JP2792639B2 - Catalyst for asymmetric nitroaldol reaction - Google Patents
Catalyst for asymmetric nitroaldol reactionInfo
- Publication number
- JP2792639B2 JP2792639B2 JP4286371A JP28637192A JP2792639B2 JP 2792639 B2 JP2792639 B2 JP 2792639B2 JP 4286371 A JP4286371 A JP 4286371A JP 28637192 A JP28637192 A JP 28637192A JP 2792639 B2 JP2792639 B2 JP 2792639B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- lanthanum
- formula
- binaphthyl
- dihydroxy
- 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.)
- Expired - Fee Related
Links
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
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、光学活性ランタン化合
物を含む不斉ニトロアルドール反応用触媒に関する。The present invention relates to a catalyst for an asymmetric nitroaldol reaction containing an optically active lanthanum compound.
【０００２】[0002]
【従来の技術】本発明者らは、無水の条件下において、
光学活性２，２′−ジヒドロキシ−１，１′−ビナフチ
ルのジリチウム塩、および三価の塩化ランタンから、光
学活性ランタン化合物を調製し、これが不斉ニトロアル
ドール反応の触媒として有用であることを見出してい
る。（日本薬学会主催、反応と合成の進歩シンポジウ
ム、１９９１年１１月７日発表）2. Description of the Related Art The present inventors, under anhydrous conditions,
An optically active lanthanum compound was prepared from a dilithium salt of optically active 2,2'-dihydroxy-1,1'-binaphthyl and trivalent lanthanum chloride, and was found to be useful as a catalyst for an asymmetric nitroaldol reaction. ing. (Symposium on Progress in Reactions and Synthesis, sponsored by the Pharmaceutical Society of Japan, announced on November 7, 1991)
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、その反
応収率あるいは不斉収率にまったく再現性がなく、本質
的には不斉ニトロアルドール反応が、生理活性化合物の
重要な合成原料を与える極めて有用な反応であるにもか
かわらず、その有用性を十分に発揮させることができな
かった。そこで不斉ニトロアルドール反応によっての
み、効率的に製造することが可能な医薬品を、工業的に
製造するためには、その反応収率および不斉収率をとも
に高く、かつ再現性のある不斉ニトロアルドール反応用
触媒を開発する必要がある。However, the reaction yield or the asymmetric yield is not reproducible at all, and essentially the asymmetric nitroaldol reaction is extremely useful for providing an important raw material for synthesizing a physiologically active compound. Despite the difficult reaction, its usefulness could not be fully exhibited. Therefore, in order to industrially produce a drug that can be efficiently produced only by the asymmetric nitroaldol reaction, the reaction yield and the asymmetric yield are both high and the reproducible asymmetric It is necessary to develop a catalyst for the nitroaldol reaction.
【０００４】本発明の目的は、不斉ニトロアルドール反
応用触媒を提供することであり、不斉ニトロアルドール
反応において再現性のある活性種を提供することであ
る。An object of the present invention is to provide a catalyst for an asymmetric nitroaldol reaction, and to provide a reproducible active species in an asymmetric nitroaldol reaction.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、原料の種
類、純度、反応条件などについて鋭意研究を行った結
果、不斉ニトロアルドール反応の不斉触媒として作用す
る光学活性ランタン化合物に原因があることを究明し、
この反応において完全な再現性が保たれる活性種を見出
し、本発明を完成するに至った。すなわちMeans for Solving the Problems The present inventors have conducted intensive studies on the type, purity, reaction conditions, and the like of the raw materials, and as a result, have found that the cause of the optically active lanthanum compound acting as an asymmetric catalyst in an asymmetric nitroaldol reaction is as follows. To determine that
An active species that maintains perfect reproducibility in this reaction was found, and the present invention was completed. Ie
【０００６】本発明の第１の不斉ニトロアルドール反応
用触媒は、式（ＩR）The first catalyst for asymmetric nitroaldol reaction of the present invention has the formula (I R )
【化１１】 もしくは、式（ＩS）Embedded image Or the formula (I S )
【化１２】 で示される光学活性２，２′−ジヒドロキシ−１，１′
−ビナフチルのジアルカリ金属塩（たゞし、式中、Ｍは
Ｌｉ，ＫもしくはＮａである）、ＬａＸ3（ＸはＦ，Ｃ
ｌ，Ｂｒ，Ｉ，ＮＯ3もしくはＣＨ3ＣＯ2である）で示
されるランタン化合物、およびＭＯＲもしくはＭＯＨ
（ＭはＬｉ，ＫもしくはＮａであり、Ｒはイソプロピル
もしくはｔ−ブチルである）で示されるアルカリ金属ア
ルコキシドもしくは水酸化アルカリ金属から、含水溶媒
存在下で調製されることを特徴とする。Embedded image Optically active 2,2'-dihydroxy-1,1 'represented by
- dialkali metal salts of binaphthyl (to Isuzu was, wherein, M is Li, is K or Na), LaX 3 (X is F, C
l, Br, I, NO 3 or CH 3 CO 2 ), and MOR or MOH
(Wherein M is Li, K or Na, and R is isopropyl or t-butyl), characterized by being prepared from an alkali metal alkoxide or an alkali metal hydroxide in the presence of a hydrous solvent.
