であるがその製造法が光学分割
を必要とするため入手は困難でありまた入手できるもの
も高価である。2. Description of the Related Art Optically active secondary alcohols are useful as raw materials for pharmaceuticals, liquid crystals, etc., but are difficult to obtain because their production method requires optical resolution, and those available are expensive. ..
【0003】従来、アルデヒドあるいはケトンから光学
活性二級アルコ−ルを製造する場合に不斉触媒として使
われる化合物としてピロリジンメタノ−ル誘導体が知ら
れているが、最も単純な(S)−2−ピロリジンメタノ
−ルでは一般に高い不斉収率は得られない為、より複雑
な誘導体に変換する必要があった(例えば K.Soaiet
al., J.Am.Chem.Soc.,109,7111 (1987))。また、分子
内にピロリジンメタノ−ル構造を2個含む化合物は少な
く、これを用いて光学活性二級アルコ−ルを製造した例
はあまり知られていなかった(例えば、 L.Colombo et
al.,Tetrahedron 38,2725 (1982) )。Conventionally, a pyrrolidine methanol derivative has been known as a compound used as an asymmetric catalyst when an optically active secondary alcohol is produced from an aldehyde or a ketone, but the simplest (S) -2- Pyrrolidine methanol generally does not give high asymmetric yields, so conversion to more complex derivatives was necessary (eg K. Soaiet
al., J. Am. Chem. Soc., 109, 7111 (1987)). In addition, there are few compounds containing two pyrrolidine methanol structures in the molecule, and an example of producing an optically active secondary alcohol using the same was not well known (for example, L. Colombo et.
al., Tetrahedron 38,2725 (1982)).
【0004】[0004]
【発明が解決しようとする課題】本発明の課題は、製造
が容易で不斉触媒として有用な2−ピロリジンメタノ−
ル誘導体を提供し、これを用いて光学活性二級アルコ−
ルを製造することである。The object of the present invention is to provide 2-pyrrolidinemethano- which is easy to produce and useful as an asymmetric catalyst.
To provide an optically active secondary alcohol.
Is to manufacture
【0005】[0005]
【課題を解決するための手段】本発明者らは、上記の課
題を解決するため検討を重ねた結果化1で示される2−
ピロリジンメタノ−ル誘導体が不斉触媒として優れてい
ることを見いだし本発明を完成した。すなわち本発明は
一般式Means for Solving the Problems The present inventors have made extensive studies to solve the above problems
The present invention was completed by discovering that pyrrolidine methanol derivatives are excellent as asymmetric catalysts. That is, the present invention has the general formula
【化6】 (式中、R1、R2は同一でも異なっていてもよく水素原
子またはハロゲン原子もしくはニトロ基が1〜5個置換
されていてもよいフェニル基を、Zは水素原子、Li、
Na、K、−MgC2H5または炭素数1〜6の置換基を
有してもよいアルキル基を示し、*は不斉炭素を示
す。)で示される2−ピロリジンメタノ−ル誘導体をア
ルデヒドのアルキル化反応やケトンの還元反応に触媒と
して使用することを特徴とする光学活性二級アルコ−ル
の製造方法に関するものである。[Chemical 6] (In the formula, R 1 and R 2 may be the same or different and each is a hydrogen atom or a phenyl group which may be substituted with 1 to 5 halogen atoms or nitro groups, Z is a hydrogen atom, Li,
Na, K, -MgC2H5 or an alkyl group having 1 to 6 carbon atoms which may have a substituent, and * represents an asymmetric carbon. The present invention relates to a method for producing an optically active secondary alcohol, which comprises using a 2-pyrrolidinemethanol derivative represented by the formula (4) as a catalyst for an aldehyde alkylation reaction or a ketone reduction reaction.
