JPS6210516B2 - - Google Patents
Info
- Publication number
- JPS6210516B2 JPS6210516B2 JP54114139A JP11413979A JPS6210516B2 JP S6210516 B2 JPS6210516 B2 JP S6210516B2 JP 54114139 A JP54114139 A JP 54114139A JP 11413979 A JP11413979 A JP 11413979A JP S6210516 B2 JPS6210516 B2 JP S6210516B2
- Authority
- JP
- Japan
- Prior art keywords
- mmol
- isocyanate
- optically active
- multiplet
- chloroform
- 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
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- 239000003446 ligand Substances 0.000 claims description 12
- -1 nitro-substituted phenyl group Chemical class 0.000 claims description 10
- 239000012948 isocyanate Substances 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 150000002513 isocyanates Chemical class 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 40
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 18
- 239000000843 powder Substances 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 239000002904 solvent Substances 0.000 description 11
- 239000013078 crystal Substances 0.000 description 9
- 238000010898 silica gel chromatography Methods 0.000 description 9
- 150000001408 amides Chemical class 0.000 description 8
- 238000000921 elemental analysis Methods 0.000 description 8
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000010948 rhodium Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical compound N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 description 4
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 3
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 description 2
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- HXBPYFMVGFDZFT-UHFFFAOYSA-N allyl isocyanate Chemical compound C=CCN=C=O HXBPYFMVGFDZFT-UHFFFAOYSA-N 0.000 description 2
- 238000009876 asymmetric hydrogenation reaction Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- KQWGXHWJMSMDJJ-UHFFFAOYSA-N cyclohexyl isocyanate Chemical compound O=C=NC1CCCCC1 KQWGXHWJMSMDJJ-UHFFFAOYSA-N 0.000 description 2
- 239000011982 enantioselective catalyst Substances 0.000 description 2
- IKGHIFGXPVLPFD-LLVKDONJSA-N methyl (2r)-2-acetamido-3-phenylpropanoate Chemical compound COC(=O)[C@H](NC(C)=O)CC1=CC=CC=C1 IKGHIFGXPVLPFD-LLVKDONJSA-N 0.000 description 2
- HAMGRBXTJNITHG-UHFFFAOYSA-N methyl isocyanate Chemical compound CN=C=O HAMGRBXTJNITHG-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical group [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- FYWJWWMKCARWQG-UHFFFAOYSA-N 1,2-dichloro-3-isocyanatobenzene Chemical compound ClC1=CC=CC(N=C=O)=C1Cl FYWJWWMKCARWQG-UHFFFAOYSA-N 0.000 description 1
- GOOVAYJIVMBWPP-UHFFFAOYSA-N 1-bromo-2-isocyanatobenzene Chemical compound BrC1=CC=CC=C1N=C=O GOOVAYJIVMBWPP-UHFFFAOYSA-N 0.000 description 1
- NOHQUGRVHSJYMR-UHFFFAOYSA-N 1-chloro-2-isocyanatobenzene Chemical compound ClC1=CC=CC=C1N=C=O NOHQUGRVHSJYMR-UHFFFAOYSA-N 0.000 description 1
- GFNKTLQTQSALEJ-UHFFFAOYSA-N 1-isocyanato-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(N=C=O)C=C1 GFNKTLQTQSALEJ-UHFFFAOYSA-N 0.000 description 1
- BDQNKCYCTYYMAA-UHFFFAOYSA-N 1-isocyanatonaphthalene Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1 BDQNKCYCTYYMAA-UHFFFAOYSA-N 0.000 description 1
- QVLWPBIUVXZGRK-UHFFFAOYSA-N 2-isocyanatothiophene Chemical compound O=C=NC1=CC=CS1 QVLWPBIUVXZGRK-UHFFFAOYSA-N 0.000 description 1
- MFUVCHZWGSJKEQ-UHFFFAOYSA-N 3,4-dichlorphenylisocyanate Chemical compound ClC1=CC=C(N=C=O)C=C1Cl MFUVCHZWGSJKEQ-UHFFFAOYSA-N 0.000 description 1
- WTDRDQBEARUVNC-LURJTMIESA-N L-DOPA Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C(O)=C1 WTDRDQBEARUVNC-LURJTMIESA-N 0.000 description 1
- WTDRDQBEARUVNC-UHFFFAOYSA-N L-Dopa Natural products OC(=O)C(N)CC1=CC=C(O)C(O)=C1 WTDRDQBEARUVNC-UHFFFAOYSA-N 0.000 description 1
- 150000001370 alpha-amino acid derivatives Chemical class 0.000 description 1
- 150000001371 alpha-amino acids Chemical class 0.000 description 1
- 235000008206 alpha-amino acids Nutrition 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004799 bromophenyl group Chemical group 0.000 description 1
- 125000000068 chlorophenyl group Chemical group 0.000 description 1
- PRVVOMNMQMTKRI-UHFFFAOYSA-N diphenyl(pyrrolidin-1-ylmethyl)phosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CN1CCCC1 PRVVOMNMQMTKRI-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000006911 enzymatic reaction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- USKHBABPFFAKJD-FLIBITNWSA-N methyl (z)-2-acetamido-3-phenylprop-2-enoate Chemical compound COC(=O)C(\NC(C)=O)=C\C1=CC=CC=C1 USKHBABPFFAKJD-FLIBITNWSA-N 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000006501 nitrophenyl group Chemical group 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
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
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】
本発明は新規な一般式
（式中R1はアルキル基、アルケニル基、シクロア
ルキル基、フエニル基、ハロゲン置換フエニル基
又はニトロ置換フエニル基であり、＊は光学活性
点を示す。）で表わされる光学活性なＮ−カルバ
モイルピロリジノジホスフイン配位子（以下
CAPPと称す。）及びその製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention provides a novel general formula (In the formula, R 1 is an alkyl group, an alkenyl group, a cycloalkyl group, a phenyl group, a halogen-substituted phenyl group, or a nitro-substituted phenyl group, and * indicates an optically active point.) dinodiphosphine ligand (hereinafter
It is called CAPP. ) and its manufacturing method.