【０００７】好ましい態様としては、エーテル系溶媒も
しくは含水エーテル系溶媒中で調製される。また、前記
活性２，２′−ジヒドロキシ−１，１′−ビナフチルの
ジアルカリ金属塩、前記ランタン化合物および前記アル
カリ金属アルコキシドもしくは水酸化アルカリ金属のモ
ル比が１：１：１から１：１：２の範囲であることが好
ましい。[0007] In a preferred embodiment, it is prepared in an ether solvent or a hydrous ether solvent. The molar ratio of the dialkali metal salt of the active 2,2'-dihydroxy-1,1'-binaphthyl, the lanthanum compound and the alkali metal alkoxide or alkali metal hydroxide is from 1: 1: 1 to 1: 1: 2. Is preferably within the range.
【０００８】本発明の第２の不斉ニトロアルドール反応
用触媒の使用方法は、式（IIR）The method for using the second asymmetric nitroaldol reaction catalyst of the present invention is represented by the formula (II R )
【化１３】 もしくは、式（IIS）Embedded image Or formula (II S)
【化１４】 で示される光学活性２，２′−ジヒドロキシ−１，１′
−ビナフチルおよびＬａ（ＯＲ）3（Ｒはイソプロピル
もしくはｔ−ブチルである）で示されるランタンアルコ
キシドから得られる活性種を塩化リチウム、含水溶媒の
存在下で用いることを特徴とする。Embedded image Optically active 2,2'-dihydroxy-1,1 'represented by
An active species obtained from lanthanum alkoxide represented by binaphthyl and La (OR) 3 (R is isopropyl or t-butyl) is used in the presence of lithium chloride and a water-containing solvent.
【０００９】好ましい態様は、前記活性種を塩化リチウ
ム、水、エーテル系溶媒の存在下で用いることが望まし
い。また、前記光学活性２，２′−ジヒドロキシ−１，
１′−ビナフチルおよび前記ランタンアルコキシドのモ
ル比は２：１〜１：１の範囲で用いることができるが
３：２が好ましい。In a preferred embodiment, it is desirable to use the active species in the presence of lithium chloride, water and an ether solvent. In addition, the optically active 2,2'-dihydroxy-1,
The molar ratio of 1'-binaphthyl and the lanthanum alkoxide can be used in the range of 2: 1 to 1: 1 but preferably 3: 2.
【００１０】本発明の不斉ニトロアルドール反応用触媒
に用いる光学活性２，２′−ジヒドロキシ−１，１′−
ビナフチルジアルカリ金属塩は、光学活性２，２′−ジ
ヒドロキシ−１，１′−ビナフチルに、ＴＨＦなどの非
プロトン性溶媒中、水素化カリウム、水素化ナトリウ
ム、あるいは水素化リチウムなどの水素化アルカリ金属
を作用させる方法、あるいは、水、アルコールなどのプ
ロトン性溶媒中、水酸化カリウム、水酸化ナトリウム、
あるいは水酸化リチウムなどの水酸化アルカリ金属を作
用させた後、乾燥させる方法のいずれによっても調製さ
れる。The optically active 2,2'-dihydroxy-1,1'- used in the catalyst for asymmetric nitroaldol reaction of the present invention.
