JP2000191676A - Production of optically active aminophosphine compound - Google Patents
Production of optically active aminophosphine compoundInfo
- Publication number
- JP2000191676A JP2000191676A JP10367754A JP36775498A JP2000191676A JP 2000191676 A JP2000191676 A JP 2000191676A JP 10367754 A JP10367754 A JP 10367754A JP 36775498 A JP36775498 A JP 36775498A JP 2000191676 A JP2000191676 A JP 2000191676A
- Authority
- JP
- Japan
- Prior art keywords
- group
- formula
- optically active
- amino
- binaphthyl
- 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
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)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は光学活性アミノホス
フィン化合物の製造方法に関する。[0001] The present invention relates to a method for producing an optically active aminophosphine compound.
【０００２】[0002]
【従来の技術】従来から、不斉合成反応としては不斉水
素化反応、不斉ヒドロシリル化反応、不斉アルキル化反
応が知られており、これら反応に共存させる触媒能を有
する錯体として、遷移金属錯体が知られている。なかで
もルテニウム、ロジウム、イリジウム、パラジウム等の
遷移金属錯体に光学活性な三級ホスフィン化合物が配位
した錯体は、不斉合成反応の触媒として優れた性質を有
するものである。2. Description of the Related Art Conventionally, asymmetric hydrogenation, asymmetric hydrosilylation, and asymmetric alkylation have been known as asymmetric synthesis reactions. Metal complexes are known. Among them, a complex in which an optically active tertiary phosphine compound is coordinated with a transition metal complex such as ruthenium, rhodium, iridium, or palladium has excellent properties as a catalyst for an asymmetric synthesis reaction.
【０００３】この性能を更に高めるために、いろいろな
構造のホスフィン化合物が数多く報告されている。（"A
symmetric Catalysis In Organic Synthesis",野依良治
著、A Wiley-Interscience Publication, 1996年）。[0003] In order to further enhance this performance, many phosphine compounds having various structures have been reported. ("A
Symmetric Catalysis In Organic Synthesis ", by Ryoji Noyori, A Wiley-Interscience Publication, 1996).
【０００４】最近、光学活性な配位子の中でリン原子だ
けでなく酸素原子や窒素原子等が共存した配位子が報告
されている。これらの配位子は従来とは異なった反応性
を示す例が多い。例えば、1-[2-(ジフェニルホスフィ
ノ)フェロセニル]エチルジメチルアミンのPd錯体を用い
た不斉ヒドロシリル化反応が報告されている(K. Yamamo
toらJ. Am. Chem. Soc., 1971 年、93巻5301頁）。同じ
く不斉ヒドロシリル化反応の例では2-ジフェニルホスフ
ィノ-2'-メトキシ-1,1'-ビナフチルのPd錯体を用いた報
告がある(Y. Uozumiら、J. Am. Chem. Soc., 1991 年、
113 巻、9887頁）。また、2-ジメチルアミノメチル-2'-
ジフェニルホスフィノ-1,1'-ビナフチルが報告されてい
るが不斉反応には用いられていない（Y. Uozumi ら、Te
trahedron1994 年、50巻、4293頁）。Recently, among optically active ligands, ligands in which not only phosphorus atoms but also oxygen atoms and nitrogen atoms coexist have been reported. In many cases, these ligands show different reactivity from conventional ones. For example, an asymmetric hydrosilylation reaction using a Pd complex of 1- [2- (diphenylphosphino) ferrocenyl] ethyldimethylamine has been reported (K. Yamamo
J. Am. Chem. Soc., 1971, 93: 5301). Similarly, in an example of asymmetric hydrosilylation reaction, there is a report using a Pd complex of 2-diphenylphosphino-2′-methoxy-1,1′-binaphthyl (Y.Uozumi et al., J. Am. Chem. Soc., In 1991,
113, 9887). Also, 2-dimethylaminomethyl-2'-
Diphenylphosphino-1,1'-binaphthyl has been reported but not used for asymmetric reactions (Y. Uozumi et al., Te.
trahedron 1994, 50, 4293).
【０００５】しかしながら、対象とする反応またはその
反応基質によってはさらに優れた結果をもたらすよう工
夫しなければならない。[0005] However, depending on the reaction of interest or its reaction substrate, it is necessary to devise even better results.
【０００６】また、光学活性2-アミノ-2'-ヒドロキシ-
1,1'-ビナフチルの合成はβ- アミノナフタレンとβ-
ナフトールとを光学活性フェネチルアミンの銅錯体を用
いてカップリングする方法(M. Smrcina ら、J. Org. Ch
em., 1992 年、57巻、1917頁）や、2-アミノ-2'-ヒドロ
キシ-1,1'-ビナフチルのアミノ基をシッフ塩基にして2-
アミノ-1,2-ジフェニルエタノールを用いて分割する方
法が報告されている(H.Mahmoundら、Tetrahedron: Asym
metry、1998年、9 巻、2035頁）。Stepan Vyskocil ら
は、ここで得られたアミノアルコールをアミノホスフィ
ンに導く例を最近報告した（Stepan VyskocilらJ. Org.
Chem., 63, 7738 (1998)）。Also, optically active 2-amino-2'-hydroxy-
1,1'-Binaphthyl is synthesized from β-aminonaphthalene and β-aminonaphthalene.
A method of coupling with naphthol using an optically active copper complex of phenethylamine (M. Smrcina et al., J. Org.
em., 1992, vol. 57, p. 1917) or 2-amino-2'-hydroxy-1,1'-binaphthyl,
A method of resolving using amino-1,2-diphenylethanol has been reported (H. Mahmound et al., Tetrahedron: Asym
Measurement, 1998, Vol. 9, p. 2035). Stepan Vyskocil et al. Recently reported an example in which the amino alcohol obtained here was converted to an aminophosphine (Stepan Vyskocil et al., J. Org.
Chem., 63, 7738 (1998)).
【０００７】しかしながら、カップリングの選択性が悪
く収率が低かったり、分割の効率も悪いなど改良の余地
が残されている。However, there is room for improvement such as poor coupling selectivity, low yield, and poor separation efficiency.