【0006】本発明に用いられる化1で示される2−ピ
ロリジンメタノ−ルの製造は、化4で示される化合物を
ジクロロメタンと反応させることにより得られる。一般
式化1の式中R1、R2は同一でも異なっていてもよく水
素原子またはハロゲン原子もしくはニトロ基が1〜5個
置換されていてもよいフェニル基を、Zは水素原子、L
i、Na、K、−MgC2H5またはメチル基、エチル基
等の炭素数1〜6の置換基を有してもよいアルキル基を
示し、*は不斉炭素を示す。The 2-pyrrolidine methanol represented by the formula 1 used in the present invention can be obtained by reacting the compound represented by the formula 4 with dichloromethane. In the formula of the general formula 1, R1 and R2 may be the same or different and each is a hydrogen atom or a phenyl group which may be substituted with 1 to 5 halogen atoms or nitro groups, Z is a hydrogen atom, L
i, Na, K, -MgC2H5 or an alkyl group which may have a substituent having 1 to 6 carbon atoms such as a methyl group or an ethyl group, and * represents an asymmetric carbon.
【0007】この反応は好ましくは無機または有機塩基
の存在下に行われ、例えば化4のジクロロメタン溶液を
水酸化ナトリウム水溶液と共に一晩加熱還流することに
よって高収率で化1の化合物を得ることができる。無機
塩基としては例えば水酸化ナトリウム、水酸化カリウム
があげられ、有機塩基としてはナトリウムメトキサイ
ド、トリエチルアミン等があげられる。塩基の量は化4
で示される出発物質に対して通常5当量以下用いる。This reaction is preferably carried out in the presence of an inorganic or organic base, for example by heating a dichloromethane solution of Chemical formula 4 under reflux with an aqueous sodium hydroxide solution overnight to obtain the compound of Chemical formula 1 in high yield. it can. Examples of the inorganic base include sodium hydroxide and potassium hydroxide, and examples of the organic base include sodium methoxide and triethylamine. The amount of base is
Usually, 5 equivalents or less are used with respect to the starting material shown in.
【0008】ジクロロメタンの使用量は通常大過剰に用
いられる。The amount of dichloromethane used is usually in a large excess.
【0009】反応温度は、25から50℃であり、反応
時間は数時間から数日である。得られた化1で示される
2−ピロリジンメタノ−ル誘導体は再結晶により容易に
単離することができる。The reaction temperature is 25 to 50 ° C., and the reaction time is several hours to several days. The obtained 2-pyrrolidinemethanol derivative represented by Chemical formula 1 can be easily isolated by recrystallization.
【0010】本発明で用いられる化1で示される2−ピ
ロリジンメタノ−ルは不斉反応触媒として不斉合成反応
に用いることができる。詳細に述べると、例えば光学活
性第二級アルコ−ルの製造に不斉触媒として用いること
ができる。光学活性第二アルコ−ルの製造方法として
は、アルデヒドをアルキル化反応する方法や、ケトンを
還元する方法、アルケンを酸化する方法等が挙げられ、
本発明の化合物を反応時に加えることによりこれらの反
応を立体選択的に行わせることができる。The 2-pyrrolidine methanol represented by Chemical formula 1 used in the present invention can be used as an asymmetric reaction catalyst in an asymmetric synthesis reaction. More specifically, it can be used as an asymmetric catalyst in the production of, for example, an optically active secondary alcohol. Examples of the method for producing the optically active second alcohol include a method of alkylating an aldehyde, a method of reducing a ketone, a method of oxidizing an alkene, and the like.
These reactions can be carried out stereoselectively by adding the compounds of the present invention during the reaction.
【0011】アルデヒドのアルキル化に用いられるアル
デヒドは一般式Aldehydes used for the alkylation of aldehydes have the general formula
【化7】 (式中、R3は炭素数1〜12のアルキル基または一般
式化8で示される官能基を示す。)で表わされる。具体
的にはアセトアルデヒド、ベンズアルデヒド等が挙げら
れる。[Chemical 7] (In the formula, R3 represents an alkyl group having 1 to 12 carbon atoms or a functional group represented by the general formula 8). Specific examples thereof include acetaldehyde and benzaldehyde.
