JPH01305039A - Production of optically active 1,1'-binaphthyl derivative - Google Patents
Production of optically active 1,1'-binaphthyl derivativeInfo
- Publication number
- JPH01305039A JPH01305039A JP13602288A JP13602288A JPH01305039A JP H01305039 A JPH01305039 A JP H01305039A JP 13602288 A JP13602288 A JP 13602288A JP 13602288 A JP13602288 A JP 13602288A JP H01305039 A JPH01305039 A JP H01305039A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- optically active
- derivative
- lower alkyl
- general formula
- 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
- ZDZHCHYQNPQSGG-UHFFFAOYSA-N 1-naphthalen-1-ylnaphthalene Chemical group C1=CC=C2C(C=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 ZDZHCHYQNPQSGG-UHFFFAOYSA-N 0.000 title claims description 9
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 239000000126 substance Substances 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 230000003287 optical effect Effects 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- 239000007818 Grignard reagent Substances 0.000 claims abstract description 6
- 150000004795 grignard reagents Chemical class 0.000 claims abstract description 6
- 125000005843 halogen group Chemical group 0.000 claims abstract description 6
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 5
- 238000006880 cross-coupling reaction Methods 0.000 claims abstract description 4
- 150000002790 naphthalenes Chemical class 0.000 claims abstract description 4
- 125000003118 aryl group Chemical group 0.000 claims abstract description 3
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 3
- 229910052762 osmium Inorganic materials 0.000 claims abstract 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 125000004429 atom Chemical group 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 21
- 238000006243 chemical reaction Methods 0.000 abstract description 16
- 239000000203 mixture Substances 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 229910052736 halogen Inorganic materials 0.000 abstract 2
- 125000001624 naphthyl group Chemical group 0.000 abstract 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 4
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 description 4
- 238000004811 liquid chromatography Methods 0.000 description 4
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 description 4
- 238000010898 silica gel chromatography Methods 0.000 description 4
- 239000002904 solvent Substances 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- CMIMBQIBIZZZHQ-UHFFFAOYSA-N 1-bromo-2-methylnaphthalene Chemical compound C1=CC=CC2=C(Br)C(C)=CC=C21 CMIMBQIBIZZZHQ-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000011914 asymmetric synthesis Methods 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- LYRLLQRVTWRTAJ-UHFFFAOYSA-M magnesium;2-methyl-1h-naphthalen-1-ide;bromide Chemical compound [Mg+2].[Br-].C1=CC=CC2=[C-]C(C)=CC=C21 LYRLLQRVTWRTAJ-UHFFFAOYSA-M 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 2
- WCXOVPQJHCPRMO-UHFFFAOYSA-N 1-bromo-2,6-dimethylnaphthalene Chemical compound BrC1=C(C)C=CC2=CC(C)=CC=C21 WCXOVPQJHCPRMO-UHFFFAOYSA-N 0.000 description 1
- JOLBERKGKHVHHL-UHFFFAOYSA-N 1-bromo-2-ethylnaphthalene Chemical compound C1=CC=CC2=C(Br)C(CC)=CC=C21 JOLBERKGKHVHHL-UHFFFAOYSA-N 0.000 description 1
- DLKQHBOKULLWDQ-UHFFFAOYSA-N 1-bromonaphthalene Chemical compound C1=CC=C2C(Br)=CC=CC2=C1 DLKQHBOKULLWDQ-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 240000006162 Chenopodium quinoa Species 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- DXTHLNYNHYKVEH-UHFFFAOYSA-M [Br-].C1=CC=CC2=C([Mg+])C(CC)=CC=C21 Chemical compound [Br-].C1=CC=CC2=C([Mg+])C(CC)=CC=C21 DXTHLNYNHYKVEH-UHFFFAOYSA-M 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000003950 cyclic amides Chemical class 0.000 description 1
