JPH06345789A - 1,2-bisdiphenylphspohinoxy-1,2-diphenylethane and its copper complex - Google Patents
1,2-bisdiphenylphspohinoxy-1,2-diphenylethane and its copper complexInfo
- Publication number
- JPH06345789A JPH06345789A JP16866893A JP16866893A JPH06345789A JP H06345789 A JPH06345789 A JP H06345789A JP 16866893 A JP16866893 A JP 16866893A JP 16866893 A JP16866893 A JP 16866893A JP H06345789 A JPH06345789 A JP H06345789A
- Authority
- JP
- Japan
- Prior art keywords
- diphenylethane
- bisdiphenylphosphinoxy
- formula
- complex
- cuprous chloride
- 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
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、光学活性１，２−ビス
ジフェニルホスフィノキシ−１，２−ジフェニルエタン
及びその銅錯体に関する。FIELD OF THE INVENTION The present invention relates to an optically active 1,2-bisdiphenylphosphinoxy-1,2-diphenylethane and a copper complex thereof.
【０００２】[0002]
【従来の技術とその問題点】光学活性なホスフィン誘導
体は、主にＶＩＩＩ族遷移金属の配位子として用いら
れ、その遷移金属錯体は様々な不斉合成触媒として、有
用な合成反応が開発されている（Ｃｈｅｍ．Ｒｅｖ．，
９２，９３５（１９９２））。例えば、ＢＩＮＡＰ
（２，２’−ビスジフェニルホスフィノ−１，１’−ビ
ナフチル）−Ｒｕ錯体やＢＩＮＡＰ−Ｒｈ錯体は、不斉
還元等の触媒として医薬品等の合成に利用されている。
しかしながら、これらの光学活性な遷移金属錯体の多く
は、その調製が容易でないことが、工業的な用途展開を
制限している。錯体調製が容易でない理由として、配位
子であるラセミもしくは光学活性なホスフィン誘導体の
合成、あるいはラセミの錯体の光学分割が、非常に多く
の工程数を必要とするため収率が極めて低いことや、技
術的に製造規模の拡大が困難なこと、あるいは非常に高
価な原料を必要とすることなどが挙げられる。2. Description of the Related Art Optically active phosphine derivatives are mainly used as ligands of Group VIII transition metals, and the transition metal complexes have been developed as useful asymmetric synthesis catalysts for useful synthetic reactions. (Chem. Rev.,
92 , 935 (1992)). For example, BINAP
The (2,2′-bisdiphenylphosphino-1,1′-binaphthyl) -Ru complex and the BINAP-Rh complex are used as a catalyst for asymmetric reduction in the synthesis of pharmaceuticals and the like.
However, the difficulty in preparing many of these optically active transition metal complexes limits the industrial application development. The reason why complex preparation is not easy is that the synthesis of a racemic or optically active phosphine derivative as a ligand, or the optical resolution of a racemic complex requires a very large number of steps, and the yield is extremely low. However, it is technically difficult to expand the production scale, or very expensive raw materials are required.
【０００３】[0003]
【発明が解決しようとする課題】従って、より実用的に
入手でき、また新規な不斉触媒機能を有する光学活性ホ
スフィン−遷移金属錯体の開発が望まれている。本発明
者らは、この課題を解決すべく鋭意検討を重ね、Ｃｈｅ
ｍ．Ｌｅｔｔ．，７６３（１９９１）の方法により、両
鏡像体ともに容易に入手できる光学活性１，２−ジフェ
ニルエタンジオ−ルを原料とし、これから容易に調製で
きる光学活性ホスフィン配位子および各種の遷移金属錯
体へ容易に変換できる光学活性ホスフィン−銅錯体の開
発に成功した。すなわち、本発明の目的は、容易に調製
できる新規な光学活性ホスフィン配位子である（Ｒ，
Ｒ）−及び（Ｓ，Ｓ）−１，２−ビスジフェニルホスフ
ィノキシ−１，２−ジフェニルエタン及びそれらの銅錯
体を提供することである。Therefore, it is desired to develop an optically active phosphine-transition metal complex which is more practically available and has a novel asymmetric catalytic function. The present inventors have conducted extensive studies to solve this problem, and
m. Lett. , 763 (1991), the optically active 1,2-diphenylethanediol, which is easily available as both enantiomers, is used as a raw material to prepare an optically active phosphine ligand and various transition metal complexes. We have succeeded in developing an optically active phosphine-copper complex that can be easily converted. That is, the object of the present invention is a novel optically active phosphine ligand which can be easily prepared (R,
R)-and (S, S) -1,2-bisdiphenylphosphinoxy-1,2-diphenylethane and their copper complexes.
【０００４】[0004]
【課題を解決するための手段】本発明は式（１）The present invention provides the formula (1).