【0012】[0012]
【化8】 (式中、XおよびYは同一でも異なっていてもよく水素
原子、ハロゲン原子、ニトロ基、シアノ基を、mおよび
nは0、1もしくは2を、αおよびβはアルキレン、エ
ステル、エ−テル結合を、R4は炭素数1〜16のアル
キル基を示す。)[Chemical 8] (In the formula, X and Y may be the same or different and each is a hydrogen atom, a halogen atom, a nitro group or a cyano group, m and n are 0, 1 or 2, and α and β are alkylene, ester or ether. R4 represents an alkyl group having 1 to 16 carbon atoms.
【0013】アルキル化反応には一般に用いられるアル
キル化剤が使用でき例えば、ジアルキル亜鉛、アルキル
リチウム等が用いられる。ケトンの還元反応に用いられ
るケトンは一般式In the alkylation reaction, a commonly used alkylating agent can be used, and examples thereof include dialkyl zinc and alkyl lithium. The ketone used in the reduction reaction of the ketone has the general formula
【化9】 (式中、R5は炭素数1〜12のアルキル基もしくは一
般式化8で示される官能基を、R6は置換基を有してい
てもよいアルキル基、アルケニル基、アリ−ル基もしく
はアラルキル基を示し、R5とR6は一緒になって環を形
成してもよい。)で表わされる。具体的には、アセトフ
ェノン、プロピオフェノン等が挙げられる。[Chemical 9] (In the formula, R5 represents an alkyl group having 1 to 12 carbon atoms or a functional group represented by the general formula 8; R6 represents an alkyl group, an alkenyl group, an aryl group or an aralkyl group which may have a substituent. And R5 and R6 may together form a ring). Specific examples include acetophenone and propiophenone.
【0014】還元剤としては、一般に用いられる還元剤
が使用でき例えば、水素化リチウムアルミニウム、水素
化ホウ素ナトリウム、ボラン等が用いられる。使用する
触媒量は基質により異なるが、通常基質に対しアルキル
化反応では0.1から1当量、還元反応では1から4当
量である。As the reducing agent, a commonly used reducing agent can be used. For example, lithium aluminum hydride, sodium borohydride, borane and the like are used. The amount of catalyst used varies depending on the substrate, but is usually 0.1 to 1 equivalent in the alkylation reaction and 1 to 4 equivalents in the reduction reaction with respect to the substrate.
【0015】[0015]
実施例1 N、N’−ビス((S)−2−ヒドロキシメ
チルピロリジニル)メタンの合成 (s)−プロリノ−ル 1.0g(9.9mmol)と
水酸化ナトリウム 2.1gをジクロロメタン20ml
と水4mlの二相系に溶かし、24時間加熱還流させ
た。終了後ジクロロメタン30mlで3回抽出して得ら
れたジクロロメタン溶液に無水硫酸ナトリウムを加え乾
燥した後、溶媒を留去して表題化合物0.99gを得た
(収率93.3%)。エ−テル−ヘキサンより再結晶し
て精製した。 融点65.0〜66.0℃ IR(KBr):3600−2400,1460,12
40−1000,950,800,750 cm-1 1H−NMR(CDCl3)δ:1.42−1.55
(m,2H),1.68−1.78(m,4H),1.
94−2.08(m,4H),2.53(ABq,J=
9.0Hz,2H),2.60−2.70(m,2
H),3.10−3.18(m,2H),3.37
(s,2H),3.58(d,J=6Hz,4H)pp
m FDMS:215(M+H)、429(2M+H) [α]20=+76.5(c=1、toluene)Example 1 Synthesis of N, N'-bis ((S) -2-hydroxymethylpyrrolidinyl) methane (s) -prolinol 1.0 g (9.9 mmol) and sodium hydroxide 2.1 g were added to dichloromethane 20 ml.