- YLQBEKUKMJWXMC-UHFFFAOYSA-N cyclopenta-1,3-diene cyclopenta-2,4-dien-1-ylphosphane iron(2+) Chemical class [Fe++].c1cc[cH-]c1.P[c-]1cccc1 YLQBEKUKMJWXMC-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000012156 elution solvent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- -1 magnesium halide Chemical class 0.000 description 1
- NXPHGHWWQRMDIA-UHFFFAOYSA-M magnesium;carbanide;bromide Chemical compound [CH3-].[Mg+2].[Br-] NXPHGHWWQRMDIA-UHFFFAOYSA-M 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006894 reductive elimination reaction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229940102001 zinc bromide Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
- C07C1/325—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a metal atom
- C07C1/326—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a metal atom the hetero-atom being a magnesium atom
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は一般式（１）
（式中、Ｒ，、Ｒ，、Ｒ５右よびＲ７は水素原子または
低級アルキル基を示す。）
〈従来の技術〉
上記の光学活性な１、ｌｏ−ビナフチル誘導体（Ｉ）の
製造法としては、玉尾ら（ＴｅｔｒａｈｅｄｒｏｎＬｅ
ｔｔ、 、 １３８９．１９７７ ）および宮野う（を
機合成化学協会誌、４４巻、８号、 ７１３（１９８６
） ）の触媒的クロスカップリングを用いる方法が知
られているが、該製造法は化学収率が２０％以下であり
、かつ光学収率が１８％と非常に低いものである。Detailed Description of the Invention <Industrial Application Field> The present invention relates to the general formula (1) (wherein, R, R, R5 and R7 represent a hydrogen atom or a lower alkyl group). Technology> As a method for producing the above optically active 1,lo-binaphthyl derivative (I), Tamao et al.
tt, , 1389.1977) and U Miyano (Journal of the Society of Synthetic Chemistry, Vol. 44, No. 8, 713 (1986)
) A method using catalytic cross-coupling is known, but the chemical yield of this production method is 20% or less, and the optical yield is very low at 18%.
また、＾、Ｉ、 Ｍｅｙｅｒｓら（Ｊ、＾、 Ｃ，Ｓ、
、、 、１０４．８７９ （１９８２） ）の方法は不
斉源として原料化合物に対して１当量の光学活性アミノ
アルコールを用いるため、不斉合成反応終了後、還元的
脱離反応を行う必要があり、化学収率も約６０％と低い
。Also, ^, I, Meyers et al. (J, ^, C, S,
, , , 104.879 (1982)) uses an optically active amino alcohol in an amount of 1 equivalent relative to the starting compound as an asymmetric source, so it is necessary to perform a reductive elimination reaction after the asymmetric synthesis reaction is completed. , the chemical yield is also low at about 60%.
上記の理由により、いずれの方法も工業的に満足できる
ものではない。For the above reasons, neither method is industrially satisfactory.
〈発明が解決すべき課題〉
このようなことから、本発明者らは工業的有利に上記の
光学活性な１．１゛−ビナフチル誘導体を製造する方法
を提供すべく鋭意検討の結果、本発明を完成した。<Problems to be Solved by the Invention> In view of the above, the present inventors have conducted intensive studies to provide an industrially advantageous method for producing the above-mentioned optically active 1.1'-binaphthyl derivative, and have developed the present invention. completed.
く課題を解決するための手段〉 本発明は、一般式（ＩＩ） Ｘ。Means to solve problems〉 The present invention provides general formula (II) X.
（式中、Ｘｌはハロゲン原子を示し、Ｒ＋及びＲ２は水
素原子または低級アルキル基を示す。）で示されるナフ
タレン誘導体と一般式（ＩＩＩ）Ｘｚ
（式中、ｘ２はハロゲン原子を示し、ＹはＭｇまたはＺ
ｎ原子を示す。Ｒ１およびＲ４は水素原子または低級ア
ルキル基を示す。）
で示されるグリニヤール試薬を、一般式（ｒＶ）（式中
、ＭはＦｅ、ＲｕまたはＯ５原子を示し、Ｚは水素原子
または低級アルコキシル基を示す。(In the formula, Xl represents a halogen atom, and R+ and R2 represent a hydrogen atom or a lower alkyl group.) and the general formula (III) Xz (wherein, x2 represents a halogen atom, and Y represents a Mg or Z
Indicates n atom. R1 and R4 represent a hydrogen atom or a lower alkyl group. ) A Grignard reagent represented by the general formula (rV) (wherein M represents Fe, Ru or O5 atom, and Z represents a hydrogen atom or a lower alkoxyl group).
