JPS6067488A - Optically active ogranotin compound containing asymmetric group - Google Patents
Optically active ogranotin compound containing asymmetric groupInfo
- Publication number
- JPS6067488A JPS6067488A JP17680283A JP17680283A JPS6067488A JP S6067488 A JPS6067488 A JP S6067488A JP 17680283 A JP17680283 A JP 17680283A JP 17680283 A JP17680283 A JP 17680283A JP S6067488 A JPS6067488 A JP S6067488A
- Authority
- JP
- Japan
- Prior art keywords
- optically active
- ogranotin
- compound containing
- group
- asymmetric group
- 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.)
- Granted
Links
- 150000001875 compounds Chemical class 0.000 title description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 12
- 239000002904 solvent Substances 0.000 abstract description 5
- OFJWFSNDPCAWDK-UHFFFAOYSA-N 2-phenylbutyric acid Chemical compound CCC(C(O)=O)C1=CC=CC=C1 OFJWFSNDPCAWDK-UHFFFAOYSA-N 0.000 abstract description 4
- 238000006717 asymmetric allylation reaction Methods 0.000 abstract description 4
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 4
- NBTOZLQBSIZIKS-UHFFFAOYSA-N methoxide Chemical compound [O-]C NBTOZLQBSIZIKS-UHFFFAOYSA-N 0.000 abstract description 2
- 238000006293 aldehyde allylation reaction Methods 0.000 abstract 1
- 150000001299 aldehydes Chemical class 0.000 abstract 1
- 150000002576 ketones Chemical class 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- -1 allyltin compound Chemical class 0.000 description 2
- 238000011914 asymmetric synthesis Methods 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- ZSPTYLOMNJNZNG-UHFFFAOYSA-N 3-Buten-1-ol Chemical compound OCCC=C ZSPTYLOMNJNZNG-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- GMDGXJQUWIQOLE-UHFFFAOYSA-N prop-2-enylborane Chemical class BCC=C GMDGXJQUWIQOLE-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、不斉基を有する光学的に活性な有機錫化合物
に関する。更に詳細には、本発明は、下記式（Ｉ）で表
わされる不斉基を右する光学活性有機錫化合物を提供す
るものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to optically active organotin compounds having an asymmetric group. More specifically, the present invention provides an optically active organotin compound having an asymmetric group represented by the following formula (I).
有機錫化合物の中には、官能基の転換試剤やＦＰＪ！媒
として有用なものが多いが、不斉合成の如く更に精密な
選択性が要求される場合には、従来公知の有機錫化合物
では全く効果がなかった。Some organotin compounds include functional group conversion reagents and FPJ! Many of them are useful as media, but in cases where more precise selectivity is required, such as in asymmetric synthesis, conventionally known organotin compounds have been completely ineffective.
本発明は、反応性官能基としてアリル基を有するアリル
錫化合物に光学活性な不斉基を導入した光学活性な新規
有機錫化合物を１１？供するものであり、このものは次
式（Ｉ）で示されるように、ケ１〜ンまたアルデヒドの
不斉アリル化反応試剤として有用であることが見出され
た。The present invention provides a new optically active organotin compound in which an optically active asymmetric group is introduced into an allyltin compound having an allyl group as a reactive functional group. It has been found that this product is useful as an asymmetric allylation reaction reagent for carbons and aldehydes, as shown in the following formula (I).
但し、上記式（Ｉ）中、Ｒ’、Ｒ２は水素原子または有
機基であり、Ｒ１とＲ２が同一であることはない。However, in the above formula (I), R' and R2 are hydrogen atoms or organic groups, and R1 and R2 are not the same.