Was dissolved in a two-phase system of 4 ml of water and heated under reflux for 24 hours. After the completion, anhydrous sodium sulfate was added to a dichloromethane solution obtained by extracting 3 times with 30 ml of dichloromethane and drying, and then the solvent was distilled off to obtain 0.99 g of the title compound (yield 93.3%). It was recrystallized from ether-hexane for purification. Melting point 65.0-66.0 ° C IR (KBr): 3600-2400, 1460, 12
40-1000,950,800,750 cm-1 1H-NMR (CDCl3) δ: 1.42-1.55
(M, 2H), 1.68-1.78 (m, 4H), 1.
94-2.08 (m, 4H), 2.53 (ABq, J =
9.0 Hz, 2H), 2.60-2.70 (m, 2
H), 3.10-3.18 (m, 2H), 3.37.
(S, 2H), 3.58 (d, J = 6Hz, 4H) pp
m FDMS: 215 (M + H), 429 (2M + H) [α] 20 = + 76.5 (c = 1, toluene)
【0016】実施例2 N、N’−ビス((S)−2−
ベンジルオキシメチルピロリジニル)メタンの合成 アルゴン雰囲気下、無水ジメチルホルムアミド5mlに
60%水素化ナトリウム(60%オイルサスペンジョ
ン)460mgを懸濁し、氷冷した。実施例1の化合物
1.07gを無水ジメチルホルムアミド1mlに溶解し
て加え、0℃で30分間、室温で1時間撹拌した。再び
0℃に氷冷し、ベンジルブロマイド1.37mlを加え
0℃で1時間、室温で21時間撹拌した。終了後、反応
液にメタノ−ル2ml、水50mlを加え、ジエチルエ
−テル30mlで3回抽出した。有機層を合わせ、飽和
食塩水で2回洗浄した後、無水硫酸マグネシウムで乾燥
し、溶媒を留去した。得られた残さをシリカゲルクロマ
トグラフィ−でエ−テル−ヘキサンの1:1混合液を溶
離液として精製し、表題化合物692.0mgを得た
(収率35.1%)。Example 2 N, N'-bis ((S) -2-
Synthesis of benzyloxymethylpyrrolidinyl) methane Under an argon atmosphere, 460 mg of 60% sodium hydride (60% oil suspension) was suspended in 5 ml of anhydrous dimethylformamide, and cooled with ice. 1.07 g of the compound of Example 1 was dissolved in 1 ml of anhydrous dimethylformamide and added, and the mixture was stirred at 0 ° C. for 30 minutes and at room temperature for 1 hour. The mixture was ice-cooled again to 0 ° C., 1.37 ml of benzyl bromide was added, and the mixture was stirred at 0 ° C. for 1 hour and at room temperature for 21 hours. After the completion, 2 ml of methanol and 50 ml of water were added to the reaction solution, and the mixture was extracted 3 times with 30 ml of diethyl ether. The organic layers were combined, washed twice with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was evaporated. The obtained residue was purified by silica gel chromatography using a 1: 1 mixed solution of ether-hexane as an eluent to obtain 692.0 mg of the title compound (yield 35.1%).