Ｒ５はアリール基を示し、Ｒ６およびＲ７は水素原子ま
たは低級アルキル基を示す。）
で示される光学活性なメタロセニルホスフィン誘導体で
修飾した金属触媒の存在下に不斉クロスカップリングさ
せて上記一般式（Ｉ）で示される光学活性な１．１゛−
ビナフチル誘導体を製造する方法を提供するものである
。R5 represents an aryl group, and R6 and R7 represent a hydrogen atom or a lower alkyl group. ) The optically active 1.1-
A method for producing binaphthyl derivatives is provided.
本発明において、原料として用いられるナフタレン誘導
体（ＩＩ）としては、１−ブロモナフタレン、２−メチ
ル−１−ナフチルブロマイド、２−エチル−１−ナフチ
ルブロマイドふよび２．６−ジメチル−１−ナフチルブ
ロマイドなどが例示される。In the present invention, the naphthalene derivative (II) used as a raw material includes 1-bromonaphthalene, 2-methyl-1-naphthyl bromide, 2-ethyl-1-naphthyl bromide, and 2,6-dimethyl-1-naphthyl bromide. Examples include.
上記例示化合物は、Ｊ、Ａ、 Ｃ９Ｓ、 、月、 ２７
７３ （１９４１）に記載の方法に準じて製造すること
ができる。The above exemplified compounds are J, A, C9S, , Moon, 27
73 (1941).
また、一般式（ＩＩＩ）で示されるグリニヤール試薬は
、上記のナフタレン誘導体（ＩＩ）と金属マグネシウム
の反応または該反応で得られた有機マグネンウムハライ
ドと臭化亜鉛の交換反応により容易に製造することがで
きる。Furthermore, the Grignard reagent represented by the general formula (III) can be easily produced by the reaction of the above-mentioned naphthalene derivative (II) with magnesium metal or the exchange reaction of the organic magnesium halide obtained in the reaction with zinc bromide. be able to.
次に、光学活性なメタロセニルホスフィンＪ”１１体（
１’Ｖ）は、一般式（ｒＶ）に右いてＭがＦｅ原子であ
るフェロセニルホスフィン誘導体が実用上好ましい。Next, optically active metallocenylphosphine J”11 body (
1'V) is practically preferable to be a ferrocenylphosphine derivative in which M in the general formula (rV) is an Fe atom.
また、一般式（ＩＶ）においてＲ３がフェニル基を、Ｒ
６が水素原子を、Ｒ１がメチル基を、Ｚが低級アルコキ
シル基をそれぞれ示す場合により好ましい。Further, in general formula (IV), R3 is a phenyl group, R
It is more preferable that 6 represents a hydrogen atom, R1 represents a methyl group, and Z represents a lower alkoxyl group.
本発明は、光学活性なメタロセニルホスフィン誘導体（
ｒＶ）で修飾した金属触媒の存在下に行われ、該触媒の
金属成分としてはニッケルおよびパラジウムが例示され
るが、ニッケルがより好ましく使用される。The present invention provides an optically active metallocenylphosphine derivative (
It is carried out in the presence of a metal catalyst modified with rV), and examples of the metal component of the catalyst include nickel and palladium, with nickel being more preferably used.
かかる金属触媒としては、たとえば臭化ニッケルまたは
塩化ニッケルと（Ｓ） −１−Ｃ（Ｒ） −２−（ジフ
ェニルホスフィノ）フェロセニル〕エチルメチルエーテ
ル（以下、（Ｓ）−（Ｒ）−ＰＰＦＯＭｅと略記する）
の錯体などが例示され、これらｉは、たとえばメチルマ
グネシウムブロマイドとの加熱処理で活性化した後、開
用することができる。Such metal catalysts include, for example, nickel bromide or nickel chloride and (S)-1-C(R)-2-(diphenylphosphino)ferrocenyl]ethyl methyl ether (hereinafter referred to as (S)-(R)-PPFOMe). abbreviated)
For example, complexes of i can be used after activation by heat treatment with methylmagnesium bromide.