本発明の前記一般式（）で表わされる光学活
性なCAPPは〔Rh（オレフイン）2Cl〕2と反応さ
せることにより〔（CAPP）Rh（オレフイン）
Cl〕なる錯体を容易に形成する。このものは例
えば光学活性なα−アミノ酸類を製造する際に不
斉触媒として有用である。従来、不斉水素化触媒
を用いてα−アミノ酸誘導体を製造するプロセス
は例えばモンサント社のＬ−ドーパ合成にもみら
れる様に酵素法と並んで工業技術としての重要性
を増しつつある。この不斉水素化触媒として最も
効果の高いものは光学活性ホスフインを配位子と
するロジウム錯体であることが示されているが、
ここで高い光学収率を達成する鍵は効果的な配位
子を開発することである。従来、この考えのもと
にすでに多くの効果的なホスフイン配位子が開発
されてきた〔例えばB.D.Vineyard、W.S.
Knowles、M.J.Sabacky、G.L.Bachman and D.
J.Weinkauff、J.Am.Chem.Soc.、99、5946
（1976）；M.D.Fryzuk and B.Bosnich、J.Am.
Chem.Soc.、99、6262（1976）；T.Hayashi、T.
Mise、S.Mitachi、K.Yamamoto and M.
Kumada、Tetrahydren Lett.、1133（1976）〕。
しかし、これらは不斉ホスフイン配位子の合成に
光学分割を含み、更に配位子そのものが空気に不
安定なものが多く、入手が困難な上に取扱いが不
便であつた。そこで天然物中の不斉炭素を利用
し、官能基変換を用いて光学分割を含まず不斉配
位子を合成する方法が開発された〔例(1)T.−P.
Dang and H.B.Kagan、J.Am.Chem.Soc.、94、
6429（1972）．例(2)K.Achiwa、J.Am.Chem.Soc.
、98、8265（1976）．〕。しかしながら、例(1)の配
位子は実用化に必要な光学収率を実現出来る程効
果的でなく、又例(2)の配位子及びそのＮ−アシル
誘導体〔特開昭54−66672号参照〕も95％以上の
光学収率は達成出来ず、又結晶性も余り良くない
為、取扱いに不便である等の欠点がある。 The optically active CAPP represented by the general formula () of the present invention can be prepared by reacting with [Rh (olefin) 2 Cl] 2 [(CAPP)Rh (olefin)
It easily forms a complex called Cl]. This product is useful as an asymmetric catalyst, for example, in producing optically active α-amino acids. Conventionally, the process of producing α-amino acid derivatives using an asymmetric hydrogenation catalyst has been gaining importance as an industrial technology along with enzymatic methods, as seen for example in Monsanto's L-dopa synthesis. It has been shown that the most effective asymmetric hydrogenation catalyst is a rhodium complex containing an optically active phosphine as a ligand.
The key to achieving high optical yields here is to develop effective ligands. Conventionally, many effective phosphine ligands have already been developed based on this idea [e.g. BDVineyard, WS
Knowles, M.J.Sabacky, G.L.Bachman and D.
J.Weinkauff, J.Am.Chem.Soc., 99 , 5946
(1976); MDFryzuk and B. Bosnich, J. Am.
Chem.Soc., 99 , 6262 (1976); T. Hayashi, T.
Mise, S. Mitachi, K. Yamamoto and M.
Kumada, Tetrahydren Lett., 1133 (1976)].
However, these methods involve optical resolution in the synthesis of the asymmetric phosphine ligand, and many of the ligands themselves are unstable in air, making them difficult to obtain and inconvenient to handle. Therefore, a method was developed that utilizes asymmetric carbons in natural products and uses functional group conversion to synthesize asymmetric ligands without optical resolution [Example (1) T.-P.
Dang and HBKagan, J.Am.Chem.Soc., 94 ,
6429 (1972). Example (2) K.Achiwa, J.Am.Chem.Soc.
, 98 , 8265 (1976). ]. However, the ligand of Example (1) is not effective enough to achieve the optical yield necessary for practical use, and the ligand of Example (2) and its N-acyl derivatives [JP-A-54-66672 ] also cannot achieve an optical yield of 95% or more, and its crystallinity is not very good, so it has drawbacks such as being inconvenient to handle.
本発明質等は斯様な従来の欠点を克服すべく検
討した結果、取扱い容易な結晶性の非常に高い本
発明の化合物が、極めて高い光学収率をもたらす
不斉触媒の配位子として有用であることを見出
し、本発明を完成するに至つた。 As a result of studies aimed at overcoming these conventional drawbacks, we have found that the compounds of the present invention, which are easy to handle and have very high crystallinity, are useful as ligands for asymmetric catalysts that provide extremely high optical yields. We have discovered that this is the case, and have completed the present invention.