【0017】実施例3 不斉アルキル化反応による1−
フェニル−1−ペンタノ−ルの合成 実施例1の化合物321mgを無水ジメトキシメタン2
0mlに溶解し、0℃で撹拌した。n−ブチルリチウム
(1.6M/lのヘキサン溶液)5.63mlを加え、
0℃で30分撹拌した。−65℃に冷却しベンズアルデ
ヒド305μlを滴下した。同温で1.5時間撹拌した
後、3N塩酸10mlを加えエ−テル10mlで3回抽
出した。飽和食塩水で洗浄後、無水硫酸マグネシウムで
乾燥した。分取用シリカゲルTLCで分取し、表題化合
物453mgを得た(収率92%)。光学活性カラム
(ダイセル Chiralcel OB)で分析したところ、光学純
度は5.6%ee(R体)であった。Example 3 1-by asymmetric alkylation reaction
Synthesis of Phenyl-1-pentanol 321 mg of the compound of Example 1 was treated with anhydrous dimethoxymethane 2
It was dissolved in 0 ml and stirred at 0 ° C. 5.63 ml of n-butyllithium (1.6 M / l hexane solution) was added,
The mixture was stirred at 0 ° C for 30 minutes. After cooling to −65 ° C., 305 μl of benzaldehyde was added dropwise. After stirring at the same temperature for 1.5 hours, 10 ml of 3N hydrochloric acid was added and the mixture was extracted 3 times with 10 ml of ether. The extract was washed with saturated saline and dried over anhydrous magnesium sulfate. Preparative silica gel TLC fractionation gave 453 mg of the title compound (yield 92%). When analyzed by an optically active column (Daicel Chiralcel OB), the optical purity was 5.6% ee (R form).
【0018】実施例4 不斉アルキル化反応による1−
フェニル−1−プロパノ−ルの合成 実施例1の化合物64.3mgをトルエン3mlに溶解
し、25℃で撹拌した。ジエチル亜鉛(1.0M/lヘ
キサン溶液)6mlを加え25℃で15分間撹拌した
後、氷冷下にベンズアルデヒド318.4mgを加え
た。5℃で21時間撹拌した後、3N塩酸10mlを加
えエ−テル10mlを加えて不溶物を濾過して除いた。
濾液を分層し、水層をエ−テル10mlで3回抽出し
た。有機層を合わせ飽和食塩水で洗浄後、無水硫酸マグ
ネシウムで乾燥した。溶媒を留去し、シリカゲルクロマ
トグラフィ−にて精製して表題化合物173.4mgを
得た(収率42.5%)。光学活性カラム(ダイセルCh
iralcel OB)で分析したところ、光学純度は29.0%
ee(R体)であった。Example 4 1-by asymmetric alkylation reaction
Synthesis of Phenyl-1-propanol 64.3 mg of the compound of Example 1 was dissolved in 3 ml of toluene and stirred at 25 ° C. After adding 6 ml of diethyl zinc (1.0 M / l hexane solution) and stirring at 25 ° C. for 15 minutes, 318.4 mg of benzaldehyde was added under ice cooling. After stirring at 5 ° C. for 21 hours, 10 ml of 3N hydrochloric acid was added, 10 ml of ether was added, and the insoluble matter was removed by filtration.
The filtrate was separated into layers, and the aqueous layer was extracted 3 times with 10 ml of ether. The organic layers were combined, washed with saturated brine, and dried over anhydrous magnesium sulfate. The solvent was evaporated, and the residue was purified by silica gel chromatography to give the title compound (173.4 mg) (yield 42.5%). Optically active column (Daicel Ch
Optical purity is 29.0% when analyzed by iralcel OB)
It was ee (R form).