なお、光学活性なメタロセニルホスフィン誘導体（１’
Ｖ）は、Ｂｕ ｌ ｌ、 Ｃｈｅｍ、 Ｓｏｃ、 Ｊｐ
ｎ、 、 ５：］、 １１３８ （１９８０）、Ａｃｃ
、Ｃｈｅｍ、 Ｒｅｓ、、１５，３９５（１９８２）
及びＪ、八、 Ｃ，Ｓ、 、 １０４、１８０（１
９８２）などに記載の方法に準じて製造することができ
、たとえば、（Ｓ）−（Ｒ）−ＰＰＦＯＭｅは下式に示
す方法で製造できる。In addition, optically active metallocenylphosphine derivative (1'
V) is Bull, Chem, Soc, JP
n, , 5:], 1138 (1980), Acc.
, Chem, Res., 15, 395 (1982)
and J, 8, C, S, , 104, 180 (1
For example, (S)-(R)-PPFOMe can be produced by the method shown in the following formula.
市
本発明の方法において金属触媒の使用量は原料のグリニ
ヤール試薬に対して０．１〜２０モル％、好ましくは１
〜５モル％である。反応は通常溶媒中で行われる。溶媒
としては、たとえば、エーテル、テトラヒドロフラン、
ベンゼン、トルエンまたはキンレンなどの有段溶媒ある
いはこれらの混合物があげられるが、エーテル及びトル
エンの混合溶媒が好ましく使用される。In the method of the present invention, the amount of metal catalyst used is 0.1 to 20 mol%, preferably 1
~5 mol%. The reaction is usually carried out in a solvent. Examples of solvents include ether, tetrahydrofuran,
Examples include staged solvents such as benzene, toluene, or quinoa, or mixtures thereof, and a mixed solvent of ether and toluene is preferably used.
かかる溶媒の使用量は原料のグリニヤール試薬に対して
、通常１〜５００重量倍、好ましくは１０〜２００重１
倍である。The amount of such a solvent used is usually 1 to 500 times by weight, preferably 10 to 200 times by weight, based on the Grignard reagent as a raw material.
It's double.
反応温度は一８０℃〜１００℃、好ましくは＝３０℃〜
２０℃である。反応時間は特に制限されないが、−船釣
には１０〜１００時間である。The reaction temperature is -80°C to 100°C, preferably =30°C to
The temperature is 20°C. The reaction time is not particularly limited, but is 10 to 100 hours for boat fishing.
〈発明の効果〉
かくして本発明の方法によれば、前記一般式（１）で示
される光学活性な１．ｌ゛−ビナフチル誘導体を好化学
収率および好光学収率で得ることができ、また、用いる
金属触媒の不斉配位子である光学活性なメタロセニルホ
スフィン誘導体（ＴＶ）の立体配置を変えることにより
、目的とする光学活性な１，１′−ビナフチル誘導体（
Ｉ）の立体配置を制御することができる。<Effects of the Invention> Thus, according to the method of the present invention, optically active 1. l'-binaphthyl derivatives can be obtained with favorable chemical and optical yields, and the configuration of the optically active metallocenylphosphine derivative (TV), which is the asymmetric ligand of the metal catalyst used, can be changed. By this, the desired optically active 1,1'-binaphthyl derivative (
The configuration of I) can be controlled.
〈実施例〉 以下、実施例により本発明を説明する。<Example> The present invention will be explained below with reference to Examples.
合成した光学活性な１，１′−ビナフチル誘導体の同定
は、文献記載のＮ Ｍ Ｒ及びＩＲのデータとの比較に
より行った。また、該誘導体の光学純度は光学活性カラ
ムを用いた液体クロマトグラフィーにより決定した。The synthesized optically active 1,1'-binaphthyl derivative was identified by comparison with NMR and IR data described in literature. Further, the optical purity of the derivative was determined by liquid chromatography using an optically active column.