本発明の前記一般式（）で表わされる光学活
性なCAPPは構造式
（式中、＊は光学活性点を示す。）で表わされる光
学活性なピロリジノジホスフインと一般式
R1−Ｎ＝Ｃ＝Ｏ −（）
（式中R1はアルキル基、アルケニル基、シクロア
ルキル基、フエニル基、ハロゲン置換フエニル基
又はニトロ置換フエニル基である。）で表わされ
るイソシアナートとを反応させることにより製造
できる。前記一般式（）の化合物は特開昭53−
65872号及び特開昭54−66672号に記載の方法によ
り容易に得られる化合物である。前者の文献に示
される化合物は2S・4S−体であり、後者の文献
に示される化合物は2S・4S−体及び2R・4R−体
である。一方の原料である前記一般式（）の化
合物は工業的に容易に入手可能な化合物である。
前記一般式（）のイソシアナートとしては、メ
チルイソシアナート、アリルイソシアナート、シ
クロヘキシルイソシアナートの如きアルキルイソ
シアナート、フエニルイソシアナート、クロロフ
エニルイソシアナート、ブロモフエニルイソシア
ナート、ｐ−ニトロフエニルイソシアナート、ト
リルイソシアナート、アニシルイソシアナート、
ジクロロフエニルイソシアナート、ナフチルイソ
シアナート、チエニルイソシアナート、フリルイ
ソシアナート、ピリジルイソシアナートの如きア
リールイソシアナートを例示することが出来る。 The optically active CAPP represented by the general formula () of the present invention has the structural formula (In the formula, * indicates an optically active point.) Optically active pyrrolidinodiphosphine represented by the general formula R 1 -N=C=O - () (wherein R 1 is an alkyl group, an alkenyl group, It can be produced by reacting with an isocyanate represented by a cycloalkyl group, a phenyl group, a halogen-substituted phenyl group, or a nitro-substituted phenyl group. The compound of the above general formula () is disclosed in Japanese Patent Application Laid-Open No. 1986-
It is a compound easily obtained by the method described in No. 65872 and JP-A-54-66672. The compounds shown in the former literature are 2S·4S-forms, and the compounds shown in the latter literature are 2S·4S-forms and 2R·4R- forms. The compound of the general formula (), which is one of the raw materials, is a compound that is easily available industrially.
Examples of the isocyanate of the general formula () include alkyl isocyanates such as methyl isocyanate, allyl isocyanate, and cyclohexyl isocyanate, phenyl isocyanate, chlorophenyl isocyanate, bromophenyl isocyanate, and p-nitrophenyl isocyanate. tolyl isocyanate, anisyl isocyanate,
Examples include aryl isocyanates such as dichlorophenyl isocyanate, naphthyl isocyanate, thienyl isocyanate, furyl isocyanate, and pyridyl isocyanate.
本発明の実施にあたつては溶媒の使用が好まし
く、クロロホルム、四塩化炭素の如きハロゲン化
炭化水素、ベンゼン、トルエン等の芳香族炭化水
素を使用できる。反応は０〜50℃で円滑に進行す
るが操作の容易な室温での反応が好ましい。 In carrying out the present invention, it is preferable to use a solvent, and halogenated hydrocarbons such as chloroform and carbon tetrachloride, aromatic hydrocarbons such as benzene and toluene can be used. Although the reaction proceeds smoothly at 0 to 50°C, the reaction is preferably carried out at room temperature for ease of operation.
以下、本発明を実施例及び参考例により更に詳
細に説明する。 Hereinafter, the present invention will be explained in more detail with reference to Examples and Reference Examples.
実施例 １
（2S・4S）−４−ジフエニルホスフイノ−２−
ジフエニルホスフイノメチルピロリジン（以下
PPMと略す）0.907ｇ（2.00ｍmol）とイソシアン
酸フエニル0.250ｇ（2.10ｍmol）を20mlのクロロ
ホルム中、アルゴン雰囲気下、室温で10分間撹拌
混合した後、薄層クロマトグラフイーで反応の完
了を確認した。溶媒を留去して得られた淡黄色粉
末をシリカゲルカラムクロマトグラフイー（クロ
ロホルム）によつて精製し、白色粉末0.949ｇ
（1.66ｍmol）を得た。このものをエタノール35ml
から再結晶し、融点180〜183℃、〔α〕２５ Ｄ−22.20
゜（c0.504、PhH）を有する（2S・4S）−Ｎ−（Ｎ
−フエニルカルバモイル）−４−ジフエニルホス
フイノメチルピリジンの無色針状結晶0.770ｇを
得た（収率67.2％）。Example 1 (2S・4S)-4-diphenylphosphino-2-
Diphenylphosphinomethylpyrrolidine (hereinafter
PPM) 0.907 g (2.00 mmol) and phenyl isocyanate 0.250 g (2.10 mmol) were stirred and mixed in 20 ml of chloroform at room temperature under an argon atmosphere for 10 minutes, and the completion of the reaction was confirmed by thin layer chromatography. did. The pale yellow powder obtained by distilling off the solvent was purified by silica gel column chromatography (chloroform) to obtain 0.949 g of white powder.
(1.66 mmol) was obtained. Add this to 35ml of ethanol
Recrystallized from, melting point 180-183℃, [α] 25D -22.20
(2S・4S)-N-(N
0.770 g of colorless needle crystals of -phenylcarbamoyl)-4-diphenylphosphinomethylpyridine were obtained (yield 67.2%).
NMR（CDCl3）：δ1.60−4.30（多重線、8H）、
5.86（一重線、1H）、6.82−7.65（多重線、
25H）．
IR（KBr disk）：3430（ 〓NH）、1645（ 〓Ｃ
＝Ｏ）、1510（アミド）cm-1.