上記式（ＩＩ）によって得られるホモアリルアルコール
類は合成中間体として有用なものが多い。従来において
は、光学活性アリルケイ素化合物や光学活性アリルホウ
素化合物による不斉アリル化反応が若干側報告されてい
るが、上記ケイ素化合物ではアリル基がフェニル買換さ
れた特別な場合に限られること、又上記ボウ索化合物で
は、このものが大気中で不安定なため取扱上の制限があ
ること、また該化合物の再使用が困難であることなどの
欠点かあった。Many of the homoallyl alcohols obtained by the above formula (II) are useful as synthetic intermediates. In the past, some asymmetric allylation reactions using optically active allyl silicon compounds and optically active allyl boron compounds have been reported, but in the above silicon compounds, it is limited to special cases where the allyl group is exchanged with phenyl. Furthermore, the above-mentioned bow rope compound has drawbacks such as being unstable in the atmosphere, which imposes restrictions on handling, and that it is difficult to reuse the compound.
本発明の式（Ｉ’）の化合物は、利用価飴の高い全水素
置換アリル基の場合でも適用でき、−殻付が高いだ【プ
でなく、空気中でも安定で、しかも光学活性有機基が再
使用可能な形で回収できるなど不斉アリル化反応試剤ど
して極めて有用性が高い。The compound of formula (I') of the present invention can be applied even in the case of a fully hydrogen-substituted allyl group with a high utility value, does not have a high shelling, is stable in air, and has an optically active organic group. It is extremely useful as an asymmetric allylation reaction reagent because it can be recovered in a reusable form.
本発明の式（Ｉ）の光学活性有機錫化合物は、次のよう
な方法で製造することができる。The optically active organotin compound of formula (I) of the present invention can be produced by the following method.
光学活性２−フェニル酪酸とジアリル錫ジメトキザイト
を無溶媒またはメタノール１５Ｊ−−チル等の溶媒中で
−１００〜１２０℃の湿度範囲で反応させることによっ
て得られる。It can be obtained by reacting optically active 2-phenylbutyric acid and diallyltin dimethoxite without a solvent or in a solvent such as methanol 15J-thyl at a humidity range of -100 to 120°C.
本発明の光学活性有機錫化合物は、前記し１〔ように、
アルデヒドまたはケ１〜ンと前記式（Ｉ）のように不斉
反応さゼ、これを加水分解することにより光学活性なホ
モアリルアルコールを得ることができる。例えばアルデ
ヒドとしＴＴＬ−Ｃａ Ｈ７ＣＪ（Ｏ，ｔ ０４１−１
ｙ ０１０、 ＴＬ Ｃｇ １１１７０１０． ＧＡ
ｌ−１ｓ （Ｈ＝ＵＩＧ１０、ＣａＨｓＣＨＯ等を用い
て対応Ｊる光学活性ホモアリルアルコールを得ることが
できる。The optically active organotin compound of the present invention can be prepared as described in 1 above.
An optically active homoallyl alcohol can be obtained by carrying out an asymmetric reaction with an aldehyde or a key as shown in the formula (I) and hydrolyzing the reaction. For example, as an aldehyde, TTL-Ca H7CJ (O, t 041-1
y 010, TL Cg 1117010. G.A.
The corresponding optically active homoallylic alcohol can be obtained using l-1s (H=UIG10, CaHsCHO, etc.).
更に、反発後適当な、処理を行なうことにより、光学活
性な置換基は繰返し使用可能な形で回収される。Furthermore, by performing appropriate treatment after repulsion, the optically active substituent can be recovered in a form that can be used repeatedly.
以下実施例によって本発明を５ｍ明する。The present invention will be further illustrated by the following examples.
実施例
金属ナトリウム０．７７ｇ （３３ｍ ｍａｔ）とメタ
ノール２０川１から調製したす１〜リウムメトキサイド
溶液にジアリル錫ジブロマイド６．０ｇ（１６，６ｍ
ｍｏｌ ）を加え、室温で１時間撹拌してジアリル錫ジ
メトキザイドを製造し、この反応液に（＋）−２−フェ
ニル酪酸く〔α〕廿＋ ８１．９°、（Ｃ２，３５６，
エーテル））５．５ｇ（３３１１１１１１０１）を加え
、室温で１時間攪拌した後減圧下でメタノールを留去し
、残渣をジクロロメタンに溶かして濾過し、濾液の溶媒
を留去して残渣をジクロロメタン−へキサンで 。Example 6.0 g (16.6 m mat) of diallytin dibromide was added to a solution of solutonium methoxide prepared from 0.77 g (33 m mat) of sodium metal and 20 m of methanol.
mol ) was added and stirred at room temperature for 1 hour to produce diallyltin dimethoxide.
