JP2007238540A5 - - Google Patents

Description

（式中、Ｒ^１は、炭素数が３以上のアルキル基又はアリール基を表し、Ｒ^２は、水素原子又は炭素数１〜４のアルキル基若しくはアルコキシ基を表し、Ｘは、−ＯＨ、又は−ＳＨを表す。）で表される配位子又はその対掌体とＭ（ＯＳＯ_２Ｒ^３）_３又はＭ（ＯＳＯ_３Ｒ^３）_３（式中、ＭはＳｃ、Ｙ又はランタノイド元素を表し、Ｒ^３は炭素数が６以上の脂肪族炭化水素基、芳香族炭化水素基又はパーフルオロアルキル基を表す。）で表されるルイス酸とを混合させて得られる触媒の存在下で、下式（式２）

（式中、Ｒ^４は、置換基を有していてもよい脂肪族炭化水素基、芳香族炭化水素基又は複素環基を表す。）で表されるエポキシドと、下式

（式中、Ｙ^１は＝ＣＨ−又は＝Ｎ−を表し、Ｙ^２は＝ＣＲ^７−又は＝Ｎ−（式中、Ｒ^７は水素原子又は炭化水素基を表す。）を表し、Ｚは−ＮＨ−、−ＮＲ^８−（式中、Ｒ^８は水素原子以外の炭化水素基を表す。）、−Ｏ−又は−Ｓ−を表す。但し、Ｙ^１が＝Ｎ−の場合には、Ｚは−ＮＨ−を表す。Ｒ^５及びＲ^６は共同して置換基を有していてもよい芳香環又は複素芳香環を形成する。）で表される複素環化合物とを反応させることから成る下式

（Ｙ^１が＝ＣＨ−の場合は式（１）又はその対掌体で表され、Ｙ^１が＝Ｎ−の場合は式（２）又はその対掌体で表され、式中、Ｒ^４〜Ｒ^６は上記と同様に定義される。）で表される光学活性アルコール化合物の製法である。
That is, the present invention provides the following formula (chemical formula 1) in an aqueous solution or a mixed solvent of water and an organic solvent.

(Wherein R ¹ represents an alkyl group or aryl group having 3 or more carbon atoms, R ² represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group, and X represents —OH, or And represents an enantiomer thereof and M (OSO ₂ R ³ ) ₃ or M (OSO ₃ R ³ ) ₃ (wherein M represents Sc, Y or a lanthanoid element). , R ³ represents an aliphatic hydrocarbon group having 6 or more carbon atoms, an aromatic hydrocarbon group or a perfluoroalkyl group.) In the presence of a catalyst obtained by mixing with a Lewis acid represented by Formula (Formula 2)

(Wherein R ⁴ represents an aliphatic hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic group which may have a substituent) and the following formula:

(Wherein Y ¹ represents ═CH— or ═N—, Y ² represents ═CR ⁷ — or ═N— (wherein R ⁷ represents a hydrogen atom or a hydrocarbon group), and Z represents —NH—, —NR ⁸ — (wherein R ⁸ represents a hydrocarbon group other than a hydrogen atom), —O— or —S—, provided that when Y ¹ is ═N— Z represents —NH—, and R ⁵ and R ⁶ jointly form an aromatic ring or a heteroaromatic ring which may have a substituent. The following formula

(When Y ¹ is = CH-, it is represented by formula (1) or an enantiomer thereof, and when Y ¹ is = N-, it is represented by formula (2) or its enantiomer , wherein R ⁴ to R ⁶ is the preparation of optically active alcohol compound represented by are as defined above.).

の配位子又はその対掌体とＭ（ＯＳＯ_２Ｒ^３）_３又はＭ（ＯＳＯ_３Ｒ^３）_３で表されるルイス酸とを混合させて得られる。
The catalyst used in the present invention has the following structure:

Or an enantiomer thereof and a Lewis acid represented by M (OSO ₂ R ³ ) ₃ or M (OSO ₃ R ³ ) ₃ are obtained.

式中、Ｒ^４〜Ｒ^６は上記と同様に定義される。


In the present invention, by mixing the catalyst and the substrate epoxide and heterocyclic compound in the solvent, the heterocyclic compound undergoes an asymmetric ring-opening reaction of the epoxide, and the optically active alcohol compound increases. Yield and highly stereoselective. In this asymmetric ring-opening reaction, the heterocyclic compound is trans-added stereospecifically. When Y ¹ in the heterocyclic compound is a carbon atom (═CH—), the product optically active alcohol compound is represented by the following formula (1) or an enantiomer thereof, and Y ¹ is a nitrogen atom (= N-) is represented by the following formula (2) or an enantiomer thereof.

In the formula, R ^{4 to} R ⁶ are defined as described above.

Claims (1)

In an aqueous solution or a mixed solvent of water and an organic solvent,

(Wherein R ¹ represents an alkyl group or aryl group having 3 or more carbon atoms, R ² represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group, and X represents —OH, or And represents an enantiomer thereof and M (OSO ₂ R ³ ) ₃ or M (OSO ₃ R ³ ) ₃ (wherein M represents Sc, Y or a lanthanoid element). , R ³ represents an aliphatic hydrocarbon group having 6 or more carbon atoms, an aromatic hydrocarbon group or a perfluoroalkyl group.) In the presence of a catalyst obtained by mixing with a Lewis acid represented by Formula (Formula 2)

(Wherein R ⁴ represents an aliphatic hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic group which may have a substituent) and the following formula:

(Wherein Y ¹ represents ═CH— or ═N—, Y ² represents ═CR ⁷ — or ═N— (wherein R ⁷ represents a hydrogen atom or a hydrocarbon group), and Z represents —NH—, —NR ⁸ — (wherein R ⁸ represents a hydrocarbon group other than a hydrogen atom), —O— or —S—, provided that when Y ¹ is ═N— Z represents —NH—, and R ⁵ and R ⁶ jointly form an aromatic ring or a heteroaromatic ring which may have a substituent. The following formula

(When Y ¹ is = CH-, it is represented by formula (1) or an enantiomer thereof, and when Y ¹ is = N-, it is represented by formula (2) or its enantiomer , wherein R ⁴ preparation of optically active alcohol compound to R ⁶ is represented by are as defined above.).