元素分析値：C36H34N2OP2
理論値；Ｃ；75.51、Ｈ；5.99、Ｎ；4.89％．
実測値；Ｃ；75.39、Ｈ；5.96、Ｎ；4.89％．
実施例 ２
PPM0.907ｇ（2.00ｍmol）とイソシアン酸ｐ−
クロロフエニル0.322ｇ（2.10ｍmol）を20mlのク
ロロホルム中で実施例１と同様に反応させた。溶
媒を留去して得られた淡黄色粉末をシリカゲルカ
ラムクロマトグラフイー（クロロホルム）によつ
て精製し、白色粉末1.20ｇ（1.98ｍmol）を得
た。このものをエタノール45mlから再結晶し、融
点180.5〜181.5℃、〔α〕２５ Ｄ−13.99゜（c0.507、
PhH）を有する（2S・4S）−Ｎ−（Ｎ−ｐ−クロ
ロフエニルカルバモイル）−４−ジフエニルホス
フイノ−２−ジフエニルホスフイノメチルピロリ
ジンの無色針状結晶0.807ｇを得た（収率66.5
％）。NMR ( CDCl3 ): δ1.60−4.30 (multiplet, 8H),
5.86 (singlet, 1H), 6.82−7.65 (multiplet,
25H). IR (KBr disk): 3430 (〓NH), 1645 (〓C
=O), 1510 (amide) cm -1 . Elemental analysis: C 36 H 34 N 2 OP 2 Theoretical value: C: 75.51, H: 5.99, N: 4.89%. Actual value: C: 75.39, H: 5.96, N: 4.89%. Example 2 PPM0.907g (2.00mmol) and isocyanic acid p-
0.322 g (2.10 mmol) of chlorophenyl was reacted in 20 ml of chloroform in the same manner as in Example 1. The pale yellow powder obtained by distilling off the solvent was purified by silica gel column chromatography (chloroform) to obtain 1.20 g (1.98 mmol) of white powder. This product was recrystallized from 45 ml of ethanol, with a melting point of 180.5-181.5°C, [α] 25 D -13.99° (c0.507,
0.807 g of colorless needle crystals of (2S・4S)-N-(N-p-chlorophenylcarbamoyl)-4-diphenylphosphino-2-diphenylphosphinomethylpyrrolidine having PhH) were obtained (yield 66.5
%).
NMR（CDCl3）：δ160−4.25（多重線、8H）、
5.96（一重線、1H）、7.03−7.66（多重線、
24H）．
IR（KBr disk）：3280（ 〓NH）、1635（ 〓Ｃ
＝Ｏ）、1520（アミド）cm-1.
元素分析：C36H33ClN2OP2
理論値；
Ｃ；71.23、Ｈ；5.48、Cl；5.84、Ｎ；4.61％．
実測値；
Ｃ；70.98、Ｈ；5.45、Cl；5.95、Ｎ；4.61％．
実施例 ３
PPM0.907ｇ（2.00ｍmol）とイソシアン酸ｐ−
ブロモフエニル0.416ｇ（2.10ｍmol）を20mlのク
ロロホルム中で実施例１と同様に反応をせた。溶
媒を留去して得られた淡黄色粉末をシリカゲルカ
ラムクロマトグラフイー（クロロホルム）によつ
て精製し、白色粉末1.17ｇ（1.80ｍmol）を得
た。このものをエタノール75mlから再結晶し、融
点181〜184℃、〔α〕２５ Ｄ−10.45゜（c0.507、PhH）
を有する（2S・4S）−Ｎ−（Ｎ−ｐ−ブロモフエ
ニルカルバモイル）−４−ジフエニルホスフイノ
−２−ジフエニルホスフイノメチルピロリジンの
無色針状結晶0.742ｇを得た（収率56.9％）。NMR ( CDCl3 ): δ160−4.25 (multiplet, 8H),
5.96 (singlet, 1H), 7.03−7.66 (multiplet,
24H). IR (KBr disk): 3280 (〓NH), 1635 (〓C
=O), 1520 (amide) cm -1 . Elemental analysis: C 36 H 33 ClN 2 OP 2 theoretical value;
C: 71.23, H: 5.48, Cl: 5.84, N: 4.61%. Actual value;
C: 70.98, H: 5.45, Cl: 5.95, N: 4.61%. Example 3 PPM0.907g (2.00mmol) and isocyanic acid p-
0.416 g (2.10 mmol) of bromophenyl was reacted in 20 ml of chloroform in the same manner as in Example 1. The pale yellow powder obtained by distilling off the solvent was purified by silica gel column chromatography (chloroform) to obtain 1.17 g (1.80 mmol) of white powder. This product was recrystallized from 75 ml of ethanol, melting point 181-184℃, [α] 25 D -10.45゜ (c0.507, PhH)
0.742 g of colorless needle crystals of (2S・4S)-N-(N-p-bromophenylcarbamoyl)-4-diphenylphosphino-2-diphenylphosphinomethylpyrrolidine were obtained (yield 56.9). %).
NMR（CDCl3）：δ1.67−4.37（多重線、8H）、
5.88（一重線、1H）、6.93−7.70（多重線、
24H）．
IR（KBr disk）：3270（ 〓NH）、1640（ 〓Ｃ
＝Ｏ）、1510（アミド）cm-1.