【０００８】又、文献記載（J. Org. Chem., 63, 7738
(1998)）の方法により、分子内に窒素原子を有するホス
フィン配位子7は、光学活性2-アミノ-2'-ヒドロキシビ
ナフチルを出発原料として合成されている。さらに、光
学活性2-アミノ-2'-ヒドロキシビナフチルは2-アミノナ
フタレンと2-ヒドロキシナフタレンとをスパルテインま
たはフェネチルアミン存在下酸化的に付加をして得られ
るか、ラセミの2-アミノ-2'-ヒドロキシビナフチルを光
学分割して得ている。[0008] In addition, the literature description (J. Org. Chem., 63, 7738)
(1998)), the phosphine ligand 7 having a nitrogen atom in the molecule has been synthesized starting from optically active 2-amino-2'-hydroxybinaphthyl. Further, optically active 2-amino-2'-hydroxybinaphthyl can be obtained by oxidative addition of 2-aminonaphthalene and 2-hydroxynaphthalene in the presence of sparteine or phenethylamine, or racemic 2-amino-2 ' -Hydroxybinaphthyl is obtained by optical resolution.
【０００９】[0009]
【発明が解決しようとする課題】そこで、本発明は光学
活性アミノホスフィン化合物を提供することを目的とす
る。また、本発明は不斉合成反応における選択性（化学
選択性、エナンチオ選択性）、触媒活性等に優れた触媒
の配位子である。Accordingly, an object of the present invention is to provide an optically active aminophosphine compound. Further, the present invention is a catalyst ligand having excellent selectivity (chemical selectivity, enantioselectivity) and catalytic activity in an asymmetric synthesis reaction.
【００１０】[0010]
【課題を解決するための手段】本発明は、上記課題を解
決するために、鋭意開発を重ねた結果、2-ジアルキル
（特にジメチル）アミノ-2'-ジフェニルホスフィノ-1,
1'-ビナフチルが不斉反応に有効であることを見出し
た。Means for Solving the Problems The present invention has been intensively developed to solve the above-mentioned problems, and as a result, 2-dialkyl (particularly dimethyl) amino-2'-diphenylphosphino-1,
1'-binaphthyl was found to be effective for asymmetric reactions.
【００１１】また、この化合物はアルデヒド類とα, β
- 不飽和カルボニル類とのBaylis-Hillman反応において
良好な触媒活性およびエナンチオ選択性を発揮すること
を見出し、更に研究を重ね、ついに本発明を完成した。Further, this compound is composed of aldehydes and α, β
-It has been found that the catalyst exhibits good catalytic activity and enantioselectivity in the Baylis-Hillman reaction with unsaturated carbonyls, and further studies have been made to finally complete the present invention.
【００１２】以下、本発明を詳細に説明する。本発明で
合成される光学活性アミノホスフィン化合物は、下記一
般式(1-1)で表される。Hereinafter, the present invention will be described in detail. The optically active aminophosphine compound synthesized in the present invention is represented by the following general formula (1-1).
【００１３】[0013]
【化１０】 式中、R1、R2は、同一又は相異なる炭素数１ないし４の
低級アルキル基、Arは同一又は相異なるフェニル基、4-
トリル基、3-トリル基、3,5-キシリル基、4-メトキシフ
ェニル基、4-クロロフェニル基を表す。アルキル基とし
てはメチル基、エチル基、プロピル基、イソプロピル
基、ブチル基、イソブチル基、sec-ブチル基、tert-ブ
チル基が例示できる。Embedded image In the formula, R 1 and R 2 are the same or different lower alkyl groups having 1 to 4 carbon atoms, Ar is the same or different phenyl group, 4-
Represents a tolyl group, a 3-tolyl group, a 3,5-xylyl group, a 4-methoxyphenyl group, or a 4-chlorophenyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.
【００１４】また、アミノホスフィンオキシド化合物は
下記一般式(1-2)で表される。The aminophosphine oxide compound is represented by the following general formula (1-2).
【化１１】 式中、R1, R2, Arは上記に示されたものと同じである。Embedded image In the formula, R 1 , R 2 and Ar are the same as those described above.
【００１５】以下、煩雑さを避けるために、本発明の光
学活性な化合物として下記で表される化合物を例にし
て、本発明を説明するが、本発明はこの例に限定される
ものではない。下式(7)Hereinafter, in order to avoid complication, the present invention will be described with reference to the following compounds as examples of the optically active compound of the present invention, but the present invention is not limited to these examples. . The following formula (7)
【化１２】 Embedded image
【００１６】本発明の化合物の好適な製法においては、
(A)先ず始めに下式(2)In a preferred method for preparing the compounds of the present invention,
(A) First, the following equation (2)
【化１３】 で表されるラセミ体を出発物質とし、N-ベンジルシンコ
ニジウムクロリドを用いて光学活性体とし、アミノ基を
保護した後、トリフラート体とし、下式(4)（R1，R2が
メチル基）Embedded image The starting material is a racemic compound represented by the formula, optically active using N-benzylcinchonium chloride, the amino group is protected, and a triflate is obtained by the following formula (4) (R 1 and R 2 are methyl groups) Base)
【化１４】 で表される光学活性なジメチルアミノモノトリフラート
体を調製し、(B)ついで、この誘導体から光学活性なモ
ノホスフィンオキシドを得、さらに還元することにより
製造することができる。この化合物は、式(6)の反応式
によって示される方法により、製造される。Embedded image An optically active dimethylaminomonotriflate represented by the formula (B) is prepared, and then an optically active monophosphine oxide is obtained from this derivative (B), followed by further reduction. This compound is produced by the method represented by the reaction formula of the formula (6).
【化１５】 Embedded image
【００１７】すなわち、K. Dingら(Chem. Commun., 199
7年、693 頁) の方法により容易に得られるラセミ体の2
-アミノ-2'-ヒドロキシ-1,1'-ビナフチル(2)とN-ベンジ
ルシンコニジウムクロリド(3) 1/2 当量反応させて(R)-
(2)-(3)の付加体と光学活体(S)-(2)が得られる。それぞ
れを分離し、付加体は塩酸で処理することにより分解
し、光学活性体それぞれを単離した。アミノ-2'-ヒドロ
キシ-1,1'-ビナフチル((S)-2)をホルムアルデヒドとギ
酸でジメチル化し(S)-5とした。さらに、塩化メチレン
中トリエチルアミン存在下に無水トリフラート(Tf2O)を
反応させ、(S)-4とした。このトリフラート体に酢酸パ
ラジウム,1,3-ビス（ジフェニルホスフィノ）プロパン
（以下DPPPということもある）とN,N-ジイソプロピルエ
チルアミンの存在下、ジフェニルホスフィンオキシドを
反応させて、モノホスフィニル化合物(S)-6を得る。つ
いで、トリエチルアミンの存在下、トリクロロシランを
用いて還元すると目的とする(S)-7が高効率で製造でき
る。That is, K. Ding et al. (Chem. Commun., 199
7 years, p. 693).