Binaphthyl dialkali metal salt is prepared by adding optically active 2,2'-dihydroxy-1,1'-binaphthyl to an alkali hydride such as potassium hydride, sodium hydride or lithium hydride in an aprotic solvent such as THF. Method of reacting metal, or water, in a protic solvent such as alcohol, potassium hydroxide, sodium hydroxide,
Alternatively, it is prepared by any method of drying after allowing an alkali metal hydroxide such as lithium hydroxide to act.
【００１１】本発明の触媒に用いるＬａＸ3で示される
ランタン化合物としては、塩化ランタンなどのハロゲン
化ランタン、硝酸ランタン、酢酸ランタンなど三価のラ
ンタン化合物である。The lanthanum compound represented by LaX 3 used in the catalyst of the present invention is a lanthanum halide such as lanthanum chloride, a trivalent lanthanum compound such as lanthanum nitrate or lanthanum acetate.
【００１２】アルカリ金属アルコキシドとしては、ナト
リウム−ｔ−ブトキシド、カリウム−ｔ−ブトキシド、
リチウム−ｔ−ブトキシド、あるいはカリウムイソプロ
ボキシド、ナトリウムイソプロボキシド、リチウムイソ
プロボキシドなどが好ましく用いられる。As the alkali metal alkoxide, sodium tert-butoxide, potassium tert-butoxide,
Lithium-t-butoxide, potassium isopropoxide, sodium isopropoxide, lithium isopropoxide and the like are preferably used.
【００１３】本発明の触媒の調製に必須の水としては、
次の方法のいずれによっても、反応系内に導入すること
ができる。１）塩化ランタン七水和物、硝酸ランタン九
水和物、酢酸ランタンｎ水和物などの三価のランタン化
合物の水和物、２）含水ＴＨＦ、含水ジオキサン、含水
ジエチルエーテルなどの含水エーテル系溶媒。この系内
に加えられた水は、有機溶媒に不溶な三価のランタン化
合物とビナフチル誘導体との円滑な反応を促進し、なら
びに高い不斉発現能を有する構造の光学活性ランタン化
合物の生成に作用する。使用する水の量は、原料の三価
のランタン化合物１に対し、１〜２０モル等量が好まし
く、特に１０モル等量が望ましい。The water essential for the preparation of the catalyst of the present invention includes:
It can be introduced into the reaction system by any of the following methods. 1) hydrates of trivalent lanthanum compounds such as lanthanum chloride heptahydrate, lanthanum nitrate nonahydrate, and lanthanum acetate n-hydrate; 2) water-containing ethers such as water-containing THF, water-containing dioxane, and water-containing diethyl ether; solvent. The water added to the system promotes a smooth reaction between the trivalent lanthanum compound insoluble in the organic solvent and the binaphthyl derivative, and acts on the formation of an optically active lanthanum compound having a structure capable of exhibiting high asymmetric expression. I do. The amount of water used is preferably 1 to 20 molar equivalents, particularly preferably 10 molar equivalents, based on the trivalent lanthanum compound 1 as a raw material.
【００１４】本発明に用いられる光学活性２，２′−ジ
ヒドロキシ−１，１′−ビナフチルの絶対配置として
は、ＲおよびＳの両鏡像体ともに使用できる。具体的に
は前記式（IIR）で示される（Ｒ）−（＋）−２，２′
−ジヒドロキシ−１，１′−ビナフチルもしくは式（II
S）で示される（Ｓ）−（−）−２，２′ジヒドロキシ
−１，１′−ビナフチルである。As the absolute configuration of the optically active 2,2'-dihydroxy-1,1'-binaphthyl used in the present invention, both R and S enantiomers can be used. Specifically, (R)-(+)-2,2 'represented by the above formula (II R )
-Dihydroxy-1,1'-binaphthyl or a compound of the formula (II
Represented by S) (S) - (- ) - 2,2 'dihydroxy-1,1'-binaphthyl.