元素分析：C36H33BrN2OP2
理論値；Ｃ；66.37、Ｈ；5.11、Br；12.26、
Ｎ；4.30％．
実測値；Ｃ；66.19、Ｈ；4.93、Br；12.14、
Ｎ；4.32％．
実施例 ４
PPM0.907ｇ（2.00ｍmol）とイソシアン酸３・
４−ジクロロフエニル0.395ｇ（2.10ｍmol）を20
mlのクロロホルム中で実施例１と同様に反応させ
た。溶媒を留去して得られた白色粉末をシリカゲ
ルカラムクロマトグラフイー（クロロホルム）に
よつて精製し、白色粉末1.17ｇ（1.82ｍmol）を
得た。このものをエタノール20mlから再結晶し、
融点148〜151℃、〔α〕２５ Ｄ−10.77゜（c0.501、
PhH）を有する（2S・4S）−Ｎ−（Ｎ−３・４−
ジクロロフエニルカルバモイル）−４−ジフエニ
ルホスフイノ−２−ジフエニルホスフイノメチル
ピロリジンの無色針状結晶0.947ｇを得た（収率
73.8％）。NMR ( CDCl3 ): δ1.67−4.37 (multiplet, 8H),
5.88 (singlet, 1H), 6.93−7.70 (multiplet,
24H). IR (KBr disk): 3270 (〓NH), 1640 (〓C
=O), 1510 (amide) cm -1 . Elemental analysis: C 36 H 33 BrN 2 OP 2 Theoretical value; C; 66.37, H; 5.11, Br; 12.26,
N; 4.30%. Actual value; C; 66.19, H; 4.93, Br; 12.14,
N; 4.32%. Example 4 PPM0.907g (2.00mmol) and isocyanic acid 3.
4-dichlorophenyl 0.395g (2.10mmol) in 20
ml of chloroform in the same manner as in Example 1. The white powder obtained by distilling off the solvent was purified by silica gel column chromatography (chloroform) to obtain 1.17 g (1.82 mmol) of white powder. This product was recrystallized from 20 ml of ethanol,
Melting point 148-151℃, [α] 25D -10.77゜(c0.501,
(2S・4S)-N-(N-3・4-
0.947 g of colorless needle crystals of (dichlorophenylcarbamoyl)-4-diphenylphosphino-2-diphenylphosphinomethylpyrrolidine were obtained (yield
73.8%).
NMR（CDCl3）：δ1.60−4.32（多重線、8H）、
5.91（一重線、1H）、6.87−7.66（多重線、
23H）
IR（KBr disk）：3280（ 〓NH）、1645（ 〓Ｃ
＝０）、1510（アミド）cm-1.
元素分析：C36H32Cl2N2OP2
理論値；Ｃ；67.40、Ｈ；5.03、Cl；11.05、
Ｎ；4.37％．
実測値；Ｃ；67.33、Ｈ；4.94、Cl；10.91、
Ｎ；4.40％．
実施例 ５
PPM0.907ｇ（2.00ｍmol）とイソシアン酸ｐ−
ニトロフエニル0.377ｇ（2.30ｍmol）を20mlのク
ロロホルム中で実施例１と同様に反応させた。溶
媒を留去して得られた黄色粉末をシリカゲルカラ
ムクロマトグラフイー（クロロホルム）によつて
精製し、黄色粉末1.25ｇ（1.97ｍmol）を得た。
このものをクロロホルム12ml、ヘキサン25mlから
再結晶し、融点103〜106℃、〔α〕２５ Ｄ−4.19゜
（c0.501、PhH）を有する（2S・4S）−Ｎ−（Ｎ−
ｐ−ニトロフエニルカルバモイル）−４−ジフエ
ニルホスフイノ−２−ジフエニルホスフイノメチ
ルピロリジンの淡黄色針状結晶0.900ｇを得た
（収率72.9％）。NMR ( CDCl3 ): δ1.60−4.32 (multiplet, 8H),
5.91 (singlet, 1H), 6.87−7.66 (multiplet,
23H) IR (KBr disk): 3280 (〓NH), 1645 (〓C
= 0), 1510 (amide) cm -1 . Elemental analysis: C 36 H 32 Cl 2 N 2 OP 2 Theoretical value; C; 67.40, H; 5.03, Cl; 11.05,
N; 4.37%. Actual value; C; 67.33, H; 4.94, Cl; 10.91,
N; 4.40%. Example 5 PPM0.907g (2.00mmol) and isocyanic acid p-
0.377 g (2.30 mmol) of nitrophenyl was reacted in the same manner as in Example 1 in 20 ml of chloroform. The yellow powder obtained by distilling off the solvent was purified by silica gel column chromatography (chloroform) to obtain 1.25 g (1.97 mmol) of yellow powder.
This product was recrystallized from 12 ml of chloroform and 25 ml of hexane to give (2S・4S)-N-(N-
0.900 g of pale yellow needle crystals of p-nitrophenylcarbamoyl)-4-diphenylphosphino-2-diphenylphosphinomethylpyrrolidine were obtained (yield 72.9%).
NMR（CDCl3）：δ1.60−4.37（多重線、8H）、
6.38（一重線、1H）、6.98−8.20（多重線、
24H）．
IR（KBr disk）：3360（ 〓Ｈ）、1655（ 〓Ｃ＝
０）、1525（アミノ）cm-1.