-Amino-2'-hydroxy-1,1'-binaphthyl (2) and N-benzylcinchonium chloride (3)
An adduct of (2)-(3) and an optically active body (S)-(2) are obtained. Each was separated, the adduct was decomposed by treating with hydrochloric acid, and each of the optically active compounds was isolated. Amino-2'-hydroxy-1,1'-binaphthyl ((S) -2) was dimethylated with formaldehyde and formic acid to give (S) -5. Further, anhydrous triflate (Tf 2 O) was reacted in methylene chloride in the presence of triethylamine to obtain (S) -4. This triflate is reacted with palladium acetate, 1,3-bis (diphenylphosphino) propane (hereinafter sometimes referred to as DPPP) and diphenylphosphine oxide in the presence of N, N-diisopropylethylamine to obtain a monophosphinyl compound (S). Get -6. Then, reduction with trichlorosilane in the presence of triethylamine can produce the desired (S) -7 with high efficiency.
【００１８】本発明の化合物は、ロジウム、ルテニウ
ム、パラジウム、イリジウム等の遷移金属と錯体を形成
し、不斉反応に用いることができるが、そのままで用い
ることができる。例えば、下に示す芳香族アルデヒド類
(A)とビニルケトン化合物(B)に付加させて、光学活性ア
ルコール(C)を製造する反応（Baylis-Hillman 反応）の
触媒として用いることができる。The compound of the present invention forms a complex with a transition metal such as rhodium, ruthenium, palladium and iridium and can be used for an asymmetric reaction, but can be used as it is. For example, the aromatic aldehydes shown below
It can be used as a catalyst for a reaction (Baylis-Hillman reaction) for producing an optically active alcohol (C) by adding (A) to a vinyl ketone compound (B).
【化１６】 Embedded image
【００１９】すなわち、上記反応においては、アミノホ
スフィン(1-1)の(R)-体、(S)-体のもののいずれか一方
を選択して用いることにより、光学活性体を合成するこ
とができ、所望する絶対配置の目的物を得ることができ
る。That is, in the above reaction, an optically active compound can be synthesized by selecting and using either (R) -form or (S) -form of aminophosphine (1-1). It is possible to obtain an object having a desired absolute configuration.
【００２０】[0020]
【実施例】以下に実施例を挙げ、本発明を具体的に説明
するが、本発明はこれらによってなんら限定されるもの
ではない。The present invention will be described in more detail with reference to the following examples, which should not be construed as limiting the invention thereto.
【００２１】なお、各物質の測定に用いた装置は次のと
おりである。1 Ｈ核磁気共鳴スペクトル（以下1Ｈ-ＮＭＲと略す）：
ＧＥＭＩＮＩ３００型（３００ＭＨｚ）（バリアン社
製）13 Ｃ核磁気共鳴スペクトル（以下13Ｃ-ＮＭＲと略
す）：ＧＥＭＩＮＩ３００型（７５ＭＨｚ）（バリアン
社製） 赤外吸収スペクトル（以下ＩＲと略す）：ＦＴ／ＩＲ―
５０００（日本分光株式会社） 旋光度計：ＤＩＰ―１４０型（日本分光株式会社） 高速液体クロマトグラフィー（以下ＨＰＬＣと略す) ＬＣ―６Ａ、ＳＰＤ―６Ａ（島津製作所）The apparatus used for measuring each substance is as follows. 1 H nuclear magnetic resonance spectrum (hereinafter abbreviated as 1 H-NMR):
GEMINI 300 (300 MHz) (manufactured by Varian) 13 C nuclear magnetic resonance spectrum (hereinafter abbreviated as 13 C-NMR): GEMINI 300 (75 MHz) (manufactured by Varian) Infrared absorption spectrum (abbreviated as IR): FT / IR ―
5000 (Nihon Bunko Co., Ltd.) Polarimeter: DIP-140 type (Nihon Bunko Co., Ltd.) High performance liquid chromatography (hereinafter abbreviated as HPLC) LC-6A, SPD-6A (Shimadzu Corporation)
【００２２】実施例１ 2-アミノ-2'-ヒドロキシ-1,1'-
ビナフチル(2) の光学分割 2-アミノ-2'-ヒドロキシ-1,1'-ビナフチル（2）5.70g,
20mmol) をアセトン100mlに溶かし、そこへN-ベンジル
シンコニジウムクロリド(4.20g, 10mmol)を加え4時間加
熱還流した。反応液を室温まで冷却し、析出した白色結
晶を濾別し、アセトン10mlで3回洗浄した。固体を酢酸
エチル100mlに溶かし1N HCl 50mlを加えて10分間撹拌し
た。固体が消失したのを確認後、分液操作を行い有機層
を飽和食塩水で洗浄後、無水硫酸ナトリウムで乾燥し
た。溶媒を留去した後ベンゼンを用いて再結晶を行うと
(R)-2-アミノ-2'-ヒドロキシ-1,1'-ビナフチルが（(R)-
2）2.51g、44%の収率で得られた。光学純度は>99% eeで
あった。(CHIRALCEL OD-H;ヘキサン：イソプロパノール
＝90:10) M.p. 167-169℃ [α]D 25 = +117.0 ° (c = 1.0, THF)1 H-NMR (300 MHz, CDCl3, TMS): δ, 3.72(bs, 2H), 5.
14(s, 1H), 7.05-7.39 (m, 8H), 7.74-7.92(m, 4H)13 C-NMR (125.7 MHz, (CD3)2SO):δ, 111.36, 115.00,
118.53, 118.87, 120.89, 122.33, 122.66, 123.53, 12
4.20, 125.82, 126.26, 127.10, 127.91, 129.19, 128.
