KR20130080709A - Method for preparation of chiral naphthoquinone derivatives - Google Patents
Method for preparation of chiral naphthoquinone derivatives Download PDFInfo
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Abstract
Description
본 발명은 생리활성이 있는 화합물로 이용되고 있는 나프토퀴논(naphthoquinone) 유도체의 제조방법에 관한 것으로, 특히 키랄(chiral) 촉매를 이용하여 광학 순도가 높은 광학활성물질을 효율적으로 제조할 수 있는 키랄 나프토퀴논 유도체의 제조방법에 관한 것이다.
The present invention relates to a method for producing a naphthoquinone derivative used as a compound having a physiological activity, in particular chiral catalyst that can efficiently produce an optically active material with high optical purity using a chiral catalyst It relates to a method for producing a naphthoquinone derivative.
광학이성질체는 밀도, 녹는점, 끓는점 등 대부분의 물리적 성질이 동일하다. 그러나, 편광된 빛을 흡수하는 정도가 다르기 때문에 선형편광된 빛을 조사(照射)했을 때 편광면이 회전하게 되며, 이러한 현상을 광학활성이라고 한다. Optical isomers have almost the same physical properties such as density, melting point, and boiling point. However, since the degree of absorption of polarized light is different, the polarization plane rotates when the linearly polarized light is irradiated. This phenomenon is called optical activity.
물질의 광학활성은 편광계를 사용하여 측정한다. 광학활성은 대칭 중심, 대칭면 또는 회전축 등의 대칭 요소를 갖지 못하는 분자에서 나타난다. 이러한 분자들은, 왼손 또는 오른손과 같이 좌우가 바뀌고 서로 겹쳐지지 않는 거울상체의 관계를 갖는 2 개의 이성질체로 존재할 수 있으며, 이런 성질을 가진 분자를 키랄성 화합물(chiral compound)이라고 한다. The optical activity of the material is measured using a polarimeter. Optical activity occurs in molecules that do not have symmetrical elements such as symmetry centers, symmetry planes, or rotational axes. These molecules can exist as two isomers with enantiomers that change left and right and do not overlap each other, such as the left or right hand, and a molecule having this property is called a chiral compound.
키랄 촉매를 이용한 비대칭 합성 방법은 키랄 화합물을 만드는 가장 효율적인 방법이다. Asymmetric synthesis methods using chiral catalysts are the most efficient methods for making chiral compounds.
키랄 나프토퀴논 유도체들은 생리 활성이 있는 화합물이기 때문에 많은 연구가 진행되고 있는 분야이다. 키랄 촉매를 이용하여 2-하이드록시-1,4-나프토퀴논과 나이트로올레핀과의 비대칭 마이클 반응은 일부 알려져 있지만 촉매량을 과량 사용하였다는 단점이 있다(Zhou, W-M.; Liu, H.; Du, D-M. Org . Lett . 2008, 13, 2817-2820).
Since chiral naphthoquinone derivatives are physiologically active compounds, much research is being conducted. Asymmetric Michael reactions of 2-hydroxy-1,4-naphthoquinone with nitroolefins using chiral catalysts are known in part but have the disadvantage of using excessive amounts of catalyst (Zhou, WM .; Liu, H .; Du , DM. Org. Lett. 2008 , 13, 2817-2820).
본 발명의 목적은 키랄 촉매를 이용하여 광학 순도가 높은 광학활성물질을 효율적으로 제조할 수 있는 키랄 나프토퀴논 유도체의 제조방법을 제공하는 것이다.
It is an object of the present invention to provide a method for preparing a chiral naphthoquinone derivative which can efficiently produce an optically active material having high optical purity using a chiral catalyst.