【化５】 で示される（Ｒ，Ｒ）−１，２−ビスジフェニルホスフ
ィノキシ−１，２−ジフェニルエタン、式（２）[Chemical 5] (R, R) -1,2-bisdiphenylphosphinoxy-1,2-diphenylethane represented by the formula (2)
【化６】 で示される（Ｓ，Ｓ）−１，２−ビスジフェニルホスフ
ィノキシ−１，２−ジフェニルエタン、式（３）[Chemical 6] (S, S) -1,2-bisdiphenylphosphinoxy-1,2-diphenylethane represented by the formula (3)
【化７】 で示される（Ｒ，Ｒ）−１，２−ビスジフェニルホスフ
ィノキシ−１，２−ジフェニルエタンと塩化第一銅から
１：１のモル比でなる錯体、および式（４）[Chemical 7] A complex consisting of (R, R) -1,2-bisdiphenylphosphinoxy-1,2-diphenylethane and cuprous chloride in a molar ratio of 1: 1, and a compound of formula (4)
【化８】 で示される（Ｓ，Ｓ）−１，２−ビスジフェニルホスフ
ィノキシ−１，２−ジフェニルエタンと塩化第一銅から
１：１のモル比でなる錯体である。[Chemical 8] Of (S, S) -1,2-bisdiphenylphosphinoxy-1,2-diphenylethane and cuprous chloride in a molar ratio of 1: 1.
【０００５】本発明の（Ｒ，Ｒ）−１，２−ビスジフェ
ニルホスフィノキシ−１，２−ジフェニルエタンは、
（Ｒ，Ｒ）−１，２−ジフェニルエタンジオ−ルにテト
ラヒドロフラン等のエ−テル系溶媒中、氷冷下でブチル
リチウム等の塩基を作用させた後、ジフェニルクロロホ
スフィンを加え、氷冷下ないし室温で反応させることに
より容易に得ることができる。同様にして、（Ｓ，Ｓ）
−１，２−ビスジフェニルホスフィノキシ−１，２−ジ
フェニルエタンは、（Ｓ，Ｓ）−１，２−ジフェニルエ
タンジオ−ルから容易に得ることができる。The (R, R) -1,2-bisdiphenylphosphinoxy-1,2-diphenylethane of the present invention is
After reacting (R, R) -1,2-diphenylethanediol with a base such as butyllithium in an ether solvent such as tetrahydrofuran under ice cooling, diphenylchlorophosphine is added, and the mixture is cooled under ice. It can be easily obtained by reacting at room temperature. Similarly, (S, S)
-1,2-bisdiphenylphosphinoxy-1,2-diphenylethane can be easily obtained from (S, S) -1,2-diphenylethanediol.
【０００６】本発明の（Ｒ，Ｒ）−１，２−ビスジフェ
ニルホスフィノキシ−１，２−ジフェニルエタンと塩化
第一銅から１：１のモル比でなる錯体は、（Ｒ，Ｒ）−
１，２−ビスジフェニルホスフィノキシ−１，２−ジフ
ェニルエタンにエタノ−ル等のアルコ−ル溶媒中、還流
下で塩化第一銅を加えることにより容易に得ることがで
きる。同様にして、（Ｓ，Ｓ）−１，２−ビスジフェニ
ルホスフィノキシ−１，２−ジフェニルエタンと塩化第
一銅から１：１のモル比でなる錯体は、（Ｓ，Ｓ）−
１，２−ビスジフェニルホスフィノキシ−１，２−ジフ
ェニルエタンから容易に得ることができる。The complex of (R, R) -1,2-bisdiphenylphosphinoxy-1,2-diphenylethane of the present invention and cuprous chloride in a molar ratio of 1: 1 is (R, R) −
It can be easily obtained by adding cuprous chloride to 1,2-bisdiphenylphosphinoxy-1,2-diphenylethane in an alcohol solvent such as ethanol under reflux. Similarly, a complex consisting of (S, S) -1,2-bisdiphenylphosphinoxy-1,2-diphenylethane and cuprous chloride at a molar ratio of 1: 1 is (S, S)-
It can be easily obtained from 1,2-bisdiphenylphosphinoxy-1,2-diphenylethane.