54, 129.23, 133.73, 134.10, 144.00, 153.38 IR (KBr, cm-1): 3408 w, 3326 m, 3225 w, 1622 vs,
1599 s, 816 vs, 756 s 元素分析 算出値 C20H15N : C 84.18, H 5.30, N 4.91%; 実測値 : C 84.50, H 5.31, N 4.77%. また、濾液を濃縮し、50mlの酢酸エチルに溶かし、1N H
Cl 10ml、飽和食塩水20mlで洗浄し、無水硫酸ナトリウ
ムで乾燥した。溶媒を留去した後ベンゼンを用いて再結
晶を行うと(S)-2-アミノ-2'-ヒドロキシ-1,1'-ビナフチ
ル（(S)-2）が2.42g、45%の収率で得られた。光学純度
は>99% ee であった。(CHIRALCEL OD-H;ヘキサン：イソ
プロパノール＝90:10) [α]D 25 = -117.0 °(c = 1.0, THF)Example 1 2-amino-2'-hydroxy-1,1'-
Optical resolution of binaphthyl (2) 2-amino-2'-hydroxy-1,1'-binaphthyl (2) 5.70 g,
20 mmol) was dissolved in 100 ml of acetone, N-benzylcinchonium chloride (4.20 g, 10 mmol) was added thereto, and the mixture was heated under reflux for 4 hours. The reaction solution was cooled to room temperature, and the precipitated white crystals were separated by filtration and washed three times with 10 ml of acetone. The solid was dissolved in 100 ml of ethyl acetate, 50 ml of 1N HCl was added, and the mixture was stirred for 10 minutes. After confirming that the solid had disappeared, a liquid separation operation was performed, and the organic layer was washed with saturated saline and dried over anhydrous sodium sulfate. After distilling off the solvent, recrystallization using benzene
(R) -2-amino-2'-hydroxy-1,1'-binaphthyl is ((R)-
2) 2.51 g, obtained in 44% yield. Optical purity was> 99% ee. (CHIRALCEL OD-H; hexane: isopropanol = 90: 10) Mp 167-169 ° C [α] D 25 = + 117.0 ° (c = 1.0, THF) 1 H-NMR (300 MHz, CDCl 3 , TMS): δ , 3.72 (bs, 2H), 5.
14 (s, 1H), 7.05-7.39 (m, 8H), 7.74-7.92 (m, 4H) 13 C-NMR (125.7 MHz, (CD 3 ) 2 SO): δ, 111.36, 115.00,
118.53, 118.87, 120.89, 122.33, 122.66, 123.53, 12
4.20, 125.82, 126.26, 127.10, 127.91, 129.19, 128.
54, 129.23, 133.73, 134.10, 144.00, 153.38 IR (KBr, cm -1 ): 3408 w, 3326 m, 3225 w, 1622 vs,
1599 s, 816 vs, 756 s Elemental analysis Calculated value C 20 H 15 N: C 84.18, H 5.30, N 4.91%; Observed value: C 84.50, H 5.31, N 4.77%. Dissolve in ethyl acetate and add 1N H
The mixture was washed with 10 ml of Cl and 20 ml of saturated saline, and dried over anhydrous sodium sulfate. After distilling off the solvent, recrystallization with benzene gave (S) -2-amino-2'-hydroxy-1,1'-binaphthyl ((S) -2) at 2.42 g, 45% yield. Was obtained. Optical purity was> 99% ee. (CHIRALCEL OD-H; hexane: isopropanol = 90: 10) [α] D 25 = -117.0 ° (c = 1.0, THF)
【００２３】実施例２ (S)-2-ジメチルアミノ-2'-ヒド
ロキシ-1,1'-ビナフチル((S)-5)の合成 37% ホルムアルデヒド(0.4 g, 5 mmol) をギ酸(2 ml)に
溶かし(S)-2-アミノ-2'-ヒドロキシ-1,1'-ビナフチル
((S)-2)(570 mg, 2 mmol) を加え、100℃で4時間撹拌し
た。室温まで冷却後、2N NaOH水溶液を加えて反応液をp
H>11 に調整した。酢酸エチル30mlで2 回抽出し、有機
層を飽和食塩水で洗浄後、無水硫酸マグネシウムで乾燥
した。溶媒を留去後、シリカゲルカラムクロマトグラフ
ィー（ヘキサン/ 酢酸エチル = 4/1）で精製したところ
収率82% で(S)-2-ジメチルアミノ-2'-ヒドロキシ-1,1'-
ビナフチル((S)-5)(512 mg) が得られた。 M.p. 184-186°C [α]D 25 = -30.8 °(c = 1.0, THF)1 H-NMR (300 MHz, CDCl3): δ = 2.46 (s, 6H), 7.02-
7.23 (m, 5H), 7.28-7.34 (m, 2H), 7.37 (d, J = 9.0
Hz, 1H), 7.84 (t, J = 8.4 Hz, 2H), 7.88 (d,J = 8.
7 Hz, 1H), 7.95 (d, J = 8.7 Hz, 1H), (the proton o
f OH is not detectable)13 C-NMR (75.5 MHz, CDCl3): δ = 43.58, 118.32, 11
8.43, 119.38, 122.07,123.18, 124.17, 125.72, 125.8
9, 126.29, 126.48, 127.89, 128.12, 129.25,129.66,
129.91, 130.06, 133.93, 134.10, 149.47, 151.58 IR(KBr): cm-1. 3070 w, 2956 w, 1618 s, 1595 s, 818
vs, 762 s HRMS 算出値C22H19NO (M+): 313.1467;実測: 313.146
6.Example 2 Synthesis of (S) -2-dimethylamino-2'-hydroxy-1,1'-binaphthyl ((S) -5) 37% formaldehyde (0.4 g, 5 mmol) was added to formic acid (2 ml). (S) -2-amino-2'-hydroxy-1,1'-binaphthyl
((S) -2) (570 mg, 2 mmol) was added, and the mixture was stirred at 100 ° C for 4 hours. After cooling to room temperature, 2N aqueous NaOH solution was added to
It was adjusted to H> 11. The mixture was extracted twice with 30 ml of ethyl acetate, and the organic layer was washed with brine and dried over anhydrous magnesium sulfate. After evaporating the solvent, the residue was purified by silica gel column chromatography (hexane / ethyl acetate = 4/1) to give (S) -2-dimethylamino-2'-hydroxy-1,1'-yield 82%.