상기 목적을 달성하기 위해 본 발명에 따른 키랄 나프토퀴논 유도체의 제조방법은 키랄 촉매를 이용한 키랄 나프토퀴논 유도체의 제조방법으로서, 적은 량의 키랄 촉매의 존재 하에서 나프토퀴논과 나이트로 올레핀과 반응시키는 것을 특징으로 한다.In order to achieve the above object, a method for preparing a chiral naphthoquinone derivative according to the present invention is a method for preparing a chiral naphthoquinone derivative using a chiral catalyst, which is reacted with naphthoquinone and nitro olefin in the presence of a small amount of chiral catalyst. It is characterized by.
상술한 바와 같이, 본 발명에 따른 키랄 나프토퀴논 유도체들의 제조방법에 의하면, 키랄 촉매를 0.1 몰% 이용하여 광학 순도가 높은 광학활성물질을 효율적으로 제조할 수 있다는 효과가 얻어진다.
As described above, according to the method for preparing chiral naphthoquinone derivatives according to the present invention, an effect of efficiently producing an optically active material having high optical purity is obtained by using 0.1 mol% of a chiral catalyst.
본 발명의 상기 및 그 밖의 목적과 새로운 특징은 본 명세서의 기술 및 첨부 도면에 의해 더욱 명확하게 될 것이다.These and other objects and novel features of the present invention will become more apparent from the description of the present specification and the accompanying drawings.
먼저 본 발명에 따른 키랄 나프토퀴논 유도체의 제조방법의 특징에 대해 설명한다.First, the process for producing the chiral naphthoquinone derivative according to the present invention will be described.
본 발명의 일 실시 예에 따른 키랄 나프토퀴논 유도체의 제조방법은 나프토퀴논을 키랄 촉매의 존재 하에서, 나이트로 올레핀과 반응시켜 키랄 나프토퀴논 유도체를 제조한다. 상기 제조방법은, 키랄 촉매를 이용하여, 광학 순도가 높은 광학활성물질을 효율적으로 제조하기 위한 것이다.In the method for preparing a chiral naphthoquinone derivative according to an embodiment of the present invention, a chiral naphthoquinone derivative is prepared by reacting naphthoquinone with nitro olefin in the presence of a chiral catalyst. The above production method is for efficiently producing an optically active substance with high optical purity using a chiral catalyst.
위 제조방법에서 사용되는 키랄 촉매는, 하기 화학식 1 또는 2의 화합물이다.The chiral catalyst used in the above manufacturing method is a compound of the following formula (1) or (2).
또 본 발명의 일 실시 예에서, 상기 키랄 촉매의 함량은 반응 물질들의 전체 몰수를 기준으로, 0.01 내지 5 몰%, 구체적으로는 0.1 내지 1 몰%이다. 상기 범위는, 광학 순도가 높은 키랄 나프토퀴논 유도체를 효율적으로 제조하기 위한 것이다. In addition, in one embodiment of the present invention, the content of the chiral catalyst is 0.01 to 5 mol%, specifically 0.1 to 1 mol% based on the total moles of the reactants. The above range is for efficiently producing chiral naphthoquinone derivatives having high optical purity.
또 본 발명의 일 실시 예에서, 나프토퀴논은 하기의 화학식 3의 구조를 갖는 화합물일 수 있다. In another embodiment of the present invention, naphthoquinone may be a compound having a structure of Formula 3 below.
상기 나이트로 올레핀은 하기 화학식 4의 구조를 갖는 화합물일 수 있다. The nitro olefin may be a compound having a structure of Formula 4 below.
상기 화학식 4에서 R은 C6-C14의 아릴기 또는 C4-C10의 방향족 헤테로고리 화합물이다.In Formula 4, R is an aryl group of C 6 -C 14 or an aromatic heterocyclic compound of C 4 -C 10 .
