金鸡纳碱类有机催化剂催化靛红及其衍生物的不对称Henry反应、Michael加成反应的研究
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摘要
本论文包括三方面工作：一、去甲奎尼丁不对称催化靛红和硝基烷烃的Henry反应；二、奎宁硫脲类催化剂不对称催化靛红不饱和腈基酯和硝基烷烃的Michael加成反应；三、奎宁胺不对称催化靛红不饱和二腈和酮的Michael加成反应。
从上个世纪初由Bredig第一次将有机催化应用于合成反应中,即利用奎宁或奎尼丁不对称催化羟氰化反应,有机催化的概念就引起人们的注意,并陆续扩展了有机催化的应用范围,直到2000年,List、BarbasⅢ、MacMillan等人在有机催化方面的杰出贡献,将有机催化的研究推向了高潮,由于有机催化本身具有无毒无害、简单易得、反应条件温和以及立体选择性强等特点,特别适合药物、天然产物、功能材料等的合成,因此,化学家们在有机催化剂的应用方面做了大量的工作,并取得了显著成果。
金鸡纳碱类催化剂的种类非常多,本文我们主要用到去甲奎尼丁、奎宁胺以及奎宁硫脲等三类催化剂,并分别将其用于三个以靛红或其衍生物作反应物的有机催化反应。
第一个靛红和硝基甲烷的Henry反应可以被去甲奎尼丁催化,在DMA (N,N-二甲基乙酰胺)作溶剂,苯甲酸作添加剂,-15℃的低温条件下得到产率99%,ee值92%的高对映选择性产物,经过二氯甲烷洗涤处理,得到的固体产物选择性高达99%ee。同时,该产物经过两步转化后可以得到天然产物(+)-Dioxibrassinin,再一步转化可得另一种天然产物(-)-S-Spirobrassinin,后者已经被证实是天然提取的植物抗菌素,这也是该化合物第一次被不对称有机催化、合成得到。
第二个有机催化的不对称Michael反应研究的是靛红不饱和腈基酯衍生物3-8和硝基烷烃3-9的加成反应,经过筛选最终采用奎宁硫脲类化合物作为手性催化剂,-10℃的无溶剂条件下可以催化得到高产率(99%)高对映选择性(88%ee)的加成产物3-10,该产物经过进一步将硝基还原成氨基的反应可以自动关环成为酰胺化合物3-11,同样得到了螺环-靛红类衍生物的重要化合物片段,且关环产物的对映选择性保持不变,增加了该不对称加成反应的研究意义。
第三个有机催化的研究内容是靛红不饱和二腈4-6与酮4-8的Michael加成反应,以奎宁胺作为手性催化剂,THF作溶剂,在该不对称反应中最重要的是采用(R)-BNPH (BINOL-磷酸)作为手性添加剂,(R)-BNPH的加入大大增强了加成产物的立体选择性(92%ee)。而且,经过进一步研究发现,靛红、丙二腈和酮的三组分“一锅法”反应,在相同反应条件下得到的产物的对映选择性甚至略高于两组分反应的产物,为95%ee,且产率基本保持不变(92-95%)。得到的手性产物4-7a经NaBH4还原后可以关环得到螺环-靛红的重要药用结构4-8a,具有重要的研究意义。
需要说明的是,论文对新合成的手性化合物的立体结构是通过X-射线单晶衍射确定的。并测定了相应的核磁共振(氢/碳谱)谱图、高分辨质谱、旋光度、熔点等数据作为支持。
The dissertation consists of three parts:(1) Enantioselective Henry reaction of isatin and nitromethene; (2) Enantioselective Michael addition of nitromethane to indolylidene-cyanoacetic acetate; (3) Enantioselective Michael addition of ketones to alkylidenemalononitriles.
Since 1910, the first organocatalytic cyanohydrin reaction in the presence of quinine/quinidine was proceeded by Bredig's method with low enantioselectivity (<10%ee). However, this kind of catalysts has arisen chemists'strong interests, and they broadened the application areas of different organocatalysts. Until 2000, the passion of organocatalytic research was pushed to the climax contributing to the excellent work of List, Barbas III, MacMillan et. al. Considering the advantages of organocatalysis, especially without metal contained, chemists would like to apply it on medicine and natural products'synthesis. And a mount of good results have been achieved.