Binaphthyl ((S) -5) (512 mg) was obtained. Mp 184-186 ° C [α] D 25 = -30.8 ° (c = 1.0, THF) 1 H-NMR (300 MHz, CDCl 3 ): δ = 2.46 (s, 6H), 7.02-
7.23 (m, 5H), 7.28-7.34 (m, 2H), 7.37 (d, J = 9.0
Hz, 1H), 7.84 (t, J = 8.4 Hz, 2H), 7.88 (d, J = 8.
7 Hz, 1H), 7.95 (d, J = 8.7 Hz, 1H), (the proton o
f OH is not detectable) 13 C-NMR (75.5 MHz, CDCl 3 ): δ = 43.58, 118.32, 11
8.43, 119.38, 122.07, 123.18, 124.17, 125.72, 125.8
9, 126.29, 126.48, 127.89, 128.12, 129.25,129.66,
129.91, 130.06, 133.93, 134.10, 149.47, 151.58 IR (KBr): cm -1 .3070 w, 2956 w, 1618 s, 1595 s, 818
vs, 762 s HRMS Calculated C 22 H 19 NO (M +): 313.1467; found: 313.146
6.
【００２４】実施例３ (S)-2- ジメチルアミノ-2'-ト
リフルオロメタンスルホニルオキシ-1,1'-ビナフチル
（(S)-4(R1,R2=Me)）の合成 (S)-2-ジメチルアミノ-2'-ヒドロキシ-1,1'-ビナフチル
((S)-5)(313 mg, 1 mmol) を塩化メチレン(3 ml)に溶か
し、トリエチルアミン(0.3 ml, 2.2 mmol)加えた。この
溶液を-78℃まで冷却し、無水トリフルオロメタンスル
ホン酸(0.185 ml, 1.1 mmol)を滴下し、3 時間撹拌し、
室温まで戻した。溶媒を留去後、シリカゲルカラムクロ
マトグラフィー（ヘキサン/酢酸エチル = 10/1）で精製
したところ収率100%で(S)-2-ジメチルアミノ-2'-トリフ
ルオロメタンスルホニルオキシ-1,1'-ビナフチル((S)-
4)(445mg) が得られた。 M.p. 125-126°C [α]D 25 = +144.2 ° (c = 1.0 in THF)1 H-NMR (300 MHz, CDCl3): δ = 2.45 (s, 6H), 6.92
(d, J = 8.4 Hz, 1H), 7.16 (t, J = 8.4 Hz, 1H), 7.
27-7.44 (m, 3H), 7.48-7.58 (m, 3H), 7.83 (d,J = 7.
8 Hz, 1H), 7.94-8.00 (m, 2H), 8.01 (d, J = 8.7 Hz,
1H)13 C-NMR (75.5 MHz, CDCl3): δ = 43.53, 116.08, 11
9.38, 119.85, 120.32, 123.69, 125.16, 126.26, 126.
72, 127.29, 127.50, 127.89, 128.30, 129.53, 129.8
8, 130.21, 132.45, 133.67, 134.22, 145.36, 150.86 IR(KBr): cm-1. 3056 m, 2940 m, 1624 s, 1595 s, 81
8 s, 748 s HRMS 算出 C23H18F3NO3S (M+): 445.0960; 実測 ： 4
45.0950.Example 3 Synthesis of (S) -2-dimethylamino-2'-trifluoromethanesulfonyloxy-1,1'-binaphthyl ((S) -4 (R 1 , R 2 = Me)) 2-dimethylamino-2'-hydroxy-1,1'-binaphthyl
((S) -5) (313 mg, 1 mmol) was dissolved in methylene chloride (3 ml), and triethylamine (0.3 ml, 2.2 mmol) was added. The solution was cooled to -78 ° C, trifluoromethanesulfonic anhydride (0.185 ml, 1.1 mmol) was added dropwise, and the mixture was stirred for 3 hours.
Return to room temperature. After evaporating the solvent, the residue was purified by silica gel column chromatography (hexane / ethyl acetate = 10/1) to give (S) -2-dimethylamino-2'-trifluoromethanesulfonyloxy-1,1 'in 100% yield. -Binaphthyl ((S)-
4) (445 mg) was obtained. Mp 125-126 ° C [α] D 25 = +144.2 ° (c = 1.0 in THF) 1 H-NMR (300 MHz, CDCl 3 ): δ = 2.45 (s, 6H), 6.92
(d, J = 8.4 Hz, 1H), 7.16 (t, J = 8.4 Hz, 1H), 7.
27-7.44 (m, 3H), 7.48-7.58 (m, 3H), 7.83 (d, J = 7.
8 Hz, 1H), 7.94-8.00 (m, 2H), 8.01 (d, J = 8.7 Hz,
1H) 13 C-NMR (75.5 MHz, CDCl 3 ): δ = 43.53, 116.08, 11
9.38, 119.85, 120.32, 123.69, 125.16, 126.26, 126.
72, 127.29, 127.50, 127.89, 128.30, 129.53, 129.8
8, 130.21, 132.45, 133.67, 134.22, 145.36, 150.86 IR (KBr): cm -1 .3056 m, 2940 m, 1624 s, 1595 s, 81
8 s, 748 s HRMS calculation C 23 H 18 F 3 NO 3 S (M +): 445.0960; found: 4
45.0950.
【００２５】実施例４ (S)-2-ジメチルアミノ-2'-ジフ
ェニルホスフィニル-1,1'-ビナフチル((S)-9) の合成 (S)-2-ジメチルアミノ-2'-トリフルオロメタンスルホニ
ルオキシ-1,1'-ビナフチル((S)-4(R1,R2=Me))(445 mg,
1 mmol) 、ジフェニルホスフィンオキシド(404mg, 2 mm
ol)、酢酸パラジウム(22.4 mg, 0.1 mmol) 、1,3-ビス
ジフェニルホスフィノプロパン(61.8 mg, 5 mmol) の混
合物の中にジメチルスルホキシド5 ml、ジイソプロピル
エチルアミン(0.87 ml, 5.0 mmol) を加え、100 °C で
20時間撹拌した。反応混合物を室温まで冷却し、減圧
下、溶媒を留去した後、酢酸エチルを加え水で洗浄し、
無水硫酸マグネシウムで乾燥した。溶媒を留去後、シリ
カゲルカラムクロマトグラフィー（酢酸エチル）で精製
したところ収率76% で(S)-2-ジメチルアミノ-2'-ジフェ
ニルホスフィニル-1,1'-ビナフチル((S)-6)(380 mg)が
得られた。 [α]D 25 =18.6° (c = 1.0 in THF)1 H-NMR (300 MHz, CDCl3): δ = 2.37 (s, 6H), 6.68
(d, J = 8.4 Hz, 1H), 6.92-7.04 (m, 3H), 7.10-7.19
(m, 10H), 7.48-7.58 (m, 5H), 7.79 (t, J =7.8Hz, 1
H), 7.86-7.92 (m, 2H)13 C-NMR (75.5 MHz, CDCl3): δ = 43.47, 119.24,122.