元素分析：C36H33N3O3P2
理論値：Ｃ；70.00、Ｈ；5.39、Ｎ；6.80％．
実測値：Ｃ；69.86、Ｈ；5.38、Ｎ；6.76％．
実施例 ６
PPM0.907ｇ（2.00ｍmol）とイソシアン酸メチ
ル0.143ｇ（2.50ｍmol）を20mlのクロロホルム中
で実施例１と同様に反応させた。溶媒をロータリ
ーエバポレーター、真空ポンプで留去したとこ
ろ、淡黄色の粉末1.03ｇが得られた。シリカゲル
カラムクロマトグラフイ−（クロロホルム：酢酸
エチル＝95：５）によつて精製し、融点73〜77
℃、〔α〕２５ Ｄ−12.35゜（c0.502、PhH）を有する
（2S・4S）−Ｎ−（Ｎ−メチルカルバモイル）−４
−ジフエニルホスフイノ−２−ジフエニルホスフ
イノメチルピロリジンの無色結晶0.939ｇを得た
（収率92.0％）。NMR ( CDCl3 ): δ1.60−4.37 (multiplet, 8H),
6.38 (singlet, 1H), 6.98−8.20 (multiplet,
24H). IR (KBr disk): 3360 (〓H), 1655 (〓C=
0), 1525 (amino) cm -1 . Elemental analysis: C 36 H 33 N 3 O 3 P 2 Theoretical values: C: 70.00, H: 5.39, N: 6.80%. Actual values: C: 69.86, H: 5.38, N: 6.76%. Example 6 0.907 g (2.00 mmol) of PPM and 0.143 g (2.50 mmol) of methyl isocyanate were reacted in the same manner as in Example 1 in 20 ml of chloroform. When the solvent was distilled off using a rotary evaporator and a vacuum pump, 1.03 g of pale yellow powder was obtained. Purified by silica gel column chromatography (chloroform:ethyl acetate = 95:5), melting point 73-77
(2S・4S)-N-(N-methylcarbamoyl)-4 with °C, [α] 25 D -12.35° (c0.502, PhH)
0.939 g of colorless crystals of -diphenylphosphino-2-diphenylphosphinomethylpyrrolidine were obtained (yield 92.0%).
NMR（CDCl3）：δ1.70−4.30（多重線、9H）、
2.58（一重線、3H）、7.04−7.72（多重線、
20H）．
IR（KBr disk）：3330（ 〓NH）、1625（ 〓Ｃ
＝０）、1525（アミド）cm-1.
元素分析：C31H32N2OP2
理論値：Ｃ；72.93、Ｈ；6.32、Ｎ；5.49％．
実測値：
実施例 ７
PPM0.907ｇ（2.00ｍmol）とイソシアン酸アリ
ル0.208ｇ（2.50ｍmol）を20mlのクロロホルム中
で実施例１と同様に反応させた。溶媒をロータリ
ーエバポレーター、真空ポンプで留出したとこ
ろ、淡黄色の粉末1.10ｇが得られた。シリカゲル
カラムクロマトグラフイー（クロロホルム）によ
つて精製し、融点76〜79℃、〔α〕２５ Ｄ−8.85゜
（c0.508、MeOH）を有する（2S・4S）−Ｎ−（Ｎ
−アリルカルバモイル）−４−ジフエニルホスフ
イノ−２−ジフエニルホスフイノメチルピロリジ
ンの淡黄色結晶0.973ｇを得た（収率90.7％）。NMR ( CDCl3 ): δ1.70−4.30 (multiplet, 9H),
2.58 (singlet, 3H), 7.04−7.72 (multiplet,
20H). IR (KBr disk): 3330 (〓NH), 1625 (〓C
=0), 1525 (amide) cm -1 . Elemental analysis: C 31 H 32 N 2 OP 2 Theoretical value: C; 72.93, H; 6.32, N; 5.49%. Measured values: Example 7 0.907 g (2.00 mmol) of PPM and 0.208 g (2.50 mmol) of allyl isocyanate were reacted in the same manner as in Example 1 in 20 ml of chloroform. When the solvent was distilled off using a rotary evaporator and a vacuum pump, 1.10 g of pale yellow powder was obtained. Purified by silica gel column chromatography ( chloroform ), ( 2S4S )-N-(N
0.973 g of pale yellow crystals of -allylcarbamoyl)-4-diphenylphosphino-2-diphenylphosphinomethylpyrrolidine were obtained (yield 90.7%).
NMR（CDCl3）：δ1.67−4.23（多重線、11H）、
4.82−5.28（多重線、2H）、5.47−6.16（多重
線、1H）、7.00−7.75（多重線、20H）．
IR（KBr disk）：3320（ 〓NH）、1625（ 〓Ｃ
＝０）、1515（アミド）cm-1.
元素分析：C33H34N2OP2
理論値；Ｃ；73.87、Ｈ；6.39、Ｎ；5.22％．
実測値：
実施例 ８
PPM0.907ｇ（2.00ｍmol）とイソシアン酸シク
ロヘキシル0.282ｇ（2.25ｍmolを20mlのクロロホ
ルム中で実施例１と同様に反応させた。溶媒をロ
ータリーエバポレーター、真空ポンプで留去した
ところ、淡黄色の粉末1.19ｇが得られた。シリカ
ゲルカラムクロマトグラフイー（クロロホルム）
によつて精製し、融点79〜82℃、〔α〕２５ Ｄ−11.80
゜（c0.500、PhH）を有する（2S・4S）−Ｎ−（Ｎ
−シクロヘキシルカルバモイル）−４−ジフエニ
ルホスフイノ−２−ジフエニルホスフイノメチル
ピロリジンの無色結晶1.08ｇを得た（収率93.3
％）。NMR ( CDCl3 ): δ1.67−4.23 (multiplet, 11H),
4.82−5.28 (multiplet, 2H), 5.47−6.16 (multiplet, 1H), 7.00−7.75 (multiplet, 20H). IR (KBr disk): 3320 (〓NH), 1625 (〓C
=0), 1515 (amide) cm -1 . Elemental analysis: C 33 H 34 N 2 OP 2 Theoretical value; C: 73.87, H: 6.39, N: 5.22%. Actual measurements: Example 8 0.907 g (2.00 mmol) of PPM and 0.282 g (2.25 mmol) of cyclohexyl isocyanate were reacted in the same manner as in Example 1 in 20 ml of chloroform. The solvent was distilled off using a rotary evaporator and a vacuum pump. , 1.19 g of pale yellow powder was obtained. Silica gel column chromatography (chloroform)
Purified by , melting point 79-82℃, [α] 25D -11.80
(2S・4S)-N-(N
1.08 g of colorless crystals of cyclohexylcarbamoyl)-4-diphenylphosphino-2-diphenylphosphinomethylpyrrolidine were obtained (yield: 93.3).