【0019】実施例5 不斉還元反応による1−フェニ
ル−1−プロパノ−ルの合成 水素化リチウムアルミニウム400mgに、アルゴン雰
囲気下、テトラヒドロフラン(THF)6mlを加え、
エタノ−ルのTHF溶液(2M/l)5.0mlを滴下
した。実施例1の化合物2.14gをTHF17mlに
溶解し滴下した。室温で30分間撹拌した後、−78℃
に冷却し、プロピオフェノン402mgのTHF溶液
(3ml)を8分間かけて滴下した。同温で5時間撹拌
した後、メタノ−ル1.2mlを加えた。室温まで昇温
し、2N塩酸24mlを加えた後、エ−テル20mlで
3回抽出した。有機層を合わせ、飽和食塩水で洗浄後、
無水硫酸マグネシウムで乾燥した。溶媒を留去し、シリ
カゲルクロマトグラフィ−にて精製して表題化合物30
0.0mgを得た(収率73.4%)。光学活性カラム
(ダイセルChiralcel OB)で分析したところ、光学純度
は67.8%ee(R体)であった。Example 5 Synthesis of 1-phenyl-1-propanol by asymmetric reduction reaction To 400 mg of lithium aluminum hydride, 6 ml of tetrahydrofuran (THF) was added under an argon atmosphere,
5.0 ml of a THF solution of ethanol (2 M / l) was added dropwise. 2.14 g of the compound of Example 1 was dissolved in 17 ml of THF and added dropwise. After stirring at room temperature for 30 minutes, -78 ° C
After cooling, the THF solution (3 ml) of 402 mg of propiophenone was added dropwise over 8 minutes. After stirring at the same temperature for 5 hours, 1.2 ml of methanol was added. The temperature was raised to room temperature, 24 ml of 2N hydrochloric acid was added, and the mixture was extracted 3 times with 20 ml of ether. After combining the organic layers and washing with saturated saline,
It was dried over anhydrous magnesium sulfate. The solvent was distilled off, and the title compound 30 was purified by silica gel chromatography.
0.0 mg was obtained (yield 73.4%). When analyzed by an optically active column (Daicel Chiralcel OB), the optical purity was 67.8% ee (R form).
【0020】[0020]
【発明の効果】本発明のピロリジンメタノ−ル誘導体を
触媒として用いることにより、高い光学収率で光学活性
二級アルコ−ルを製造することができる。By using the pyrrolidinemethanol derivative of the present invention as a catalyst, an optically active secondary alcohol can be produced with a high optical yield.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 池村 治 神奈川県川崎市川崎区鈴木町1−1 味の 素株式会社中央研究所内 (72)発明者 井澤 邦輔 神奈川県川崎市川崎区鈴木町1−1 味の 素株式会社中央研究所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor, Osamu Ikemura 1-1, Suzuki-cho, Kawasaki-ku, Kanagawa Prefecture Central Research Institute of Ajinomoto Co., Inc. 1 Central Research Laboratory, Ajinomoto Co., Inc.
Claims (4)
子またはハロゲン原子もしくはニトロ基が1〜5個置換
されていてもよいフェニル基を、Zは水素原子、Li、
Na、K、−MgC2H5または炭素数1〜6の置換基を
有してもよいアルキル基を示し、*は不斉炭素を示
す。)で表わされる2−ピロリジンメタノ−ル誘導体を
触媒として使用することを特徴とするアルデヒドのアル
キル化反応による光学活性二級アルコ−ルの製造方法。1. A general formula: (In the formula, R 1 and R 2 may be the same or different and each is a hydrogen atom or a phenyl group which may be substituted with 1 to 5 halogen atoms or nitro groups, Z is a hydrogen atom, Li,
Na, K, -MgC2H5 or an alkyl group having 1 to 6 carbon atoms which may have a substituent, and * represents an asymmetric carbon. 2. A method for producing an optically active secondary alcohol by an alkylation reaction of an aldehyde, which comprises using a 2-pyrrolidinemethanol derivative represented by the formula) as a catalyst.
子またはハロゲン原子もしくはニトロ基が1〜5個置換
されていてもよいフェニル基を、Zは水素原子、Li、
Na、K、−MgC2H5または炭素数1〜6の置換基を
有してもよいアルキル基を示し、*は不斉炭素を示
す。)で表わされる2−ピロリジンメタノ−ル誘導体を
触媒として使用することを特徴とするケトンの還元反応
による光学活性二級アルコ−ルの製造方法。2. A general formula: (In the formula, R 1 and R 2 may be the same or different and each is a hydrogen atom or a phenyl group which may be substituted with 1 to 5 halogen atoms or nitro groups, Z is a hydrogen atom, Li,
Na, K, -MgC2H5 or an alkyl group having 1 to 6 carbon atoms which may have a substituent, and * represents an asymmetric carbon. 2. A method for producing an optically active secondary alcohol by a reduction reaction of a ketone, which comprises using a 2-pyrrolidinemethanol derivative as a catalyst.