実施例１
（Ｓ）−（Ｒ）−ＰＰＦＯＭｅ ０．３４ｇ（０，８
ミｌＪモル）及び無水臭化ニッケル ８７ｆｆ１ｇ（０
，４ミリモル）を反応フラスコに仕込み、Ｎ２雰囲気中
、０．２Ｍ−メチルマグネシウムブロマイド・エーテル
溶液５ｉ及び２−メチル−１−ナフチルブロマイド ２
．９２ｇ（１３ミリモル）を加えて、１０分間還流し、
ニッケル触媒の活性化を行った。Example 1 (S)-(R)-PPFOMe 0.34 g (0,8
mil J mole) and anhydrous nickel bromide 87ff1g (0
, 4 mmol) into a reaction flask, and in a N2 atmosphere, 0.2 M-methylmagnesium bromide in ether solution 5i and 2-methyl-1-naphthyl bromide 2
．． Add 92 g (13 mmol) and reflux for 10 minutes.
The nickel catalyst was activated.
次に、−５℃に冷却し、２−メチル−１−ナフチルマグ
ネシウムブロマイド（１０ミリモル）、エーテル１５ｍ
１及びトルエン１５ｒｎｌの混合物を加えて同温度で９
６時間撹拌した。Next, cool to -5°C, add 2-methyl-1-naphthylmagnesium bromide (10 mmol), ether 15 m
Add a mixture of 1 and 15 rnl of toluene and stir at the same temperature.
Stirred for 6 hours.
反応終了後、希塩酸で加水分解し、加水分解液をエーテ
ルで抽出処理した後、シリカゲルカラムクロマトグラフ
ィー（溶離溶媒 ｎ−ヘキサン）で精製処理して（Ｒ）
（） ２，２°−ジメチル−１，１′−ビナ
フチル １．９１ ｇを得た。After completion of the reaction, hydrolyze with dilute hydrochloric acid, extract the hydrolyzed solution with ether, and purify with silica gel column chromatography (eluent: n-hexane) (R).
() 1.91 g of 2,2°-dimethyl-1,1'-binaphthyl was obtained.
化学収率６８％〔α〕ル’ ＝ −３５，６° （ｃ＝
１．０１ＣＨＣＩ、）、９４％ｅｅ （（Ｒ）−（−）
配置〕光学純度（％ｅｅ）は上記の生成物を下記の方法
により環状アミドに誘導し、液体クロマトグラフィで分
析して算出した。Chemical yield 68% [α]ru' = -35,6° (c=
1.01CHCI, ), 94%ee ((R)-(-)
Configuration] Optical purity (%ee) was calculated by converting the above product into a cyclic amide by the method described below and analyzing it by liquid chromatography.
なお、下記反応式中、ＮＢＳはＮ−ブロムコハク酸イミ
ドであり、ＢＰＯは過酸化ベンゾイルであり、ＤＭ・Ｆ
はジメチルホルムアミドである。In addition, in the reaction formula below, NBS is N-bromosuccinimide, BPO is benzoyl peroxide, and DM・F
is dimethylformamide.
上記で得た光学純度９４％ｅｅの生成物を９０％エタノ
ールで１回再結晶することにより、光学純度９９％以上
の（Ｒ）−（−）−２，２−ジメチル−１，１’−ビナ
フチルが回収率７０％で得られた。By recrystallizing the product with an optical purity of 94% ee obtained above once with 90% ethanol, (R)-(-)-2,2-dimethyl-1,1'- with an optical purity of 99% or more was obtained. Binaphthyl was obtained with a recovery rate of 70%.
なお、触媒として使用した不斉配位子（Ｓ）−（Ｒ）−
ＰＰＦＯＭｅは上記のシリカゲルカラムクロマトグラフ
ィーにおいて、ｎ−へキサン：酢酸エチル（５： １）
の溶離溶媒で溶出させることにより、仕込量に対して８
０％の回収率で回収でき、次の不斉合成反応に再使用し
た。In addition, the asymmetric ligand (S)-(R)- used as a catalyst
PPFOMe was prepared using n-hexane:ethyl acetate (5:1) in the above silica gel column chromatography.
By elution with an elution solvent of 8
It was recovered with a recovery rate of 0% and reused in the next asymmetric synthesis reaction.