97, 125.53, 125.68, 126.78, 127.08, 127.18, 127.3
4, 127.52, 127.76,128.01, 128.98, 129.59, 129.66,
129.75, 130.37, 130.80, 131.03, 131.16,131.55, 13
1.66, 134.09, 134.65, 150.3131 P-NMR (109.25 MHz): δ = 28.93 IR(KBr): cm-1 , 3058 m, 2940 w, 1620 s, 1597 s, 11
99 vs, 818 s, 748 vs,700 vs HRMS算出 C34H29NOP ([M+H]+): 498.1987;実測：498.19
92.Example 4 Synthesis of (S) -2-dimethylamino-2'-diphenylphosphinyl-1,1'-binaphthyl ((S) -9) (S) -2-dimethylamino-2'- Trifluoromethanesulfonyloxy-1,1′-binaphthyl ((S) -4 (R 1 , R 2 = Me)) (445 mg,
1 mmol), diphenylphosphine oxide (404 mg, 2 mm
ol), palladium acetate (22.4 mg, 0.1 mmol) and 1,3-bisdiphenylphosphinopropane (61.8 mg, 5 mmol) in a mixture of dimethyl sulfoxide (5 ml) and diisopropylethylamine (0.87 ml, 5.0 mmol). At 100 ° C
Stirred for 20 hours. The reaction mixture was cooled to room temperature, the solvent was distilled off under reduced pressure, ethyl acetate was added, and the mixture was washed with water.
It was dried over anhydrous magnesium sulfate. After evaporating the solvent, the residue was purified by silica gel column chromatography (ethyl acetate) to give (S) -2-dimethylamino-2'-diphenylphosphinyl-1,1'-binaphthyl ((S) in a yield of 76%. -6) (380 mg) was obtained. [α] D 25 = 18.6 ° (c = 1.0 in THF) 1 H-NMR (300 MHz, CDCl 3 ): δ = 2.37 (s, 6H), 6.68
(d, J = 8.4 Hz, 1H), 6.92-7.04 (m, 3H), 7.10-7.19
(m, 10H), 7.48-7.58 (m, 5H), 7.79 (t, J = 7.8Hz, 1
H), 7.86-7.92 (m, 2H) 13 C-NMR (75.5 MHz, CDCl 3 ): δ = 43.47, 119.24, 122.
97, 125.53, 125.68, 126.78, 127.08, 127.18, 127.3
4, 127.52, 127.76,128.01, 128.98, 129.59, 129.66,
129.75, 130.37, 130.80, 131.03, 131.16,131.55, 13
1.66, 134.09, 134.65, 150.31 31 P-NMR (109.25 MHz): δ = 28.93 IR (KBr): cm -1 , 3058 m, 2940 w, 1620 s, 1597 s, 11
99 vs, 818 s, 748 vs, 700 vs HRMS calculation C 34 H 29 NOP ([M + H] +): 498.1987; found: 498.19
92.
【００２６】実施例５ (S)-2-ジメチルアミノ-2'-ジフ
ェニルホスフィノ-1,1'-ビナフチル((S)-9) の合成 (S)-2-ジメチルアミノ-2'-ジフェニルホスフィニル-1,
1'-ビナフチル((S)-6)(498 mg, 1 mmol) とトリエチル
アミン(3 ml)をトルエン10 mlに溶かし、0℃まで冷却す
る。トリクロロシラン(1 ml)を加えた後、100℃で6 時
間撹拌した。反応混合物を室温まで冷却し、ジエチルエ
ーテルを加え、飽和重曹水で中和する。反応混合物をセ
ライトを用いてろ過した。有機層を無水硫酸マグネシウ
ムで乾燥した。溶媒を留去後、シリカゲルカラムクロマ
トグラフィー（ヘキサン/酢酸エチル=10/1）で精製した
ところ収率90%で(S)-2-ジメチルアミノ-2'-ジフェニル
ホスフィノ-1,1'-ビナフチル((S)-7)(432 mg) が得られ
た。 [α]D 25 = +26.6 ° (c = 1.0, THF) ee > 98% (HPLCカラム分析（CHIRALPAK AD：ヘキサン−
イソプロパノール＝ 99:1とし、 0.8 ml/min, R: 5.41
min, S: 8.88 min.によって決定した。)1 H-NMR (300 MHz, CDCl3): δ = 2.22 (s, 6H), 6.70
(d, J = 9.3 Hz, 1H), 6.92-7.15 (m, 6H), 7.20-7.36
(m, 7H), 7.38 (d, J = 9.0 Hz, 1H), 7.41(d, J= 9.0
Hz, 1H), 7.45-7.50 (m, 2H), 7.80-7.89 (m, 3H), 7.
94 (d, J = 8.7 Hz, 1H)13 C-NMR (75.5 MHz, CDCl3): δ = 43.07, 119.08, 12
3.36, 125.68, 125.84, 126.29, 126.57, 127.46, 127.