After stirring at room temperature for 1 hour, methanol was distilled off under reduced pressure, the residue was dissolved in dichloromethane and filtered, the solvent of the filtrate was distilled off, and the residue was dissolved in dichloromethane. In Kisan.
再結晶せしめて、目的物（＋）−ジアリル錫ビス（２−
フェニル酸１） ７．９を得たく収率印２）。目的物の
核磁気共鳴スペクトル（ＣＣ１２４溶媒、ＴＭＳ規準）
と赤外線吸収スペクトル（Ｋ Ｂｒ法）を第１図及び第
２図に示した。After recrystallization, the target product (+)-diallyltin bis(2-
Phenyl acid 1) I want to obtain 7.9 yield mark 2). Nuclear magnetic resonance spectrum of target product (CC124 solvent, TMS standard)
The infrared absorption spectra (K Br method) are shown in FIGS. 1 and 2.
（光学活性アリルアルコールの合成例）実施例によって
得られたく＋）−ジアリル錫ビス（２−フェニル酪酸）
１０ｕ＋ ｍｏｌと三フッ化ホウ素エチラート５ｍｍ
ｏｌを含むエーテル溶液２０ｍ ｌに、”ｎ、−Ｃａ
Ｈ７０１０２０ｍ ｍｏｌを一７８℃にて滴下して５時
間反応させた。反応混合物を０．５Ｎ−苛性ソーダ水溶
液３０ ｍ ｌで加水分解けしめ、続いて１Ｎ−塩酸溶
液、水の順で洗浄した後、硫酸マグネシウムで乾燥し、
エーテルを留去して残渣を蒸留覆°ると ６−へブテン
−４−オールが４６％の収率で得られた。(Synthesis example of optically active allyl alcohol) Diallyltin bis(2-phenylbutyric acid) obtained in Example
10u+ mol and 5mm of boron trifluoride ethylate
Into 20 ml of ether solution containing ol, add "n, -Ca
1,020 mmol of H70 was added dropwise at -78°C and reacted for 5 hours. The reaction mixture was hydrolyzed with 30 ml of 0.5N aqueous sodium hydroxide solution, washed successively with 1N hydrochloric acid solution and water, and dried over magnesium sulfate.
The ether was distilled off and the residue was distilled to give 6-hebuten-4-ol in a yield of 46%.
得られたアルコール （ Ｃ Ｉｏ．２，ベンゼン）であっＩζ。alcohol obtained (C Io.2, benzene) and Iζ.
第１図は実施例によって得られた＜ −＋− 、、）
−ジアリル錫ビス（ ２−フェニル酪酸）の核磁赤外線
吸収スペクトルを示す。
出願人 大阪曹達株式会社
代理人 弁理士 間予 透
型咽駄−ち
手続補正書（自発）
昭和５９年 ６月１９日
１、事件の表示 昭和５８年特許願第１７６８０２号２
、発明の名称 不斉基を有する光学活性有機錫化合物３
、補正をＪる者
事件どの関係 特許出願人
４、代理人
〒５５０ 大阪市西区江戸堀１丁目１０番８号（１）明
細書箱１頁下第３行〜下第１行「不斉基を有する・・・
提供する−ものである。」を「不斉基を有し、不斉合成
反応に有用な光学活性有機錫化合物に関するものである
。」と８］正Ｊる。
（２）同書第２頁下第５行〜下第４行「をｌ；Ｉ供りる
」を１に関する」と訂正する。Figure 1 shows < −+− ,,) obtained in the example.