%).
NMR（CDCl3）：δ0.60−4.17（多重線、20H）、
6.94−7.78（多重線、20H）．
IR（KBr disk）：3320（ 〓NH）、1625（ 〓Ｃ
＝０）、1510（アミド）cm-1.
元素分析：C36H40N2OP2
理論値；Ｃ；74.72、Ｈ；6.97、Ｎ；4.84％．
実測値；Ｃ；74.48、Ｈ；6.96、Ｎ；4.82％．
実施例 ９
（2R・4R）−４−ジフエニルホスフイノ−２−
ジフエニルホスフイノメチルピロリジン0.454ｇ
（1.00ｍmol）とイソシアン酸３・４−ジクロロフ
エニル0.207ｇ（1.10ｍmol）を10mlのクロロホル
ム中で実施例１と同様に反応させた。溶媒を留去
して得られた白色粉末をシリカゲルカラムクロマ
トグラフイー（クロロホルム）によつて精製し、
白色粉末0.617ｇ（0.961ｍmol）を得た。このも
のをエタノール10mlから再結晶し、融点147〜149
℃、〔α〕２５ Ｄ−10.79゜（c0.506、PhH）を有する
（2R・4R）−Ｎ−（Ｎ−３・４−ジクロロフエニル
カルバモイル）−４−ジフエニルホスフイノ−２
−ジフエニルホスフイノメチルピロリジンの無色
針状結晶0.501ｇを得た（収率78.1％）。NMR ( CDCl3 ): δ0.60−4.17 (multiplet, 20H),
6.94−7.78 (multiplet, 20H). IR (KBr disk): 3320 (〓NH), 1625 (〓C
= 0), 1510 (amide) cm -1 . Elemental analysis: C 36 H 40 N 2 OP 2 Theoretical value; C: 74.72, H: 6.97, N: 4.84%. Actual value: C: 74.48, H: 6.96, N: 4.82%. Example 9 (2R・4R)-4-diphenylphosphino-2-
Diphenylphosphinomethylpyrrolidine 0.454g
(1.00 mmol) and 0.207 g (1.10 mmol) of 3,4-dichlorophenyl isocyanate were reacted in the same manner as in Example 1 in 10 ml of chloroform. The white powder obtained by distilling off the solvent was purified by silica gel column chromatography (chloroform),
0.617 g (0.961 mmol) of white powder was obtained. This product was recrystallized from 10 ml of ethanol, with a melting point of 147-149.
(2R·4R)-N-(N-3·4-dichlorophenylcarbamoyl)-4-diphenylphosphino-2 with ℃, [α] 25 D −10.79° (c0.506, PhH)
- 0.501 g of colorless needle crystals of diphenylphosphinomethylpyrrolidine were obtained (yield 78.1%).
NMR（CDCl3）：δ1.60−4.32（多重線、8H）、
5.93（一重線、1H）、6.87−7.67（多重線、
23H）．
IR（KBr disk）：3280（ 〓NH）、1645（ 〓Ｃ
＝０）、1510（アミド）cm-1.
参考例 １
パイレツクス反応器に（2S・4S）−Ｎ−（Ｎ−
ｐ−ブロモフエニルカルバモイル）−４−ジフエ
ニルホスフイノ−２−ジフエニルホスフイノメチ
ルピロリジン15.6mg（0.024ｍmol）と〔Rh
（１・５−シクロオクタジエン）C1〕24.93mg
（0.010ｍmol）をエタノール16ml中で30分間撹拌
して触媒を調整した。NMR ( CDCl3 ): δ1.60−4.32 (multiplet, 8H),
5.93 (singlet, 1H), 6.87−7.67 (multiplet,
23H). IR (KBr disk): 3280 (〓NH), 1645 (〓C
= 0), 1510 (amide) cm -1 . Reference example 1 (2S・4S)-N-(N-
15.6 mg (0.024 mmol) of p-bromophenylcarbamoyl)-4-diphenylphosphino-2-diphenylphosphinomethylpyrrolidine and [Rh
(1,5-cyclooctadiene)C1] 2 4.93mg
(0.010 mmol) was stirred in 16 ml of ethanol for 30 minutes to prepare the catalyst.