また（Ｓ）−（Ｒ）−ＰＰＦＯＭｅの構造は、次のとお
りである。The structure of (S)-(R)-PPFOMe is as follows.
Ｈ
実施例２
（Ｓ）−（Ｒ）−ＰＰＦＯＭｅに代えて（Ｒ）−（Ｓ）
−ＰＰＦＯＭｅを用いる以外は実施例１と同様に反応
（但し、反応温度は０℃にした）及び後処理して（Ｓ）
−（＋） −２，２′ジメチル−１、１°−ビナフチル
２．０８ ｇを得た。化学収ｆ！７４％、〔α］ｏ’
＝＋３５．２° （ｃ＝１．ｏ、ＣＨＣｌ、）、９３％
ｅｅ ［（Ｓ）−（＋）配置〕実施例３
（Ｓ）−（Ｒ）−ＰＰＦＯＭｅ １７．１ｍｇ（０，
０４ミ’Ｊモル）及び無水臭化ニッケル４．４ ｍｇ（
０，０２ミｌＪモル）を反応フラスコに仕込み、Ｎ２雰
囲気中、０．２Ｍ−メチルマグネンウムブロマイド・エ
ーテル溶液１−及びｌ−ブロモナフタレン３１１ｍｇ（
１，５ミリモル）を加えて、１０分間還流し、二／ケル
触媒の活性化を行った。H Example 2 (R)-(S) in place of (S)-(R)-PPFOMe
- Reacted in the same manner as in Example 1 except for using PPFOMe (however, the reaction temperature was 0°C) and post-treated (S)
2.08 g of -(+)-2,2'dimethyl-1,1°-binaphthyl was obtained. Chemical yield f! 74%, [α]o'
=+35.2° (c=1.o, CHCl,), 93%
ee [(S)-(+) configuration] Example 3 (S)-(R)-PPFOMe 17.1 mg (0,
04 mmol) and 4.4 mg of anhydrous nickel bromide (
0.2 M-methylmagnenium bromide in ether solution (311 mg of 1- and l-bromonaphthalene) was charged in a reaction flask in a N2 atmosphere.
1.5 mmol) was added and refluxed for 10 minutes to activate the di/Kel catalyst.
次に、−３０℃に冷却し、２−メチル−１−ナフチルマ
グネシウムブロマイド（１ミリモル）、エーテル １．
１５ｍ１及びトルエン１．１５ ｍｅの混合物を加えて
同温度で９６時間撹拌した。Next, it was cooled to -30°C, and 2-methyl-1-naphthylmagnesium bromide (1 mmol) and ether were added.
A mixture of 15 ml and 1.15 me of toluene was added and stirred at the same temperature for 96 hours.
反応終了後、希塩酸で加水分解し、加水分解液をエーテ
ルで抽出処理した後、シリカゲルカラムクロマトグラフ
ィ−（溶離溶媒ｎ−へキサン）で精製処理して（Ｒ）
−（−）−２−メチル−１゜ビービナフチル２４８ ｍ
ｇを得た。After completion of the reaction, hydrolyze with dilute hydrochloric acid, extract the hydrolyzed solution with ether, and purify with silica gel column chromatography (eluent: n-hexane).
-(-)-2-methyl-1゜bibinaphthyl 248 m
I got g.
化学収率９２％、〔α［’＝−３３，２° （ｃ−１，
０、ＣＨＣｌ３） ３’３％ｅｅ Ｃ（Ｒ） −（−
）配ゴ〕。光学純度（％ｅｅ）は上記の生成物を下記の
方法によりアルコールに誘導し、液体クロマトグラフィ
で分析して算出した。Chemical yield 92%, [α['=-33,2° (c-1,
0, CHCl3) 3'3%ee C(R) -(-
) Raigo]. Optical purity (%ee) was calculated by converting the above product into alcohol by the following method and analyzing it by liquid chromatography.
上記で得た光学純度８３％ｅｅの生成物をｎ−ヘキサン
で１回再結晶することにより、光学純度９９％の（Ｒ）
−（−）−２−メチル−１，１′−ビナフチルが回収率
７５％で得られた。By recrystallizing the product with an optical purity of 83% ee obtained above once from n-hexane, (R) with an optical purity of 99% was obtained.