子またはハロゲン原子もしくはニトロ基が1〜5個置換
されていてもよいフェニル基を、Zは水素原子、Li、
Na、K、−MgC2H5または炭素数1〜6の置換基を
有してもよいアルキル基を示し、*は不斉炭素を示
す。)で表わされる2−ピロリジンメタノ−ル誘導体。3. A general formula: (In the formula, R 1 and R 2 may be the same or different and each is a hydrogen atom or a phenyl group which may be substituted with 1 to 5 halogen atoms or nitro groups, Z is a hydrogen atom, Li,
Na, K, -MgC2H5 or an alkyl group having 1 to 6 carbon atoms which may have a substituent, and * represents an asymmetric carbon. ) 2-pyrrolidine methanol derivative represented by
子またはハロゲン原子もしくはニトロ基が1〜5個置換
されていてもよいフェニル基を、Zは水素原子、Li、
Na、K、−MgC2H5または炭素数1〜6の置換基を
有してもよいアルキル基を示し、*は不斉炭素を示
す。)で表わされる化合物にジクロロメタンを反応させ
ることを特徴とする一般式 【化5】 (式中、R1、R2は同一でも異なっていてもよく水素原
子またはハロゲン原子もしくはニトロ基が1〜5個置換
されていてもよいフェニル基を、Zは水素原子、Li、
Na、K、−MgC2H5または炭素数1〜6の置換基を
有してもよいアルキル基を示し、*は不斉炭素を示
す。)で表される2−ピロリジンメタノ−ル誘導体の製
造方法。4. A general formula: (In the formula, R 1 and R 2 may be the same or different and each is a hydrogen atom or a phenyl group which may be substituted with 1 to 5 halogen atoms or nitro groups, Z is a hydrogen atom, Li,
Na, K, -MgC2H5 or an alkyl group having 1 to 6 carbon atoms which may have a substituent, and * represents an asymmetric carbon. ) A compound represented by the general formula: (In the formula, R 1 and R 2 may be the same or different and each is a hydrogen atom or a phenyl group which may be substituted with 1 to 5 halogen atoms or nitro groups, Z is a hydrogen atom, Li,
Na, K, -MgC2H5 or an alkyl group having 1 to 6 carbon atoms which may have a substituent, and * represents an asymmetric carbon. ) The manufacturing method of the 2-pyrrolidine methanol derivative represented by these.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3263702A JPH0597735A (en) | 1991-10-11 | 1991-10-11 | Production of optically active secondary alcohol |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3263702A JPH0597735A (en) | 1991-10-11 | 1991-10-11 | Production of optically active secondary alcohol |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH0597735A true JPH0597735A (en) | 1993-04-20 |
Family
ID=17393143
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP3263702A Pending JPH0597735A (en) | 1991-10-11 | 1991-10-11 | Production of optically active secondary alcohol |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0597735A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010248089A (en) * | 2009-04-10 | 2010-11-04 | Kyoto Univ | Compound comprising heterocyclic skeleton, and method of producing optically active compound using the same as asymmetric catalyst |
CN103539633A (en) * | 2013-09-27 | 2014-01-29 | 安徽华印机电股份有限公司 | Palladium carbon catalyzed alpha-alkylation reaction of methyl ketone |
-
1991
- 1991-10-11 JP JP3263702A patent/JPH0597735A/en active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010248089A (en) * | 2009-04-10 | 2010-11-04 | Kyoto Univ | Compound comprising heterocyclic skeleton, and method of producing optically active compound using the same as asymmetric catalyst |
CN103539633A (en) * | 2013-09-27 | 2014-01-29 | 安徽华印机电股份有限公司 | Palladium carbon catalyzed alpha-alkylation reaction of methyl ketone |
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