상기 아릴기는 C1-C10의 알콕시기, 알킬기, C1-C10알킬 아민기가 치환된 아릴기 또는 할로겐으로 치환된 아릴기일 수 있다. 상기 R은 방향족 헤테로고리 화합물인 퓨릴(furyl), 싸이에닐(thienyl) 또는 피리딜(pyridyl)일 수 있다.The aryl group may be an aryl group substituted with an alkoxy group of C 1 -C 10 , an alkyl group, a C 1 -C 10 alkyl amine group or a halogen. R may be an aromatic heterocyclic compound, furyl, thienyl, or pyridyl.
상기 키랄 나프토퀴논 유도체는 화학식 5를 갖는 화합물일 수 있다.The chiral naphthoquinone derivative may be a compound having Formula 5.
상기 화학식 5에서 R은 C6-C14의 아릴기 또는 C4-C10의 방향족 헤테로고리 화합물이다.In Formula 5, R is an aryl group of C 6 -C 14 or an aromatic heterocyclic compound of C 4 -C 10 .
상기 아릴기는 C1-C10의 알콕시기, 알킬기, C1-C10알킬 아민기가 치환된 아릴기 또는 할로겐으로 치환된 아릴기일 수 있다. 상기 R은 방향족 헤테로고리 화합물인 퓨릴(furyl), 싸이에닐(thienyl) 또는 피리딜(pyridyl)일 수 있다.
The aryl group may be an aryl group substituted with an alkoxy group of C 1 -C 10 , an alkyl group, a C 1 -C 10 alkyl amine group or a halogen. R may be an aromatic heterocyclic compound, furyl, thienyl, or pyridyl.
또 본 발명의 일 실시 예에서, 나프토퀴논을 키랄 촉매 존재 하에서 나이트로 올레핀과 반응시켜 키랄 나프토퀴논 유도체를 제조할 수 있다. 구체적인 반응식은 하기 반응식 1과 같다. In addition, in one embodiment of the present invention, a chiral naphthoquinone derivative may be prepared by reacting naphthoquinone with nitro olefin in the presence of a chiral catalyst. Specific reaction schemes are the same as in Scheme 1 below.
[ 반응식 1 ]Scheme 1
상기 반응식 1에서, R은 위에서 정의한 바와 같다.In Scheme 1, R is as defined above.
이하, 하기 실시 예 등에 의하여 본 발명을 더욱 상세하게 설명하고자 한다. 다만, 하기 실시 예 등은 본 발명을 예시하기 위한 것일 뿐 본 발명의 범위가 이들만으로 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples and the like are intended to illustrate the present invention, but the scope of the present invention is not limited thereto.
입체 선택적인 키랄 나프토퀴논 유도체의 합성을 위해 하기 반응식 2와 같이, 키랄 촉매를 이용한 비대칭 반응을 수행하였으며, 하기 표 1에서 알 수 있는 바와 같이, 작은 양의 촉매량으로 높은 입체선택성 나타내었다.For the synthesis of the stereoselective chiral naphthoquinone derivative, as shown in Scheme 2, an asymmetric reaction was performed using a chiral catalyst, and as shown in Table 1, high stereoselectivity was exhibited with a small amount of catalyst.
[반응식 2][Reaction Scheme 2]
표 1에서 수율은 컬럼크로마토 그래피로 분리 정제하여 측정하였고, 거울상 이성질체 비율은 HPLC 분석 방법으로 결정하였다. 표 1에서 알 수 있는 바와 같이, 촉매량을 줄여도 높은 입체 선택성을 나타나고 있다. The yield in Table 1 was determined by column chromatography separated purification, enantiomeric ratio was determined by HPLC analysis method. As can be seen from Table 1, even if the amount of catalyst is reduced, high stereoselectivity is shown.
하기 반응식 3과 같이, 0.1 몰% 의 촉매량을 사용하여 나프토 퀴논 유도체를 합성하였고, 그 결과를 표 2에 나타내었다.As shown in Scheme 3, a naphthoquinone derivative was synthesized using a catalytic amount of 0.1 mol%, and the results are shown in Table 2.