【００１５】本発明の触媒に用いるランタンアルコキシ
ドは、既知の方法（J. Am. Chem. Soc. 110, 1841 (198
8)）により反応系内で調製し、これをそのまま、あるい
は単離精製してから使用しても、いずれの方法も可能で
ある。The lanthanum alkoxide used in the catalyst of the present invention can be prepared by a known method (J. Am. Chem. Soc. 110, 1841 (198
Either method is possible even if it is prepared in a reaction system according to 8)) and used as it is or after isolation and purification.
【００１６】本発明の触媒は、次式で示されるランタン
ビナフトキシドの基本構造単位を有する光学活性ランタ
ン化合物を含有するものである。The catalyst of the present invention contains an optically active lanthanum compound having a basic structural unit of lanthanum binaphthoxide represented by the following formula.
【化１５】 Embedded image
【化１６】 Embedded image
【化１７】 もしくはEmbedded image Or
【化１８】 すなわち、ランタンの希土類元素特有の性質である多様
な結合様式ゆえに、この光学活性ランタン化合物は、単
量体を初めとして、ハロゲン原子やランタン原子あるい
はアルカリ金属原子を橋掛け原子とする二量体、三量体
からオリゴマー、ポリマーあるいはこれらの混合物であ
る。これらは、その調製時に水が存在するとき初めて、
構造的にも、かつ構成比の点においても、不斉ニトロア
ルドール反応に対し、高い触媒活性を有する活性種とし
て安定して生成する。Embedded image In other words, because of the variety of bonding modes that are unique properties of lanthanum rare earth elements, this optically active lanthanum compound includes monomers, dimers having halogen atoms, lanthanum atoms or alkali metal atoms as bridging atoms, It may be a trimer to an oligomer, a polymer or a mixture thereof. These are only when water is present at the time of their preparation,
In terms of the structure and the composition ratio, the compound is stably generated as an active species having high catalytic activity against the asymmetric nitroaldol reaction.
【００１７】本発明の触媒は、たとえば、以下の方法に
より容易に得ることができる。ランタントリｔ−ブトキ
シドを含水ＴＨＦに懸濁させ、これに光学活性２，２′
−ジヒドロキシ−１，１′−ビナフチルを室温で加え、
さらに２時間撹拌後、水、塩化リチウムを加えて調製す
る。あるいは三塩化ランタン七水和物を含水ＴＨＦに懸
濁させ、これに光学活性２，２′−ジヒドロキシ−１，
１′−ビナフチルのジリチウム塩を加え、ついでナトリ
ウムｔ−ブトキシドもしくはアルカリ金属水酸化物およ
び水を加え、この混合物を室温で３日間撹拌することに
よっても調製できる。以下、実施例によって本発明を説
明する。The catalyst of the present invention can be easily obtained, for example, by the following method. Lanthanum tri-t-butoxide is suspended in aqueous THF, and this is added to the optically active 2,2 '.
-Dihydroxy-1,1'-binaphthyl is added at room temperature,
After stirring for another 2 hours, the mixture is prepared by adding water and lithium chloride. Alternatively, lanthanum trichloride heptahydrate is suspended in hydrated THF, and optically active 2,2'-dihydroxy-1,
It can also be prepared by adding the dilithium salt of 1'-binaphthyl, followed by the addition of sodium t-butoxide or an alkali metal hydroxide and water, and stirring the mixture at room temperature for 3 days. Hereinafter, the present invention will be described with reference to examples.
【００１８】[0018]
【実施例】実施例１ 窒素雰囲気下、ランタントリｔ−ブトキシドのＴＨＦ溶
液（単量体として４．９×１０-2ｍｏｌ・ｄｍ-3）７．
５６ｃｍ3へ（Ｓ）−２，２′−ジヒドロキシ−１，
１′−ビナフチル１５９ｍｇ（０．５６ｍｍｏｌ）を室
温で加え、２時間撹拌することによって不斉ニトロアル
ドール反応用触媒を調製した。該触媒の溶媒を除去し、
ＪＥＯＬ ＧＸ−２７０スペトルメーターで1Ｈ−ＮＭ
Ｒ（ＴＨＦ−ｄ8）および13Ｃ−ＮＭＲ（ＴＨＦ−ｄ8）
を測定した。結果をそれぞれ図（１）および図（２）に
示す。EXAMPLE 1 A THF solution of lanthanum tri-t-butoxide (4.9 × 10 −2 mol · dm −3 as a monomer) under a nitrogen atmosphere.
