JPH07300485A - Chiral zinc compound - Google Patents
Chiral zinc compoundInfo
- Publication number
- JPH07300485A JPH07300485A JP11432194A JP11432194A JPH07300485A JP H07300485 A JPH07300485 A JP H07300485A JP 11432194 A JP11432194 A JP 11432194A JP 11432194 A JP11432194 A JP 11432194A JP H07300485 A JPH07300485 A JP H07300485A
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- JP
- Japan
- Prior art keywords
- zinc
- compound
- asymmetric
- formula
- tartrate
- Prior art date
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、キラルな亜鉛化合物に
関し、さらに詳細には、不斉合成用不斉誘起剤として有
用なキラルな亜鉛化合物に関する。TECHNICAL FIELD The present invention relates to a chiral zinc compound, and more particularly to a chiral zinc compound useful as an asymmetric inducer for asymmetric synthesis.
【０００２】[0002]
【従来の技術】従来、キラルな亜鉛化合物としては、ジ
アルキル亜鉛とキラルなアミノアルコールから得られる
亜鉛化合物が、ジアルキル亜鉛のアルデヒドへの不斉付
加反応の触媒になることが知られている。しかし、酒石
酸エステルとジアルキル亜鉛から得られるキラルな亜鉛
化合物はこれまで知られていない。2. Description of the Related Art Conventionally, as a chiral zinc compound, it has been known that a zinc compound obtained from a dialkylzinc and a chiral aminoalcohol serves as a catalyst for an asymmetric addition reaction of a dialkylzinc to an aldehyde. However, no chiral zinc compound obtained from a tartaric acid ester and a dialkylzinc has been known so far.
【０００３】[0003]
【発明が解決しようとする課題】そこで本発明の目的
は、新たな不斉反応の不斉誘起剤となる新規なキラルな
亜鉛化合物を提供することにある。Therefore, an object of the present invention is to provide a novel chiral zinc compound which serves as a new asymmetric inducer of an asymmetric reaction.
【０００４】[0004]
【課題を解決するための手段】本発明は、下記一般式
［Ｉ］で表されるキラルな亜鉛化合物に関する。 （式中、Ｒ1 及びＲ3 は炭素数１〜６の低級アルキル基
を示し、Ｒ2 は水素又はＺｎＲ1 を示し、＊は不斉炭素
であることを示す。） 以下に本発明を詳細に説明する。The present invention relates to a chiral zinc compound represented by the following general formula [I]. (In the formula, R 1 and R 3 represent a lower alkyl group having 1 to 6 carbon atoms, R 2 represents hydrogen or ZnR 1 , and * represents an asymmetric carbon.) Hereinafter, the present invention will be described in detail. Explained.
【０００５】一般式［Ｉ］のＲ1 及びＲ3 の炭素数１か
ら６の低級アルキル基は、例えば、メチル、エチル、ｎ
−プロピル、イソプロピル、ｎ−ブチル、イソブチル、
sec−ブチル、tert−ブチル、ｎ−ペンチル、及びｎ−
ヘキシル等を挙げることができる。特に、Ｒ1 としては
メチル、エチルが好ましく、Ｒ3 としてはエチル、イソ
プロピルが好ましい。The lower alkyl group having 1 to 6 carbon atoms represented by R 1 and R 3 in the general formula [I] is, for example, methyl, ethyl or n.
-Propyl, isopropyl, n-butyl, isobutyl,
sec-butyl, tert-butyl, n-pentyl, and n-
Hexyl and the like can be mentioned. Particularly, R 1 is preferably methyl or ethyl, and R 3 is preferably ethyl or isopropyl.
【０００６】なお、本発明の化合物は会合体として存在
することも可能で、会合数は濃度により異なるが、通常
２から15である。The compound of the present invention can exist in the form of an aggregate, and the number of associations is usually 2 to 15, though it varies depending on the concentration.
【０００７】以下に本発明の化合物の製造法を説明す
る。本発明の化合物は、一般式［II］で示されるＬ−酒
石酸エステル又はＤ−酒石酸エステルとジアルキル亜鉛
を反応させることにより得られる。 The method for producing the compound of the present invention will be described below. The compound of the present invention can be obtained by reacting an L-tartrate or D-tartrate represented by the general formula [II] with a dialkylzinc.