50, 127.75, 127.88, 127.96, 127.99, 128.04, 129.1
7, 129.40, 131.65, 132.79, 132.96, 133.04, 133.23,
133.55, 133.73, 134.10, 150.3631 P-NMR (109.25 MHz): δ = -12.72; IR(KBr), cm-1 : 3056 m, 2938 w, 1620 m, 1595 m, 81
6 s, 745 s, 696 vs HR-MS 算出 C34H28NP (M+): 481.1959;実測： 481.197
8.Example 5 Synthesis of (S) -2-dimethylamino-2'-diphenylphosphino-1,1'-binaphthyl ((S) -9) (S) -2-dimethylamino-2'-diphenyl Phosphinyl-1,
1′-Binaphthyl ((S) -6) (498 mg, 1 mmol) and triethylamine (3 ml) are dissolved in 10 ml of toluene and cooled to 0 ° C. After adding trichlorosilane (1 ml), the mixture was stirred at 100 ° C for 6 hours. The reaction mixture is cooled to room temperature, added with diethyl ether and neutralized with saturated aqueous sodium hydrogen carbonate. The reaction mixture was filtered using celite. The organic layer was dried over anhydrous magnesium sulfate. After evaporating the solvent, the residue was purified by silica gel column chromatography (hexane / ethyl acetate = 10/1) to give (S) -2-dimethylamino-2'-diphenylphosphino-1,1'-yield 90%. Binaphthyl ((S) -7) (432 mg) was obtained. [α] D 25 = +26.6 ° (c = 1.0, THF) ee> 98% (HPLC column analysis (CHIRALPAK AD: hexane-
0.8 ml / min, R: 5.41, with isopropanol = 99: 1
min, S: determined by 8.88 min. ) 1 H-NMR (300 MHz, CDCl 3 ): δ = 2.22 (s, 6H), 6.70
(d, J = 9.3 Hz, 1H), 6.92-7.15 (m, 6H), 7.20-7.36
(m, 7H), 7.38 (d, J = 9.0 Hz, 1H), 7.41 (d, J = 9.0
Hz, 1H), 7.45-7.50 (m, 2H), 7.80-7.89 (m, 3H), 7.
94 (d, J = 8.7 Hz, 1H) 13 C-NMR (75.5 MHz, CDCl 3 ): δ = 43.07, 119.08, 12
3.36, 125.68, 125.84, 126.29, 126.57, 127.46, 127.
50, 127.75, 127.88, 127.96, 127.99, 128.04, 129.1
7, 129.40, 131.65, 132.79, 132.96, 133.04, 133.23,
133.55, 133.73, 134.10, 150.36 31 P-NMR (109.25 MHz): δ = -12.72; IR (KBr), cm -1 : 3056 m, 2938 w, 1620 m, 1595 m, 81
6 s, 745 s, 696 vs HR-MS calculation C 34 H 28 NP (M +): 481.1959; found: 481.197
8.
【００２７】実施例６ 3-[(4-トリフルオロメチルフェ
ニル) ヒドロキシメチル]-3-ブテン-2-オン(C) の合成 メチルビニルケトン(B)(0.65 ml, 7.8 mmol)、4-トリフ
ルオロメチルベンズアルデヒド(A)(0.5 ml, 3.7 mmol)
、(S)-2-ジメチルアミノ-2'-ジフェニルホスフィノ-1,
1'-ビナフチル(72 mg, 0.15 mmol)をアセトニトリル4 m
lに溶かし、室温で6 日間撹拌した。反応混合物を飽和
塩化アンモニウム水に注ぎ、酢酸エチルで抽出した。有
機層を飽和食塩水で洗浄後無水硫酸マグネシウムで乾燥
した。溶媒を留去後、シリカゲルカラムクロマトグラフ
ィー（ヘキサン/酢酸エチル）で精製したところ収率10%
で3-[(4-トリフルオロメチルフェニル) ヒドロキシメチ
ル]-3-ブテン-2- オン(C)(92mg) が得られた。不斉収率
はキラルＨＰＬＣカラム分析（ダイセルCHIRALPAK AS:
ヘキサン−イソプロパノール＝98:2）によって14％eeと
決定した。1 H-NMR (300 MHz, CDCl3) δ 2.35 (s, 3H), 3.37 (br,
1H), 5.64 (d(br), J =5.1 Hz, 1H), 6.01 (d, J =0.9
Hz, 1H), 6.23 (s, 1H), 7.48 (d, J = 8.4 Hz,2H),
7.58 (d, J = 8.4 Hz, 2H).13 C-NMR (75 MHz, CDCl3) δ 26.2, 71.8, 124.1 (q, J
C-F = 270.5 Hz), 125.2(q,JC-C-C-F = 3.7 Hz), 126.
8, 127.0, 129.6 (q, JC-C-F = 31.5 Hz), 145.9,149.
6, 200.0. IR (neat) 3312, 1676, 1622, 1419, 1369, 1325, 116
6, 1125, 1069, 959, 837 cm-1.Example 6 Synthesis of 3-[(4-trifluoromethylphenyl) hydroxymethyl] -3-buten-2-one (C) Methyl vinyl ketone (B) (0.65 ml, 7.8 mmol), Fluoromethylbenzaldehyde (A) (0.5 ml, 3.7 mmol)
, (S) -2-dimethylamino-2'-diphenylphosphino-1,
1'-binaphthyl (72 mg, 0.15 mmol) in acetonitrile 4 m
and stirred at room temperature for 6 days. The reaction mixture was poured into saturated aqueous ammonium chloride and extracted with ethyl acetate. The organic layer was washed with saturated saline and dried over anhydrous magnesium sulfate. After evaporating the solvent, the residue was purified by silica gel column chromatography (hexane / ethyl acetate), yield 10%
This gave 3-[(4-trifluoromethylphenyl) hydroxymethyl] -3-buten-2-one (C) (92 mg). Chiral HPLC column analysis (Daisel CHIRALPAK AS:
Hexane-isopropanol = 98: 2) to determine 14% ee. 1 H-NMR (300 MHz, CDCl 3 ) δ 2.35 (s, 3H), 3.37 (br,
1H), 5.64 (d (br), J = 5.1 Hz, 1H), 6.01 (d, J = 0.9
Hz, 1H), 6.23 (s, 1H), 7.48 (d, J = 8.4 Hz, 2H),
7.58 (d, J = 8.4 Hz , 2H). 13 C-NMR (75 MHz, CDCl 3) δ 26.2, 71.8, 124.1 (q, J
CF = 270.5 Hz), 125.2 (q, J CCCF = 3.7 Hz), 126.
8, 127.0, 129.6 (q, J CCF = 31.5 Hz), 145.9, 149.
6, 200.0.IR (neat) 3312, 1676, 1622, 1419, 1369, 1325, 116
6, 1125, 1069, 959, 837 cm -1 .