To 56 cm 3 (S) -2,2′-dihydroxy-1,
159 mg (0.56 mmol) of 1'-binaphthyl was added at room temperature, and the mixture was stirred for 2 hours to prepare a catalyst for asymmetric nitroaldol reaction. Removing the solvent of the catalyst,
1 H-NM with JEOL GX-270 spectrum meter
R (THF-d 8) and 13 C-NMR (THF-d 8)
Was measured. The results are shown in FIG. 1 and FIG. 2, respectively.
【００１９】実施例２ 窒素雰囲気下、塩化ランタン・七水和物３７１ｍｇ（１
ｍｍｏｌ）のＴＨＦ懸濁液９ｃｍ3に、（Ｒ）−２，
２′−ジヒドロキシ−１，１′−ビナフチルのジリチウ
ム塩２９８ｍｇ（１ｍｍｏｌ）、ナトリウムｔ−ブトキ
シド１９２ｍｇ（２ｍｍｏｌ）、ついで水１８０ｍｇ
（１０ｍｍｏｌ）のＴＨＦ１ｃｍ3溶液を順に加え、室
温で３日間撹拌し、不斉ニトロアルドール反応用触媒を
調製した。Example 2 In a nitrogen atmosphere, 371 mg of lanthanum chloride / heptahydrate (1
mmol) in 9 cm 3 of a THF suspension.
298 mg (1 mmol) of dilithium salt of 2'-dihydroxy-1,1'-binaphthyl, 192 mg (2 mmol) of sodium t-butoxide, and 180 mg of water
(10 mmol) in THF (1 cm 3 ) was added in order, and the mixture was stirred at room temperature for 3 days to prepare an asymmetric nitroaldol reaction catalyst.
【００２０】実施例３ 窒素雰囲気下、塩化ランタン（１ｍｍｏｌ）のＴＨＦ懸
濁液９ｃｍ3に、（Ｓ）−（−）−２，２′−ジヒドロ
キシ−１，１′−ビナフチルのジリチウム塩（１ｍｍｏ
ｌ）、ナトリウムｔ−ブトキシド（２ｍｍｏｌ）、つい
で水（１０ｍｍｏｌ）のＴＨＦ１ｃｍ3溶液を順に加
え、室温で３日間撹拌し、不斉ニトロアルドール反応用
触媒を調製した。Example 3 Under a nitrogen atmosphere, a dilithium salt of (S)-(−)-2,2′-dihydroxy-1,1′-binaphthyl (1 mmol) was added to 9 cm 3 of a suspension of lanthanum chloride (1 mmol) in THF.
l), sodium t-butoxide (2 mmol) and then a solution of water (10 mmol) in 1 cm 3 of THF were added in that order, and the mixture was stirred at room temperature for 3 days to prepare a catalyst for an asymmetric nitroaldol reaction.
【００２１】実施例４ 窒素雰囲気下、ランタントリｔ−ブトキシドのＴＨＦ溶
液（単量体として４．９×１０-2ｍｏｌ・ｄｍ-3）７．
５６ｃｍ3へ（Ｓ）−２，２′−ジヒドロキシ−１，
１′−ビナフチル１５９ｍｇ（０．５６ｍｍｏｌ）を室
温で加え、２時間撹拌して得られた溶液１０モル％（Ｌ
ａベース）、ＬｉＣｌ ２モル当量（Ｌａに対し）、お
よび水１０モル当量（Ｌａに対し）の存在下、シクロヘ
キシルアルデヒドとニトロメタン（１０当量）とをテト
ラヒドロフラン中、−４２℃で１８時間反応を行ない次
式Example 4 A THF solution of lanthanum tri-t-butoxide in a nitrogen atmosphere (4.9 × 10 -2 mol · dm -3 as a monomer)
To 56 cm 3 (S) -2,2′-dihydroxy-1,
159 mg (0.56 mmol) of 1'-binaphthyl was added at room temperature, and the mixture was stirred for 2 hours and the resulting solution was 10 mol% (L
a), cyclohexylaldehyde and nitromethane (10 equivalents) are reacted in tetrahydrofuran at -42 ° C for 18 hours in the presence of 2 molar equivalents of LiCl (relative to La) and 10 molar equivalents of water (relative to La). Next formula
【化１９】 で示される１−シクロヘキシル−２−ニトロエタノール
を９１％の収率で得た。エナンチオマー過剰率は９０％
ｅｅであった。Embedded image 1-cyclohexyl-2-nitroethanol represented by the formula was obtained in a yield of 91%. 90% enantiomeric excess
ee.