[반응식 3]Scheme 3
표 2에서 수율은 컬럼크로마토 그래피로 분리 정제하여 측정하였다. 거울상 이성질체 비율은 HPLC 분석 방법으로 결정하였다.
The yield in Table 2 was measured by separation and purification by column chromatography. Enantiomeric ratios were determined by HPLC analysis.
[실시 예 1][Example 1]
(R)-2-Hydroxy-3-(2-nitro-1-phenylethyl)-1,4-naphthoquinone(R) -2-Hydroxy-3- (2-nitro-1-phenylethyl) -1,4-naphthoquinone
플라스크에 2-하이드록시-1,4-나프토퀴논 0.1mmol, THF 0.4 mL, 상기 촉매 0.001 mmol 을 넣고 상온에서 교반한다. 나이트로 올레핀 0.1 mmol을 넣고 상온에서 2시간 교반한다. 반응진행이 완료되면 반응 혼합물을 농축 후, 컬럼크로마토크래피로 분리 정제하여 화학식 5를 98% 수율, 99% ee(enantiomeric excess)의 거울상 입체선택성으로 얻었다. 0.1 mmol of 2-hydroxy-1,4-naphthoquinone, 0.4 mL of THF in the flask, the catalyst Add 0.001 mmol and stir at room temperature. 0.1 mmol of olefin is added and stirred at room temperature for 2 hours. Upon completion of the reaction, the reaction mixture was concentrated and separated and purified by column chromatography to obtain Formula 5 in enantiomeric stereoselectivity of 98% yield and 99% ee (enantiomeric excess).
[a]17 D = -44.8 (c = 1, acetone); 1H NMR (200 MHz, CDCl3): δ= 8.21 (d, J = 7.5 Hz, 1H), 8.16 (d, J = 7.5 Hz, 1H), 7.77-7.28(m, 7H), 5.51 (m, 1H), 5.37-5.34 (m, 1H), 5.16 (m, 1H); HPLC (30 : 70 n-hexane : i-PrOH, 254 nm, 1.0 mL/min) Chiralcel OJ-H column, tR = 26.3 min (minor), tR = 61.7 min (major), 99% ee.[a] 17 D = -44.8 (c = 1, acetone); 1 H NMR (200 MHz, CDCl 3 ): δ = 8.21 (d, J = 7.5 Hz, 1H), 8.16 (d, J = 7.5 Hz, 1H), 7.77-7.28 (m, 7H), 5.51 (m, 1H), 5.37-5.34 (m, 1H), 5.16 (m, 1H); HPLC (30: 70 n-hexane: i-PrOH, 254 nm, 1.0 mL / min) Chiralcel OJ-H column, t R = 26.3 min (minor), t R = 61.7 min (major), 99% ee.
[실시 예 2][Example 2]
(R)-2-Hydroxy-3-[1-(4-methylphenyl)-2-nitroethyl]-1,4-naphthoquinone(R) -2-Hydroxy-3- [1- (4-methylphenyl) -2-nitroethyl] -1,4-naphthoquinone
상기 실시 예 1과 동일한 방법으로 화학식 5를 97% 수율, 95% ee의 입체선택성으로 얻었다.In the same manner as in Example 1, Formula 5 was obtained in 97% yield and stereoselectivity of 95% ee.
[a]17 D = -24.8 (c = 1, acetone); 1H NMR (200 MHz, CDCl3): δ= 8.12 (d, J = 7.5 Hz, 1H), 8.16 (d, J = 7.5 Hz, 1H), 7.79-7.12(m, 6H), 5.46 (m, 1H), 5.28 (m, 1H), 5.12 (m, 1H), 2.30 (s, 3H). HPLC (30 : 70 n-hexane : i-PrOH, 254 nm, 1.0 mL/min) Chiralcel OJ-H column, tR = 22.3 min (minor), tR = 71.7 min (major), 95% ee.[a] 17 D = -24.8 (c = 1, acetone); 1 H NMR (200 MHz, CDCl 3 ): δ = 8.12 (d, J = 7.5 Hz, 1H), 8.16 (d, J = 7.5 Hz, 1H), 7.79-7.12 (m, 6H), 5.46 (m, 1H), 5.28 (m, 1H), 5.12 (m, 1H), 2.30 (s, 3H). HPLC (30: 70 n-hexane: i-PrOH, 254 nm, 1.0 mL / min) Chiralcel OJ-H column, t R = 22.3 min (minor), t R = 71.7 min (major), 95% ee.