【０００８】上記反応に用いる酒石酸エステルとして
は、Ｌ−酒石酸ジメチル、Ｌ−酒石酸ジエチル、Ｌ−酒
石酸ジイソプロピル、Ｌ−酒石酸ジｎ−ブチル、Ｌ−酒
石酸ジイソブチル、Ｄ−酒石酸ジエチル、及びＤ−酒石
酸ジイソプロピル等を例示できる。またジアルキル亜鉛
としては、ジメチル亜鉛、ジエチル亜鉛、ジｎ−プロピ
ル亜鉛、ジイソプロピル亜鉛、ジｎ−ブチル亜鉛、及び
ジｎ−ヘキシル亜鉛等を例示できる。Examples of the tartrate ester used in the above reaction include L-dimethyl tartrate, L-diethyl tartrate, L-diisopropyl tartrate, L-di-n-butyl L-tartrate, L-diisobutyl tartrate, D-diethyl tartrate, and D-diisopropyl tartrate. Etc. can be illustrated. Examples of dialkyl zinc include dimethyl zinc, diethyl zinc, di-n-propyl zinc, di-isopropyl zinc, di-n-butyl zinc, and di-n-hexyl zinc.
【０００９】ジアルキル亜鉛の使用量は一般式［II］の
酒石酸エステルに対して１当量又は２当量である。該当
量数が１の場合、一般式［Ｉ］中の置換基Ｒ2 は水素と
なり、一方、該当量数が２の場合Ｒ2 は、−ＺｎＲ1 と
等しくなる。The amount of dialkylzinc used is 1 equivalent or 2 equivalents based on the tartaric acid ester of the general formula [II]. When the corresponding quantity is 1, the substituent R 2 in the general formula [I] is hydrogen, while when the corresponding quantity is 2, R 2 is equal to —ZnR 1 .
【００１０】さらに該反応は、ジクロロメタン、ヘキサ
ン、トルエン、あるいはジエチルエーテル等の溶媒の存
在下で好ましく実施することができる。反応温度として
は−30℃から50℃で、特に好ましくは０℃である。反応
時間は 0.1から３時間であり、窒素又はアルゴン等の不
活性ガス雰囲気下、常圧下で好ましく行うことができ
る。Further, the reaction can be preferably carried out in the presence of a solvent such as dichloromethane, hexane, toluene or diethyl ether. The reaction temperature is -30 ° C to 50 ° C, particularly preferably 0 ° C. The reaction time is 0.1 to 3 hours, and the reaction can be preferably carried out under an atmosphere of an inert gas such as nitrogen or argon under normal pressure.
【００１１】[0011]
【発明の効果】本発明のキラルな亜鉛化合物は、亜鉛上
のアルキル置換基と各種の求核剤との置換反応により、
アルキル基以外の置換基を導入することが可能である。
例えば、tert−ブチルベンゼンチオールとの反応によ
り、亜鉛上にtert−ブチルフェニルメルカプト基を導入
することができ、さらに対称アジリジン化合物との反応
により、高い光学収率で開環生成物を与える不斉反応へ
使用することができる。このように本発明の化合物は不
斉反応の不斉誘起剤として有用である。INDUSTRIAL APPLICABILITY The chiral zinc compound of the present invention is produced by the substitution reaction of an alkyl substituent on zinc with various nucleophiles.
It is possible to introduce substituents other than alkyl groups.
For example, a reaction with tert-butylbenzenethiol can introduce a tert-butylphenylmercapto group onto zinc, and further reaction with a symmetrical aziridine compound gives an asymmetric ring-opening product in high optical yield. It can be used for the reaction. Thus, the compound of the present invention is useful as an asymmetric inducer of an asymmetric reaction.