Claims (3)
ナフチルと式(3) 【化２】 で表されるN-ベンジルシンコニジウムクロリドを2-アミ
ノ-2'-ヒドロキシ-1,1'-ビナフチルの1/2当量を反応さ
せ、式(2)の化合物の(R)-体の付加体と(S)-体を得て、
これらを優先晶析で単離し、(R)-体の付加体を加水分解
することによって、光学活性な2-アミノ-2'-ヒドロキシ
-1,1'-ビナフチルを得て、この光学活性な2-アミノ-2'-
ヒドロキシ-1,1'-ビナフチルのアミノ基を保護基によっ
て保護し、さらに三級アミンの存在下に無水トリフラー
トを反応させ、式(4) 【化３】 （式中、R1、R2は、同一または相異なる、炭素数１−４
のアルキル基である）で表されるトリフラートを得、こ
れに酢酸パラジウム、1,3-ビス（ジフェニルホスフィ
ノ）プロパンとN,N−ジイソプロピルエチルアミンの存
在下、ジアリールホスフィンオキシド誘導体を反応さ
せ、式(1-2) 【化４】 （式中、R1、R2は前記と同一意味を示し、Arは、同一ま
たは相異なる、フェニル基、4-トリル基、3-トリル基、
3,5-キシリル基、4-メトキシフェニル基、4-クロロフェ
ニル基を示す）で表される光学活性ホスフィニル化合物
を得て、前記光学活性ホスフィニル化合物を、トリエチ
ルアミンの存在下、トリクロロシランを用いて還元し
て、式(1-1) 【化５】 （式中、R1、R2は、同一または相異なる、炭素数１−４
のアルキル基である；ｎは０又は１；Arは、同一または
相異なる、フェニル基、4-トリル基、3-トリル基、3,5-
キシリル基、4-メトキシフェニル基、4-クロロフェニル
基を示す）で表される光学活性ホスフィンを製造する方
法。(1) Formula (2) And a racemic 2-amino-2'-hydroxy-1,1'-binaphthyl represented by the formula (3) Is reacted with 1/2 equivalent of 2-amino-2'-hydroxy-1,1'-binaphthyl to add the (R) -form of the compound of formula (2) Get body and (S) -body,
These are isolated by preferential crystallization, and the (R) -adduct is hydrolyzed to give optically active 2-amino-2'-hydroxy.
-1,1'-binaphthyl was obtained and this optically active 2-amino-2'-
The amino group of hydroxy-1,1'-binaphthyl is protected with a protecting group, and further reacted with anhydrous triflate in the presence of a tertiary amine to give a compound of formula (4) (Wherein, R 1 and R 2 are the same or different and each have 1 to 4 carbon atoms)
Is obtained by reacting a diarylphosphine oxide derivative with palladium acetate, 1,3-bis (diphenylphosphino) propane and N, N-diisopropylethylamine in the presence of (1-2) (Wherein, R 1 and R 2 have the same meanings as described above, and Ar is the same or different, and is a phenyl group, a 4-tolyl group, a 3-tolyl group,
3,5-xylyl group, 4-methoxyphenyl group, 4-chlorophenyl group), and the optically active phosphinyl compound is reduced with trichlorosilane in the presence of triethylamine. And the formula (1-1) (Wherein, R 1 and R 2 are the same or different and each have 1 to 4 carbon atoms)
N is 0 or 1; Ar is the same or different and is a phenyl group, a 4-tolyl group, a 3-tolyl group, a 3,5-
Xylyl group, 4-methoxyphenyl group and 4-chlorophenyl group).
ナフチルと式(3) 【化７】 N-ベンジルシンコニジウムクロリドを2-アミノ-2'-ヒド
ロキシ-1,1'-ビナフチルの1/2当量を反応させ、式(2)の
化合物の(R)-体の付加体と(S)-体を得て、これらを優先
晶析で単離し、(R)-体の付加体は加水分解することによ
って光学活性な2-アミノ-2'-ヒドロキシ-1,1'-ビナフチ
ル式(1)を製造する方法。 【化８】 (2) Formula (2) And a racemic 2-amino-2'-hydroxy-1,1'-binaphthyl represented by the formula (3) N-benzylcinchonidium chloride is reacted with 1/2 equivalent of 2-amino-2'-hydroxy-1,1'-binaphthyl, and the (R) -form adduct of the compound of formula (2) and (S )-Isomers, these are isolated by preferential crystallization, and the adduct of the (R) -isomer is hydrolyzed to give an optically active 2-amino-2'-hydroxy-1,1'-binaphthyl formula ( 1) How to manufacture. Embedded image
のアルキル基である；Arは、同一または相異なる、フェ
ニル基、4-トリル基、3-トリル基、3,5-キシリル基、4-
メトキシフェニル基、4-クロロフェニル基を示す；ｎは
０を示す）を使用して、Baylis-Hillman反応を行い、光
学活性体を製造する方法。3. The general formula (1-1) obtained in claim 1. (Wherein, R 1 and R 2 are the same or different and each have 1 to 4 carbon atoms)
Ar is the same or different, phenyl group, 4-tolyl group, 3-tolyl group, 3,5-xylyl group, 4-
A methoxyphenyl group or a 4-chlorophenyl group; n represents 0) to carry out a Baylis-Hillman reaction to produce an optically active substance.
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|---|---|---|---|
| JP10367754A JP2000191676A (en) | 1998-12-24 | 1998-12-24 | Production of optically active aminophosphine compound |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10367754A JP2000191676A (en) | 1998-12-24 | 1998-12-24 | Production of optically active aminophosphine compound |
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|---|---|
| JP2000191676A true JP2000191676A (en) | 2000-07-11 |
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ID=18490116
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| JP (1) | JP2000191676A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009090957A1 (en) * | 2008-01-18 | 2009-07-23 | Sumitomo Chemical Company, Limited | Process for production of optically active amines |
-
1998
- 1998-12-24 JP JP10367754A patent/JP2000191676A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009090957A1 (en) * | 2008-01-18 | 2009-07-23 | Sumitomo Chemical Company, Limited | Process for production of optically active amines |
| JP2009191063A (en) * | 2008-01-18 | 2009-08-27 | Erick M Carreira | Method for producing optically active [4-(2-diphenylphosphanylnaphthalen-1-yl)phthalazin-1-yl]-(1-phenylethyl)amine |
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