[실시 예 3][Example 3]
(R)-2-Hydroxy-3-[1-(4-methoxyphenyl)-2-nitroethyl]-1,4-naphthoquinone(R) -2-Hydroxy-3- [1- (4-methoxyphenyl) -2-nitroethyl] -1,4-naphthoquinone
상기 실시 예 1과 동일한 방법으로 화학식 5를 98% 수율, 99% ee의 입체선택성으로 얻었다.In the same manner as in Example 1, Formula 5 was obtained in stereoselectivity of 98% yield and 99% ee.
[a]17 D = -12.7 (c = 1, acetone); 1H NMR (300 MHz, CDCl3): δ= 8.11 (d, J = 7.5 Hz, 1H), 8.06 (d, J = 7.5 Hz, 1H), 7.87-6.84(m, 6H), 5.44 (m, 1H), 5.26 (m, 1H), 5.12 (m, 1H), 3.76 (s, 3H); HPLC (30 : 70 n-hexane : i-PrOH, 254 nm, 1.0 mL/min) Chiralcel OJ-H column, tR = 13.3 min (minor), tR = 52.7 min (major), 99% ee.[a] 17 D = -12.7 (c = 1, acetone); 1 H NMR (300 MHz, CDCl 3 ): δ = 8.11 (d, J = 7.5 Hz, 1H), 8.06 (d, J = 7.5 Hz, 1H), 7.87-6.84 (m, 6H), 5.44 (m, 1H), 5.26 (m, 1H), 5.12 (m, 1H), 3.76 (s, 3H); HPLC (30: 70 n-hexane: i-PrOH, 254 nm, 1.0 mL / min) Chiralcel OJ-H column, t R = 13.3 min (minor), t R = 52.7 min (major), 99% ee.
[실시 예 4][Example 4]
(R)-2-[1-(4-Fluorophenyl)-2-nitroethyl]-3-hydroxy-1,4-naphthoquinone(R) -2- [1- (4-Fluorophenyl) -2-nitroethyl] -3-hydroxy-1,4-naphthoquinone
상기 실시 예 1과 동일한 방법으로 화학식 5를 95% 수율, 95% ee의 입체선택성으로 얻었다.In the same manner as in Example 1, Chemical Formula 5 was obtained in 95% yield and stereoselectivity of 95% ee.
[a]17 D = -37.0 (c = 1, acetone); 1H NMR (200 MHz, CDCl3): δ= 8.12 (d, J = 7.5 Hz, 1H), 8.07 (d, J = 7.5 Hz, 1H), 7.81?6.98(m, 6H), 5.41 (m, 1H), 5.30 (m, 1H), 5.16(m, 1H); HPLC (30 : 70 n-hexane : i-PrOH, 254 nm, 1.0 mL/min) Chiralcel OJ-H column, tR = 17.3 min (minor), tR = 60.7 min (major), 95% ee.[a] 17 D = -37.0 (c = 1, acetone); 1 H NMR (200 MHz, CDCl 3 ): δ = 8.12 (d, J = 7.5 Hz, 1H), 8.07 (d, J = 7.5 Hz, 1H), 7.81-6.98 (m, 6H), 5.41 (m, 1H), 5.30 (m, 1 H), 5.16 (m, 1 H); HPLC (30: 70 n-hexane: i-PrOH, 254 nm, 1.0 mL / min) Chiralcel OJ-H column, t R = 17.3 min (minor), t R = 60.7 min (major), 95% ee.