【００１２】[0012]
【実施例】次に実施例により本発明を更に具体的に説明
するが、本発明はこれら実施例に限定されるものではな
い。The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
【００１３】（実施例１）アルゴン雰囲気下、攪拌機を
有するガラス製常圧反応装置にＬ−酒石酸ジイソプロピ
ル0.96ｇ（4.1mmol)及びジクロロメタン35mlを加え、０
℃に冷却した。ここにジエチル亜鉛0.42ml（4.1mmol)を
加え、０℃で30分間攪拌した。減圧下濃縮し、1.34ｇの
油状物を得た。Example 1 0.96 g (4.1 mmol) of L-diisopropyl tartrate and 35 ml of dichloromethane were added to an atmospheric pressure glass reactor equipped with a stirrer under an argon atmosphere, and 0
Cooled to ° C. 0.42 ml (4.1 mmol) of diethyl zinc was added thereto, and the mixture was stirred at 0 ° C for 30 minutes. Concentration under reduced pressure gave 1.34 g of oil.
【００１４】250MHz 1ＨＮＭＲ（ＣＤＣｌ3 ）；δ0.
12（ｑ，Ｊ＝7.9Hz)、1.1 （ｔ，Ｊ＝7.9Hz)、 1.2−1.
4 （ｍ）、 3.8−3.9 （ｍ）、4.38（ｓ）、 5.1（sep
t，Ｊ＝6.7Hz)250 MHz 1 H NMR (CDCl 3 ); δ0.
12 (q, J = 7.9Hz), 1.1 (t, J = 7.9Hz), 1.2-1.
4 (m), 3.8-3.9 (m), 4.38 (s), 5.1 (sep
(t, J = 6.7Hz)
【００１５】ベンゼン中における凝固点降下法による分
子量測定結果から、生成物は濃度により３〜10の会合体
を形成していた。結果を表１に示した。From the result of measuring the molecular weight by the freezing point depression method in benzene, the product formed 3 to 10 aggregates depending on the concentration. The results are shown in Table 1.
【００１６】[0016]
【表１】 [Table 1]
【００１７】（実施例２）アルゴン雰囲気下、攪拌機を
有するガラス製常圧反応装置にＬ−酒石酸ジエチル0.84
ｇ（4.1mmol)及びジクロロメタン35mlを加え、０℃に冷
却した。ここにジエチル亜鉛0.42ml（4.1mmol)を加え、
０℃で30分間攪拌した。減圧下濃縮し、1.21ｇの油状物
を得た。(Example 2) Under an argon atmosphere, 0.84 L-diethyl tartrate was placed in a glass atmospheric pressure reactor equipped with a stirrer.
g (4.1 mmol) and 35 ml of dichloromethane were added, and the mixture was cooled to 0 ° C. Diethyl zinc 0.42 ml (4.1 mmol) was added here,
The mixture was stirred at 0 ° C for 30 minutes. Concentration under reduced pressure gave 1.21 g of an oil.
【００１８】250MHz 1ＨＮＭＲ（ＣＤＣｌ3 ）；δ0.
13（ｑ，Ｊ＝7.9Hz)、1.1 （ｔ，Ｊ＝7.9Hz)、 1.4−1.
6 （ｍ）、 3.8−4.8 （ｍ）250 MHz 1 H NMR (CDCl 3 ); δ0.
13 (q, J = 7.9Hz), 1.1 (t, J = 7.9Hz), 1.4-1.
6 (m), 3.8-4.8 (m)
【００１９】（実施例３）アルゴン雰囲気下、攪拌機を
有するガラス製常圧反応装置にＬ−酒石酸ジイソプロピ
ル0.96ｇ（4.1mmol)及びジクロロメタン35mlを加え、０
℃に冷却した。ここにジエチル亜鉛0.84ml（8.2mmol)を
加え、０℃で30分間攪拌した。減圧下濃縮し、1.73ｇの
油状物を得た。Example 3 0.96 g (4.1 mmol) of L-diisopropyl tartrate and 35 ml of dichloromethane were added to an atmospheric pressure glass reactor equipped with a stirrer under an argon atmosphere, and 0
Cooled to ° C. 0.84 ml (8.2 mmol) of diethyl zinc was added thereto, and the mixture was stirred at 0 ° C for 30 minutes. Concentration under reduced pressure gave 1.73 g of an oil.