【００２２】実施例５〜６アルデヒドの種類をかえて実
施例４と同様に行った結果を表１に示す。Examples 5 to 6 Table 1 shows the results obtained in the same manner as in Example 4 except that the type of aldehyde was changed.
【００２３】[0023]
【表１】 [Table 1]
【００２４】[0024]
【発明の効果】本発明の触媒は、医薬品例えば光学活性
体プロプラノロールなどの光学活性な化合物の重要な合
成原料であるβ−ヒドロキシニトロ化合物の合成に有用
な不斉ニトロアルドール反応の不斉触媒として極めて有
用である。Industrial Applicability The catalyst of the present invention is useful as an asymmetric catalyst for asymmetric nitroaldol reactions useful for the synthesis of β-hydroxynitro compounds, which are important raw materials for the synthesis of optically active compounds such as optically active compounds such as propranolol. Extremely useful.
【図１】本発明の不斉ニトロアルドール反応用触媒の1
Ｈ−ＮＭＲスペクトル。[1] 1 asymmetric nitroaldol reaction catalyst of the present invention
1 H-NMR spectrum.
【図２】本発明の不斉ニトロアルドール反応用触媒の13
Ｃ−ＮＭＲスペクトル。FIG. 2 shows 13 of the catalyst for asymmetric nitroaldol reaction of the present invention.
C-NMR spectrum.
Claims (8)
−ビナフチルのジアルカリ金属塩（たゞし、式中、Ｍは
Ｌｉ，ＫもしくはＮａである）、ＬａＸ3（ＸはＦ，Ｃ
ｌ，Ｂｒ，Ｉ，ＮＯ3もしくはＣＨ3ＣＯ2である）で示
されるランタン化合物、およびＭＯＲもしくはＭＯＨ
（ＭはＬｉ，ＫもしくはＮａであり、Ｒはイソプロピル
もしくはｔ−ブチルである）で示されるアルカリ金属ア
ルコキシドもしくは水酸化アルカリ金属から、含水溶媒
存在下で調製された式 【化３】 【化４】 【化５】 もしくは 【化６】 で示される基本構造単位を有する不斉ニトロアルドール
反応用触媒。1. A compound of the formula (I R ) Or the formula (I S ) Optically active 2,2'-dihydroxy-1,1 'represented by
- dialkali metal salts of binaphthyl (to Isuzu was, wherein, M is Li, is K or Na), LaX 3 (X is F, C
l, Br, I, NO 3 or CH 3 CO 2 ), and MOR or MOH
Wherein M is Li, K or Na, and R is isopropyl or t-butyl, prepared from an alkali metal alkoxide or an alkali metal hydroxide in the presence of a water-containing solvent. Embedded image Embedded image Or An asymmetric nitroaldol reaction catalyst having a basic structural unit represented by the formula:
項１記載の不斉ニトロアルドール反応用触媒。2. The catalyst for asymmetric nitroaldol reaction according to claim 1, which is prepared in a hydrous ether solvent.
１′−ビナフチルのジアルカリ金属塩、前記ランタン化
合物、および前記アルカリ金属アルコキシドもしくは水
酸化アルカリ金属のモル比が１：１：１から１：１：２
の範囲である請求項１記載の不斉ニトロアルドール反応
用触媒。3. An optically active 2,2'-dihydroxy-1,
The molar ratio of the dialkali metal salt of 1'-binaphthyl, the lanthanum compound, and the alkali metal alkoxide or alkali metal hydroxide is from 1: 1: 1 to 1: 1: 2.