[실시 예 5][Example 5]
(R)-2-[1-(4-Bromophenyl)-2-nitroethyl]-3-hydroxy-1,4-naphthoquinone(R) -2- [1- (4-Bromophenyl) -2-nitroethyl] -3-hydroxy-1,4-naphthoquinone
상기 실시예 1과 동일한 방법으로 화학식 5를 96% 수율, 95% ee의 입체선택성으로 얻었다.In the same manner as in Example 1, Formula 5 was obtained in a stereoselectivity of 96% yield and 95% ee.
[a]17 D = -43.4 (c = 1, acetone); 1H NMR (200 MHz, CDCl3): δ= 8.12 (d, J = 7.5 Hz, 1H), 8.08 (d, J = 7.5 Hz, 1H), 7.79-7.19(m, 6H), 5.40 (m, 1H), 5.28 (m, 1H), 5.17 (m, 1H); HPLC (30 : 70 n-hexane : i-PrOH, 254 nm, 1.0 mL/min) Chiralcel OJ-H column, tR = 22.3 min (minor), tR = 80.7 min (major), 95% ee.
[a] 17 D = -43.4 (c = 1, acetone); 1 H NMR (200 MHz, CDCl 3 ): δ = 8.12 (d, J = 7.5 Hz, 1H), 8.08 (d, J = 7.5 Hz, 1H), 7.79-7.19 (m, 6H), 5.40 (m, 1H), 5.28 (m, 1H), 5.17 (m, 1H); HPLC (30: 70 n-hexane: i-PrOH, 254 nm, 1.0 mL / min) Chiralcel OJ-H column, t R = 22.3 min (minor), t R = 80.7 min (major), 95% ee.
이상 본 발명자에 의해서 이루어진 발명을 상기 실시 예에 따라 구체적으로 설명하였지만, 본 발명은 상기 실시 예에 한정되는 것은 아니고 그 요지를 이탈하지 않는 범위에서 여러 가지로 변경 가능한 것은 물론이다.
Although the present invention has been described in detail with reference to the above embodiments, it is needless to say that the present invention is not limited to the above-described embodiments, and various modifications may be made without departing from the spirit of the present invention.
본 발명에 따른 키랄 나프토퀴논 유도체의 제조방법은 광학 순도가 높은 광학활성물질의 효율적 제조에 이용된다.
The method for producing a chiral naphthoquinone derivative according to the present invention is used for the efficient preparation of an optically active material having high optical purity.
Claims (7)
나프토퀴논과, 키랄 촉매의 존재 하에서 나이트로 올레핀과 반응시키며,
상기 키랄 촉매로서 0.1 몰%의 키랄 유기 촉매를 이용하는 것을 특징으로 하는 키랄 나프토퀴논 유도체의 제조방법.As a method for producing a chiral naphthoquinone derivative using a chiral catalyst,
Reacting with naphthoquinone and nitro olefins in the presence of a chiral catalyst,
A method for producing a chiral naphthoquinone derivative, characterized in that 0.1 mol% chiral organic catalyst is used as the chiral catalyst.
상기 나프토 퀴논은 하기 화학식 3의 구조를 갖는 것을 특징으로 하는 키랄 나프토퀴논 유도체의 제조방법.
[화학식 3]
The naphthoquinone has a structure of the following formula (3).
(3)
상기 나이트로 올레핀은 하기 화학식 4의 구조를 갖는 것을 특징으로 하는 키랄 나프토퀴논 유도체의 제조방법.