【００２０】250MHz 1ＨＮＭＲ（ＣＤＣｌ3 ）；δ0.
12（ｑ，Ｊ＝7.9Hz)、0.27（ｑ，Ｊ＝7.9Hz)、 1.4
（ｔ，Ｊ＝7.9Hz)、 1.2−1.4 （ｍ）、 3.8−3.9
（ｍ）、4.38（ｓ）、4.45（ｄ，Ｊ＝1.8Hz)、 5.1（se
pt、Ｊ＝6.7Hz)250 MHz 1 H NMR (CDCl 3 ); δ0.
12 (q, J = 7.9Hz), 0.27 (q, J = 7.9Hz), 1.4
(T, J = 7.9Hz), 1.2-1.4 (m), 3.8-3.9
(M), 4.38 (s), 4.45 (d, J = 1.8Hz), 5.1 (se
(pt, J = 6.7Hz)
【００２１】ベンゼン中における凝固点降下法による分
子量測定結果から、生成物は２量体を形成していた。結
果を表２に示した。From the result of the measurement of the molecular weight by the freezing point depression method in benzene, the product formed a dimer. The results are shown in Table 2.
【００２２】[0022]
【表２】 [Table 2]
【００２３】（実施例４）アルゴン雰囲気下、攪拌機を
有するガラス製常圧反応装置にＬ−酒石酸ジエチル0.84
ｇ（4.1mmol)及びジクロロメタン35mlを加え、０℃に冷
却した。ここにジエチル亜鉛0.84ml（8.2mmol)を加え、
０℃で30分間攪拌した。減圧下濃縮し、1.60ｇの油状物
を得た。Example 4 Under an argon atmosphere, 0.84 L-diethyl tartrate was placed in a glass atmospheric pressure reactor equipped with a stirrer.
g (4.1 mmol) and 35 ml of dichloromethane were added, and the mixture was cooled to 0 ° C. 0.84 ml (8.2 mmol) of diethyl zinc was added to this,
The mixture was stirred at 0 ° C for 30 minutes. Concentration under reduced pressure gave 1.60 g of an oil.
【００２４】250MHz 1ＨＮＭＲ（ＣＤＣｌ3 ）；δ0.
13（ｑ，Ｊ＝7.9Hz)、0.27（ｑ，Ｊ＝7.9Hz)、1.1
（ｔ，Ｊ＝7.9Hz)、1.31（ｔ，Ｊ＝7.4Hz)、3.85（ｑ，
Ｊ＝7.3Hz）、 4.1−4.6 （ｍ）250 MHz 1 H NMR (CDCl 3 ); δ0.
13 (q, J = 7.9Hz), 0.27 (q, J = 7.9Hz), 1.1
(T, J = 7.9 Hz), 1.31 (t, J = 7.4 Hz), 3.85 (q,
J = 7.3Hz), 4.1-4.6 (m)
Claims (1)
鉛化合物。 （式中、Ｒ1 及びＲ3 は炭素数１〜６の低級アルキル基
を示し、Ｒ2 は水素又はＺｎＲ1 を示し、＊は不斉炭素
であることを示す。）1. A chiral zinc compound represented by the following general formula [I]. (In the formula, R 1 and R 3 represent a lower alkyl group having 1 to 6 carbon atoms, R 2 represents hydrogen or ZnR 1 , and * represents an asymmetric carbon.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11432194A JP3584989B2 (en) | 1994-04-28 | 1994-04-28 | Chiral zinc compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11432194A JP3584989B2 (en) | 1994-04-28 | 1994-04-28 | Chiral zinc compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07300485A true JPH07300485A (en) | 1995-11-14 |
| JP3584989B2 JP3584989B2 (en) | 2004-11-04 |
Family
ID=14634923
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11432194A Expired - Fee Related JP3584989B2 (en) | 1994-04-28 | 1994-04-28 | Chiral zinc compounds |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3584989B2 (en) |
-
1994
- 1994-04-28 JP JP11432194A patent/JP3584989B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP3584989B2 (en) | 2004-11-04 |
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