-(-)-2-methyl-1,1'-binaphthyl was obtained with a recovery rate of 75%.
実施例４
（Ｓ）−（Ｒ）−ＰＰＦＯＭｅ ４２．８ｍｇ （０
、１０ミ’Ｊモル）及び無水臭化ニッケル１０．９ ｍ
ｇ（０，０５ミｌＪモル）を反応フラスコに仕込み、Ｎ
２雪囲気中、０．２Ｍ−メチルマグネシウムブロマイド
・エーテル溶１１ｍｊ！及びｌ−ブロモナフタレン４１
４ｍｇ（２，０ミリモル）を加えて、１０分間還流し、
ニッケル触媒の活性化を行った。Example 4 (S)-(R)-PPFOMe 42.8 mg (0
, 10 mmol) and anhydrous nickel bromide 10.9 m
g (0.05 mlJ mol) into a reaction flask, and
2 In a snowy atmosphere, 11mj of 0.2M-methylmagnesium bromide in ether! and l-bromonaphthalene 41
Add 4 mg (2.0 mmol) and reflux for 10 minutes.
The nickel catalyst was activated.
次に、０℃に冷却し、２−エチル−１−ナフチルマグネ
シウムブロマイド（１，０ミリモル）、エーテル１．０
５ｍ１！及びトルエン１．０５ｍ１の混合物を加えて同
温度で４５時間撹拌した。Next, cool to 0°C, add 2-ethyl-1-naphthylmagnesium bromide (1.0 mmol), ether 1.0
5m1! A mixture of 1.05 ml of toluene and 1.05 ml of toluene was added thereto, and the mixture was stirred at the same temperature for 45 hours.
反応終了後、希塩酸で加水分解し、加水分解液をエーテ
ルで抽出処理した後、シリカゲルカラムクロマトグラフ
ィー（溶離溶媒ｎ−へキサン）で精製処理して（Ｒ）−
（〜）−２−エチル−１゜１°ビナフチル２３０ ｍｇ
を得た。After the reaction was completed, it was hydrolyzed with dilute hydrochloric acid, the hydrolyzed solution was extracted with ether, and then purified by silica gel column chromatography (eluent: n-hexane) to obtain (R)-
(~)-2-ethyl-1゜1゜binaphthyl 230 mg
I got it.
化学数−１！８１％ｌ：α〕Ａ’＝ ２５．６° （
ｃ＝１．５、ＣＨＣｌ、） ７１％ｅｅ （（Ｒ）−
（−）配置〕光学純度（％ｅｅ）は上記の生成物を実施
例３の方法により下記のアルコールに誘導し、液体クロ
マトグラフィで分析して算出した。Chemical number -1!81%l:α〕A'= 25.6° (
c=1.5, CHCl, ) 71%ee ((R)-
(-) Configuration] Optical purity (%ee) was calculated by deriving the above product into the following alcohol by the method of Example 3 and analyzing it by liquid chromatography.
（Ｊ・人−Ｆ；哨【白ン(J・人-F;
Claims (4)
＿２は水素原子または低級アルキル基を示す。）で示さ
れるナフタレン誘導体と一般式 ▲数式、化学式、表等があります▼ （式中、Ｘ＿２はハロゲン原子を、ＹはＭｇまたはＺｎ
原子を示し、Ｒ＿３およびＲ＿４は水素原子または低級
アルキル基を示す。） で示されるグリニヤール試薬を一般式 ▲数式、化学式、表等があります▼ （式中、Ｒ＿５はアリール基を示し、Ｒ＿６およびＲ＿
７は水素原子または低級アルキル基を示す。ＭはＦｅ、
ＲｕまたはＯｓ原子を示し、Ｚは水素原子または低級ア
ルコキシル基を示す。） で示される光学活性なメタロセニルホスフィン誘導体で
修飾した金属触媒の存在下に不斉クロスカップリングす
ることを特徴とする一般式 ▲数式、化学式、表等があります▼ （式中、Ｒ＿１、Ｒ＿２、Ｒ＿３およびＲ＿４は前記と
同じ意味を有する。） で示される光学活性な１，１′−ビナフチル誘導体の製
造法。(1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, X_1 represents a halogen atom, R_1 and R
_2 represents a hydrogen atom or a lower alkyl group. ) Naphthalene derivatives and general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, X_2 is a halogen atom, Y is Mg or Zn
R_3 and R_4 represent a hydrogen atom or a lower alkyl group. ) The Grignard reagent is expressed by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_5 represents an aryl group, R_6 and R_
7 represents a hydrogen atom or a lower alkyl group. M is Fe,
It represents Ru or Os atom, and Z represents hydrogen atom or lower alkoxyl group. ) A general formula characterized by asymmetric cross-coupling in the presence of a metal catalyst modified with an optically active metallocenylphosphine derivative ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_1, R_2, R_3 and R_4 have the same meanings as above.) A method for producing an optically active 1,1'-binaphthyl derivative.