[화학식 4]
상기 화학식 4에서 R은 C6-C14의 아릴기 또는 C4-C10의 방향족 헤테로고리 화합물이고, 상기 아릴기는 C1-C10의 알콕시기, 알킬기, C1-C10알킬 아민기가 치환된 아릴기 또는 할로겐으로 치환된 아릴기이며, 상기 R은 방향족 헤테로고리 화합물인 퓨릴(furyl), 싸이에닐(thienyl) 또는 피리딜(pyridyl) 임.The method of claim 1,
The nitro olefin has a structure of the formula (4) characterized in that the method for producing a chiral naphthoquinone derivative.
[Chemical Formula 4]
In Formula 4, R is a C 6 -C 14 aryl group or C 4 -C 10 aromatic heterocyclic compound, wherein the aryl group is a C 1 -C 10 alkoxy group, alkyl group, C 1 -C 10 alkyl amine group is substituted Aryl group or an aryl group substituted with a halogen, wherein R is an aromatic heterocyclic compound furyl, thienyl or pyridyl.
상기 나프토퀴논을 키랄 촉매의 존재 하에서 나이트로 올레핀과 반응시켜, 하기 화학식 5의 구조를 갖는 것을 특징으로 하는 키랄 나프토퀴논 유도체의 제조방법.
[화학식 5]
상기 화학식 5에서 R은 C6-C14의 아릴기 또는 C4-C10의 방향족 헤테로고리 화합물이고, 상기 아릴기는 C1-C10의 알콕시기, 알킬기, C1-C10알킬 아민기가 치환된 아릴기 또는 할로겐으로 치환된 아릴기이며, 상기 R은 방향족 헤테로고리 화합물인 퓨릴(furyl), 싸이에닐(thienyl) 또는 피리딜(pyridyl)임.The method of claim 1,
The naphthoquinone is reacted with nitro olefins in the presence of a chiral catalyst to produce a chiral naphthoquinone derivative.
[Chemical Formula 5]
In Formula 5, R is a C 6 -C 14 aryl group or C 4 -C 10 aromatic heterocyclic compound, wherein the aryl group is substituted with a C 1 -C 10 alkoxy group, alkyl group, C 1 -C 10 alkyl amine group Aryl group or an aryl group substituted with a halogen, wherein R is an aromatic heterocyclic compound furyl, thienyl or pyridyl.
상기 키랄 촉매는, 하기 화학식 1, 화학식 2 또는 그 광학 이성질체를 특징으로 하는 키랄 나프토퀴논 유도체의 제조방법.
[화학식 1]
[화학식 2]
The chiral catalyst is a method for producing a chiral naphthoquinone derivative characterized by the following formula (1), (2) or optical isomers thereof.
[Formula 1]
(2)
상기 키랄 촉매의 함량은 반응 물질들의 전체 몰수를 기준으로, 0.01 내지 5 몰%인 것을 특징으로 하는 키랄 나프토퀴논 유도체의 제조방법. The method of claim 1,
The content of the chiral catalyst is 0.01 to 5 mol% based on the total number of moles of the reaction materials, the method for producing a chiral naphthoquinone derivative.
[ 반응식 1]
상기 R은 C6-C14의 아릴기 또는 C4-C10의 방향족 헤테로고리 화합물이고, 상기 아릴기는 C1-C10의 알콕시기, 알킬기, C1-C10알킬 아민기가 치환된 아릴기 또는 할로겐으로 치환된 아릴기이며, 상기 R은 방향족 헤테로고리 화합물인 퓨릴(furyl), 싸이에닐(thienyl) 또는 피리딜(pyridyl)임.
A method for producing a chiral naphthoquinone derivative by reacting naphthoquinone with nitro olefin in the presence of a chiral catalyst as in Scheme 1 below.
Scheme 1
R is an aryl group of C 6 -C 14 or an aromatic heterocyclic compound of C 4 -C 10 , wherein the aryl group is an aryl group substituted with a C 1 -C 10 alkoxy group, an alkyl group, a C 1 -C 10 alkyl amine group Or an aryl group substituted with halogen, wherein R is an aromatic heterocyclic compound furyl, thienyl or pyridyl.
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