【０００７】本発明の（Ｒ，Ｒ）−ないし（Ｓ，Ｓ）−
１，２−ビスジフェニルホスフィノキシ−１，２−ジフ
ェニルエタン及び（Ｒ，Ｒ）−ないし（Ｓ，Ｓ）−１，
２−ビスジフェニルホスフィノキシ−１，２−ジフェニ
ルエタンと塩化第一銅から１：１のモル比でなる錯体は
いずれも、不斉合成に用いられる遷移金属を共存させる
ことにより、その反応系内で、対応する１，２−ビスジ
フェニルホスフィノキシ−１，２−ジフェニルエタン−
遷移金属触媒が生成し、その不斉触媒機能を発揮する。(R, R)-to (S, S)-of the present invention
1,2-bisdiphenylphosphinoxy-1,2-diphenylethane and (R, R)-to (S, S) -1,
All of the complexes of 2-bisdiphenylphosphinoxy-1,2-diphenylethane and cuprous chloride in a molar ratio of 1: 1 can be prepared by coexisting a transition metal used for asymmetric synthesis to produce a reaction system thereof. In which the corresponding 1,2-bisdiphenylphosphinoxy-1,2-diphenylethane-
A transition metal catalyst is produced and exerts its asymmetric catalytic function.
【０００８】[0008]
【実施例】以下、実施例にて本発明を説明する。 実施例１ 窒素雰囲気下、（Ｓ，Ｓ）−１，２−ジフェニルエタン
ジオ−ル１．００ｇ（４．９７ｍｍｏｌ）をテトラヒド
ロフラン１０ｍｌに溶解させ、氷冷下で１．５７ｍｏｌ
／ｌブチルリチウム／ヘキサン溶液６．３５ｍｌ（９．
９７ｍｍｏｌ）を滴下した。ついでジフェニルクロロホ
スフィン２．２０ｇ（９．９７ｍｍｏｌ）を滴下し、氷
冷下で１０分間攪拌した。析出物を濾過し、濾液を減圧
下に濃縮して得られた残渣にエ−テルを加え、結晶化さ
せ、濾過し、結晶を減圧下で乾燥し、（Ｓ，Ｓ）−１，
２−ビスジフェニルホスフィノキシ−１，２−ジフェニ
ルエタン１．２０ｇ（２．０６ｍｍｏｌ）を収率４１％
で得た。ＩＲ（ＫＢｒ−ｄｉｓｋ）：１０１０（Ｐ−
Ｏ）EXAMPLES The present invention will be described below with reference to examples. Example 1 Under a nitrogen atmosphere, 1.00 g (4.97 mmol) of (S, S) -1,2-diphenylethanediol was dissolved in 10 ml of tetrahydrofuran, and 1.57 mol was obtained under ice cooling.
/ L butyllithium / hexane solution 6.35 ml (9.
97 mmol) was added dropwise. Then, 2.20 g (9.97 mmol) of diphenylchlorophosphine was added dropwise, and the mixture was stirred under ice cooling for 10 minutes. The precipitate was filtered, the filtrate was concentrated under reduced pressure, ether was added to the residue obtained for crystallization, and the crystals were filtered and dried under reduced pressure to obtain (S, S) -1,
2-bisdiphenylphosphinoxy-1,2-diphenylethane 1.20 g (2.06 mmol) yield 41%
Got with. IR (KBr-disk): 1010 (P-
O)
【０００９】実施例２ （Ｒ，Ｒ）−１，２−ジフェニルエタンジオ−ルから、
実施例１と同様にして（Ｒ，Ｒ）−１，２−ビスジフェ
ニルホスフィノキシ−１，２−ジフェニルエタンを得
た。 ＩＲ（ＫＢｒ−ｄｉｓｋ）：１０１０（Ｐ−Ｏ）Example 2 From (R, R) -1,2-diphenylethanediol,
In the same manner as in Example 1, (R, R) -1,2-bisdiphenylphosphinoxy-1,2-diphenylethane was obtained. IR (KBr-disk): 1010 (P-O)
【００１０】実施例３ 実施例１で得た（Ｓ，Ｓ）−１，２−ビスジフェニルホ
スフィノキシ−１，２−ジフェニルエタン１．２０ｇ
（２．０６ｍｍｏｌ）と塩化第一銅２０４ｍｇ（２．０
６ｍｍｏｌ）にエタノ−ル２０ｍｌを加え、６時間還流
した。放冷後、析出物を１０ｍｌのクロロホルムに溶か
し、不溶物を濾過し、濾液を減圧下で濃縮し、（Ｓ，
Ｓ）−１，２−ビスジフェニルホスフィノキシ−１，２
−ジフェニルエタンと塩化第一銅から１：１のモル比で
なる錯体６９９ｍｇを収率５０％で得た。 ｍｐ：２７２〜２７４℃ ＮＭＲ（ＣＤＣｌ3 ）：６．５〜８．０（ｍ）； ＩＲ（ＫＢｒ−ｄｉｓｋ）：１０１０（Ｐ−Ｏ）； ［α］D 25 −１５６°（ｃ １．０， ＣＨＣｌ3 ）； 分析値：Ｃ，６６．４２；Ｈ，４．７８；Ｃｌ，５．２
８． 計算値（Ｃ38Ｈ32ＣｌＣｕＯ2 Ｐ2 ）：Ｃ，６６．９
６；Ｈ，４．７３；Ｃｌ，５．２０．Example 3 1.20 g of (S, S) -1,2-bisdiphenylphosphinoxy-1,2-diphenylethane obtained in Example 1
(2.06 mmol) and 204 mg of cuprous chloride (2.0
20 ml of ethanol was added to 6 mmol) and the mixture was refluxed for 6 hours. After cooling, the precipitate was dissolved in 10 ml of chloroform, the insoluble material was filtered, and the filtrate was concentrated under reduced pressure.