に記載の光学活性な１，１′−ビナフチル誘導体の製造
法。(2) Claim 1 wherein the metal catalyst is a nickel-based metal catalyst.
A method for producing an optically active 1,1'-binaphthyl derivative as described in .
式 ▲数式、化学式、表等があります▼ （式中、ＭはＦｅ、ＲｕまたはＯｓ原子であり、Ｚは低
級アルコキシル基である） である請求項１に記載の光学活性な１，１′−ビナフチ
ル誘導体の製造法。(3) A claim that the optically active metallocenylphosphine derivative has the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, M is an Fe, Ru or Os atom, and Z is a lower alkoxyl group) Item 1. A method for producing an optically active 1,1'-binaphthyl derivative according to item 1.
式 ▲数式、化学式、表等があります▼ （式中、ＭはＦｅ、ＲｕまたはＯｓ原子である。）であ
る請求項３に記載の光学活性な１，１′−ビナフチル誘
導体の製造法。(4) The optical activity according to claim 3, wherein the optically active metallocenylphosphine derivative has a general formula ▲A mathematical formula, a chemical formula, a table, etc.▼ (wherein M is an Fe, Ru or Os atom) A method for producing a 1,1'-binaphthyl derivative.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13602288A JPH01305039A (en) | 1988-06-01 | 1988-06-01 | Production of optically active 1,1'-binaphthyl derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13602288A JPH01305039A (en) | 1988-06-01 | 1988-06-01 | Production of optically active 1,1'-binaphthyl derivative |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01305039A true JPH01305039A (en) | 1989-12-08 |
Family
ID=15165356
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13602288A Pending JPH01305039A (en) | 1988-06-01 | 1988-06-01 | Production of optically active 1,1'-binaphthyl derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01305039A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0653396A1 (en) * | 1993-11-13 | 1995-05-17 | Hoechst Aktiengesellschaft | Process for the preparation of 1,1'-binaphthylene |
| JP2010229130A (en) * | 1999-06-04 | 2010-10-14 | Nagase & Co Ltd | OPTICALLY ACTIVE QUATERNARY AMMONIUM SALT HAVING AXIAL ASYMMETRY, METHOD FOR PRODUCING THE SAME AND APPLICATION OF THE SAME TO ASYMMETRIC SYNTHESIS OF alpha-AMINO ACID DERIVATIVE |
-
1988
- 1988-06-01 JP JP13602288A patent/JPH01305039A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0653396A1 (en) * | 1993-11-13 | 1995-05-17 | Hoechst Aktiengesellschaft | Process for the preparation of 1,1'-binaphthylene |
| US5510554A (en) * | 1993-11-13 | 1996-04-23 | Hoechst Aktiengesellschaft | Process for preparing 1,1'-binaphthyls |
| JP2010229130A (en) * | 1999-06-04 | 2010-10-14 | Nagase & Co Ltd | OPTICALLY ACTIVE QUATERNARY AMMONIUM SALT HAVING AXIAL ASYMMETRY, METHOD FOR PRODUCING THE SAME AND APPLICATION OF THE SAME TO ASYMMETRIC SYNTHESIS OF alpha-AMINO ACID DERIVATIVE |
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