次に、Ｚ−α−アセトアミド桂皮酸メチル438
mg（2.00ｍmol）と上記で調整した触媒0.020ｍ
mol（1.0mol％）を含むエタノール溶液を１気圧
の水素圧下25℃で18時間撹拌した。反応の終了は
ガスビユレツトによる水素吸収量により確認し
た。反応混合物にイオン交換樹脂（ダウコーニン
グ社、50W−X2、H+型）0.5ｇと0.05ｇ程度の活
性炭を加えて10分間撹拌した後、ろ別した。ろ液
から溶媒をロータリーエバポレーター、真空ポン
プで十分に留去して〔α〕２６ Ｄ−15.49゜（c2.001、
MeOH）（97.4％e.e.）を有する（Ｒ）−Ｎ−アセ
チルフエニルアラニンメチルエステル437mgを得
た（収率98.7％）。 Next, methyl Z-α-acetamidocinnamate 438
mg (2.00 mmol) and 0.020 m of the catalyst prepared above
mol (1.0 mol%) was stirred at 25° C. for 18 hours under 1 atmosphere of hydrogen pressure. Completion of the reaction was confirmed by the amount of hydrogen absorbed by the gas bottle. 0.5 g of an ion exchange resin (Dow Corning, 50W-X 2 , H + type) and about 0.05 g of activated carbon were added to the reaction mixture, stirred for 10 minutes, and then filtered. The solvent was sufficiently distilled off from the filtrate using a rotary evaporator and a vacuum pump to obtain [α] 26 D -15.49° (c2.001,
437 mg of (R)-N-acetylphenylalanine methyl ester with MeOH) (97.4% ee) was obtained (yield 98.7%).
参考例 ２
参考例１と同様にして（2S・4S）−Ｎ−（Ｎ−
３・４−ジクロロフエニルカルバモイル）−４−
ジフエニルホスフイノ−２−ジフエニルホスフイ
ノメチルピロリジン15.4mg（0.024ｍmol）と
〔Rh（１・５−シクロオクタジエン）C1〕24.93mg
（0.010ｍmol）から中性ロジウム錯体エタノール
溶液（16ml）を調整し、Ｚ−α−アセトアミド桂
皮酸メチルエステル438mg（2.00ｍmol）に加え、
１気圧の水素圧下25℃で16時間撹拌した。参考例
１と同様に後処理を行い、〔α〕２６ Ｄ−15.49゜
（c2.007、MeOH）（97.4％e.e.）を有する（Ｒ）−
Ｎ−アセチルフエニルアラニンメチルエステル
434mgを得た（収率98.0％）。Reference example 2 Same as reference example 1, (2S・4S)-N-(N-
3,4-dichlorophenylcarbamoyl)-4-
Diphenylphosphino-2-diphenylphosphinomethylpyrrolidine 15.4mg (0.024mmol) and [Rh(1,5-cyclooctadiene)C1] 2 4.93mg
A neutral rhodium complex ethanol solution (16 ml) was prepared from (0.010 mmol) and added to 438 mg (2.00 mmol) of Z-α-acetamidocinnamic acid methyl ester.
Stirred at 25° C. for 16 hours under 1 atmosphere of hydrogen pressure. Post-treatment was performed in the same manner as in Reference Example 1, and (R)- having [α] 26 D −15.49° (c2.007, MeOH) (97.4% ee)
N-acetylphenylalanine methyl ester
434 mg was obtained (yield 98.0%).
Claims (1)
ジノジホスフイン配位子（式中R1はアルキル
基、アルケニル基、シクロアルキル基、フエニル
基、ハロゲン置換フエニル基又はニトロ置換フエ
ニル基であり、＊は光学活性点を示す。）。 ２ ＊で示した二個所の活性点の異性体の配位が
共にＳ又はＲである特許請求の範囲第１項に記載
の化合物。 ３ 構造式 で表わされる光学活性なピロリジノジホスフイン
と一般式 R1−Ｎ＝Ｃ＝Ｏ で表わされるイソシアナートとを反応させること
からなる一般式 で表わされる光学活性なＮ−カルバモイルピロリ
ジノジホスフイン配位子の製造方法（式中R1は
アルキル基、アルケニル基、シクロアルキル基、
フエニル基、ハロゲン置換フエニル基又はニトロ
置換フエニル基であり、＊は光学活性点を示
す。）。[Claims] 1. General formula An optically active N - carbamoylpyrrolidinodiphosphine ligand represented by (indicates an optically active point). 2. The compound according to claim 1, wherein the isomers at the two active sites indicated by * are both S or R in coordination. 3 Structural formula A general formula consisting of reacting an optically active pyrrolidinodiphosphine represented by with an isocyanate represented by the general formula R 1 -N=C=O A method for producing an optically active N-carbamoylpyrrolidinodiphosphine ligand represented by (wherein R 1 is an alkyl group, an alkenyl group, a cycloalkyl group,
It is a phenyl group, a halogen-substituted phenyl group, or a nitro-substituted phenyl group, and * indicates an optically active point. ).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11413979A JPS5639097A (en) | 1979-09-07 | 1979-09-07 | Optically active n-carbamoylpyrrolidinodiphosphine ligand and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11413979A JPS5639097A (en) | 1979-09-07 | 1979-09-07 | Optically active n-carbamoylpyrrolidinodiphosphine ligand and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5639097A JPS5639097A (en) | 1981-04-14 |
| JPS6210516B2 true JPS6210516B2 (en) | 1987-03-06 |
Family
ID=14630107
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11413979A Granted JPS5639097A (en) | 1979-09-07 | 1979-09-07 | Optically active n-carbamoylpyrrolidinodiphosphine ligand and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5639097A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4539411A (en) * | 1982-02-05 | 1985-09-03 | Hoffmann-La Roche Inc. | Rhodium complexes of chiral phosphines |
-
1979
- 1979-09-07 JP JP11413979A patent/JPS5639097A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5639097A (en) | 1981-04-14 |
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