S) -1,2-bisdiphenylphosphinoxy-1,2
699 mg of a complex having a molar ratio of 1: 1 was obtained from diphenylethane and cuprous chloride in a yield of 50%. mp: 272~274 ℃ NMR (CDCl 3 ): 6.5~8.0 (m); IR (KBr-disk): 1010 (P-O); [α] D 25 -156 ° (c 1.0 , CHCl 3 ); analytical value: C, 66.42; H, 4.78; Cl, 5.2.
8. Calculated value (C 38 H 32 ClCuO 2 P 2 ): C, 66.9
6; H, 4.73; Cl, 5.20.
【００１１】実施例４ 実施例２で得た（Ｒ，Ｒ）−１，２−ビスジフェニルホ
スフィノキシ−１，２−ジフェニルエタンから、実施例
３と同様にして、（Ｒ，Ｒ）−１，２−ビスジフェニル
ホスフィノキシ−１，２−ジフェニルエタンと塩化第一
銅から１：１のモル比でなる錯体を得た。 ［α］D 25 ＋１５６°（ｃ １．０， ＣＨＣｌ3 ）Example 4 From (R, R) -1,2-bisdiphenylphosphinoxy-1,2-diphenylethane obtained in Example 2 in the same manner as in Example 3, (R, R)- A complex having a molar ratio of 1: 1 was obtained from 1,2-bisdiphenylphosphinoxy-1,2-diphenylethane and cuprous chloride. [Α] D 25 + 156 ° (c 1.0, CHCl 3 )
【００１２】[0012]
【発明の効果】本発明の（Ｒ，Ｒ）−及び（Ｓ，Ｓ）−
１，２−ビスジフェニルホスフィノキシ−１，２−ジフ
ェニルエタン及びそれらの銅錯体は、不斉合成触媒の配
位子として非常に容易に調製でき、かつ新規な不斉触媒
機能の不斉合成に使用することが可能である。EFFECTS OF THE INVENTION (R, R)-and (S, S)-of the present invention
1,2-Bisdiphenylphosphinoxy-1,2-diphenylethane and copper complexes thereof can be prepared very easily as a ligand of an asymmetric synthesis catalyst and have a novel asymmetric catalytic function. Can be used for.
Claims (4)
ィノキシ−１，２−ジフェニルエタン1. Formula (1): (R, R) -1,2-bisdiphenylphosphinoxy-1,2-diphenylethane represented by
ィノキシ−１，２−ジフェニルエタン2. Formula (2): (S, S) -1,2-bisdiphenylphosphinoxy-1,2-diphenylethane represented by
ィノキシ−１，２−ジフェニルエタンと塩化第一銅から
１：１のモル比でなる錯体3. Formula (3): A complex consisting of (R, R) -1,2-bisdiphenylphosphinoxy-1,2-diphenylethane and cuprous chloride in a molar ratio of 1: 1
ィノキシ−１，２−ジフェニルエタンと塩化第一銅から
１：１のモル比でなる錯体4. Formula (4): A complex consisting of (S, S) -1,2-bisdiphenylphosphinoxy-1,2-diphenylethane and cuprous chloride in a molar ratio of 1: 1
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16866893A JPH06345789A (en) | 1993-06-15 | 1993-06-15 | 1,2-bisdiphenylphspohinoxy-1,2-diphenylethane and its copper complex |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16866893A JPH06345789A (en) | 1993-06-15 | 1993-06-15 | 1,2-bisdiphenylphspohinoxy-1,2-diphenylethane and its copper complex |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06345789A true JPH06345789A (en) | 1994-12-20 |
Family
ID=15872289
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16866893A Pending JPH06345789A (en) | 1993-06-15 | 1993-06-15 | 1,2-bisdiphenylphspohinoxy-1,2-diphenylethane and its copper complex |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06345789A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104402928A (en) * | 2014-11-27 | 2015-03-11 | 薛峰 | Novel chirality dibenzothiophene framework diphosphine ligand and synthetizing method thereof |
-
1993
- 1993-06-15 JP JP16866893A patent/JPH06345789A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104402928A (en) * | 2014-11-27 | 2015-03-11 | 薛峰 | Novel chirality dibenzothiophene framework diphosphine ligand and synthetizing method thereof |
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