- Nuclear magnetic infrared absorption spectrum of diallyltin bis(2-phenylbutyric acid) is shown. Applicant Osaka Soda Co., Ltd. Agent Patent Attorney Masayo Transparent Throat-chi Procedural Amendment (Spontaneous) June 19, 1980 1, Case Indication 1981 Patent Application No. 176802 2
, Title of the invention Optically active organotin compound having an asymmetric group 3
, What is the relationship between the case of the person who made the amendment? Patent applicant 4, agent 1-10-8 Edobori, Nishi-ku, Osaka 550 (1) Specification box 1, bottom line 3 to bottom line 1 "Asymmetric group have...
provide - something. 8] Sei J. ``Relates to optically active organotin compounds having an asymmetric group and useful for asymmetric synthesis reactions.'' (2) In the same book, page 2, bottom line 5 to bottom line 4, ``wo l; I offer'' is corrected to read ``related to 1''.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17680283A JPS6067488A (en) | 1983-09-24 | 1983-09-24 | Optically active ogranotin compound containing asymmetric group |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17680283A JPS6067488A (en) | 1983-09-24 | 1983-09-24 | Optically active ogranotin compound containing asymmetric group |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6067488A true JPS6067488A (en) | 1985-04-17 |
| JPS6225677B2 JPS6225677B2 (en) | 1987-06-04 |
Family
ID=16020093
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17680283A Granted JPS6067488A (en) | 1983-09-24 | 1983-09-24 | Optically active ogranotin compound containing asymmetric group |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6067488A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023209506A1 (en) * | 2022-04-25 | 2023-11-02 | Seastar Chemicals Ulc | Tin containing organometallic compounds |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0390824U (en) * | 1989-07-03 | 1991-09-17 |
-
1983
- 1983-09-24 JP JP17680283A patent/JPS6067488A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023209506A1 (en) * | 2022-04-25 | 2023-11-02 | Seastar Chemicals Ulc | Tin containing organometallic compounds |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6225677B2 (en) | 1987-06-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Rane et al. | Potassium triisopropylsilanethiolate: Vinyl and aryl sulfides through Pd-catalyzed cross coupling | |
| JP2792046B2 (en) | Optically active amine-boron compound, asymmetric reducing agent containing the same as an active ingredient, and method for producing optically active compound using the same | |
| US5681978A (en) | Method for the stereocontrolled synthesis of stegobinone and useful borane intermediates | |
| JPS6067488A (en) | Optically active ogranotin compound containing asymmetric group | |
| Walkup | Silicon-functionalized silyl enol ethers: A novel dialkylchlorosilyl enol ether and its conversion to alkoxy-and aminosilyl enol ethers | |
| JPH10130289A (en) | Ruthenium-diamine complex and method for producing optically active alcohols using the same as catalyst | |
| US4565892A (en) | Process for the preparation of bisphosphine dioxides | |
| EP1389174A1 (en) | Preparation and use of diols | |
| WO1997045391A1 (en) | Process for preparing optically active alcoholic compounds | |
| JP2860676B2 (en) | Method for producing 1-isoquinolines | |
| JPS591435A (en) | Method for producing trimethyl orthoformate or triethyl ester | |
| Yong‐Gui et al. | Fructose derived pyridyl alcohol ligands: synthesis and application in the asymmetric diethylzinc addition to aldehydes | |
| RU2290367C1 (en) | Method of preparing 1-[3-hydroxy-3-arylprop-1-yl]-1,2-dihydro[60]fullerenes | |
| SU1567565A1 (en) | Method of obtaining 1-chlor-4-methylpentan 2-ol | |
| SU715580A1 (en) | Method of preparing silicon acetylenic carbonylic compounds | |
| CN120647585A (en) | Method for preparing imidazolone derivatives by dehydrogenation conversion of manganese-catalyzed dihydric alcohol | |
| JP3770678B2 (en) | Optically active alcohol and its carboxylic acid ester | |
| JPH0586936B2 (en) | ||
| JPH11228453A (en) | Method for producing homoallylic alcohols | |
| JPH01216965A (en) | Production of 2-alkoxypropionic acid amide derivative | |
| JPH02209855A (en) | Beta-diketone compound | |
| JPH0313225B2 (en) | ||
| JP2003104966A (en) | Method for producing dialkyl peroxide | |
| JPS61271258A (en) | Production of optically active amino alcohol | |
| JPH08277256A (en) | Optically active (s)-2-benzyloxycarbonylamino-1-(4-methoxyphenyl)ethanol and its production |