The catalyst for an asymmetric nitroaldol reaction according to claim 1, which is in the range of:
媒が含水エーテル系溶媒である請求項１記載の不斉ニト
ロアルドール反応用触媒。4. The catalyst for asymmetric nitroaldol reaction according to claim 1, wherein the lanthanum compound is a hydrate and the aqueous solvent is an aqueous ether solvent.
−ビナフチルのジアルカリ金属塩（たゞし、ＭはＬｉ，
ＫもしくはＮａである）、塩化ランタンの７水和物、お
よびナトリウムｔ−ブトキシドもしくは水酸化ナトリウ
ムから、含水テトラヒドロフラン中で合成された請求項
１記載の不斉ニトロアルドール反応用触媒。5. A compound of the formula (I R ) Or the formula (I S ) Optically active 2,2'-dihydroxy-1,1 'represented by
A dialkali metal salt of binaphthyl (where M is Li,
K or Na), lanthanum chloride heptahydrate and sodium t-butoxide or sodium hydroxide in an aqueous tetrahydrofuran catalyst for the asymmetric nitroaldol reaction according to claim 1.
−ビナフチルおよびＬａ（ＯＲ）3（Ｒはイソプロピル
もしくはｔ−ブチルである）で示されるランタンアルコ
キシドからエーテル系溶媒中で得られる活性種を塩化リ
チウム、含水溶媒の存在下で用いることを特徴とする不
斉ニトロアルドール反応用触媒の使用方法。6. A compound of the formula (II R ) Or the formula (II S ) Optically active 2,2'-dihydroxy-1,1 'represented by
An active species obtained from a lanthanum alkoxide represented by binaphthyl and La (OR) 3 (R is isopropyl or t-butyl) in an ether solvent is used in the presence of lithium chloride and a water-containing solvent. How to use a catalyst for asymmetric nitroaldol reaction.
在下で用いる請求項６記載の不斉ニトロアルドール反応
用触媒の使用方法。7. The method according to claim 6, wherein the catalyst is used in the presence of lithium chloride, water and an ether solvent.
１，１′−ビナフチルおよび前記ランタンアルコキシド
のモル比が２：１から１：１の範囲である請求項６記載
の不斉ニトロアルドール反応用触媒の使用方法。8. The optically active 2,2′-dihydroxy-
The use of the catalyst for asymmetric nitroaldol reaction according to claim 6, wherein the molar ratio of 1,1'-binaphthyl and the lanthanum alkoxide is in the range of 2: 1 to 1: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4286371A JP2792639B2 (en) | 1992-10-23 | 1992-10-23 | Catalyst for asymmetric nitroaldol reaction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4286371A JP2792639B2 (en) | 1992-10-23 | 1992-10-23 | Catalyst for asymmetric nitroaldol reaction |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06154618A JPH06154618A (en) | 1994-06-03 |
| JP2792639B2 true JP2792639B2 (en) | 1998-09-03 |
Family
ID=17703529
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4286371A Expired - Fee Related JP2792639B2 (en) | 1992-10-23 | 1992-10-23 | Catalyst for asymmetric nitroaldol reaction |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2792639B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE69633252T2 (en) * | 1995-09-26 | 2005-09-08 | Hokko Chemical Industry Co. Ltd. | PROCESS FOR THE PRODUCTION OF OPTICALLY ACTIVE 1-AMINOPHOSPHONIC ACID DERIVATIVES AND PHOSPHONATE COMPOUNDS |
| JP4357332B2 (en) | 2004-03-24 | 2009-11-04 | 三井化学株式会社 | Process for producing optically active nitroalcohols |
| EP1759765A1 (en) * | 2005-09-01 | 2007-03-07 | Ludwig-Maximilians-Universität München | Solutions of anhydrous lanthanide salts and its preparation |
-
1992
- 1992-10-23 JP JP4286371A patent/JP2792639B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06154618A (en) | 1994-06-03 |
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