Cinchona Alkaloids are very useful in asymmetric catalysis. In this dissertation, we used three of them, cuprine, quinine thiourea, and amino quinine, to catalyze Henry reaction and Michael addition with high enantioselectivity. Enantioselective Henry reaction of isatin and nitromethene was performed at-15℃in DMA, catalyzed by cuprine (10mol%) with 10mol% PhCOOH as additive. The chiral product could be obtained with 99% yield and 92%ee, and after the further treatment by CH2Cl2, enantioselectivity was raised up to 99%ee. The addition product could be transformed into (+)-Dioxibrassinin with two steps or (-)-S-Spirobrassinin with an additional step, the later is natural cruciferous phytoalexins.
The enantioselective Michael reaction of nitromethane to indolylidene-cyanoacetic acetate 3-8, catalyzed by quinine thiourea without solvent at -10℃, was the second topic research. The product could be obtained with high yield (99%) and high enantioselectivity (88%ee). After the reduction of -NO2 into -NH2, the addition product 3-10b could be transformed into spiro[oxindole] amide compound 3-11 whose crystal structure helped us determine the stereo-configuration of product 3-10.
The third topic was about enantioselective Michael addition of ketones to alkylidenemalononitriles 4-6 which was catalyzed by amino quinine with high yield (92-95%) and high ee value (92%ee). The enantioselectivity would become better (95%ee) if the three-component "one pot" addition of isatin, malononitrile, and acetone was reacted under the same condition. As we found that the addition of (R)-BNPH as additive could increase the ee value greatly from 75% to 92%. Then cycloaddition of chiral product 4-7a with NaBH4 occurred to give the corresponding spiro dihydropyran compounds 4-8a.
Additionally, The stero-structures of new compounds were determined by X-ray tests, followed by nuclear magnetic resonance spectroscopy (1H and 13C), high performance mass spectrometry, optical rotation, and melting point.
从上个世纪初由Bredig第一次将有机催化应用于合成反应中,即利用奎宁或奎尼丁不对称催化羟氰化反应,有机催化的概念就引起人们的注意,并陆续扩展了有机催化的应用范围,直到2000年,List、BarbasⅢ、MacMillan等人在有机催化方面的杰出贡献,将有机催化的研究推向了高潮,由于有机催化本身具有无毒无害、简单易得、反应条件温和以及立体选择性强等特点,特别适合药物、天然产物、功能材料等的合成,因此,化学家们在有机催化剂的应用方面做了大量的工作,并取得了显著成果。
金鸡纳碱类催化剂的种类非常多,本文我们主要用到去甲奎尼丁、奎宁胺以及奎宁硫脲等三类催化剂,并分别将其用于三个以靛红或其衍生物作反应物的有机催化反应。
第一个靛红和硝基甲烷的Henry反应可以被去甲奎尼丁催化,在DMA (N,N-二甲基乙酰胺)作溶剂,苯甲酸作添加剂,-15℃的低温条件下得到产率99%,ee值92%的高对映选择性产物,经过二氯甲烷洗涤处理,得到的固体产物选择性高达99%ee。同时,该产物经过两步转化后可以得到天然产物(+)-Dioxibrassinin,再一步转化可得另一种天然产物(-)-S-Spirobrassinin,后者已经被证实是天然提取的植物抗菌素,这也是该化合物第一次被不对称有机催化、合成得到。
第二个有机催化的不对称Michael反应研究的是靛红不饱和腈基酯衍生物3-8和硝基烷烃3-9的加成反应,经过筛选最终采用奎宁硫脲类化合物作为手性催化剂,-10℃的无溶剂条件下可以催化得到高产率(99%)高对映选择性(88%ee)的加成产物3-10,该产物经过进一步将硝基还原成氨基的反应可以自动关环成为酰胺化合物3-11,同样得到了螺环-靛红类衍生物的重要化合物片段,且关环产物的对映选择性保持不变,增加了该不对称加成反应的研究意义。
第三个有机催化的研究内容是靛红不饱和二腈4-6与酮4-8的Michael加成反应,以奎宁胺作为手性催化剂,THF作溶剂,在该不对称反应中最重要的是采用(R)-BNPH (BINOL-磷酸)作为手性添加剂,(R)-BNPH的加入大大增强了加成产物的立体选择性(92%ee)。而且,经过进一步研究发现,靛红、丙二腈和酮的三组分“一锅法”反应,在相同反应条件下得到的产物的对映选择性甚至略高于两组分反应的产物,为95%ee,且产率基本保持不变(92-95%)。得到的手性产物4-7a经NaBH4还原后可以关环得到螺环-靛红的重要药用结构4-8a,具有重要的研究意义。
需要说明的是,论文对新合成的手性化合物的立体结构是通过X-射线单晶衍射确定的。并测定了相应的核磁共振(氢/碳谱)谱图、高分辨质谱、旋光度、熔点等数据作为支持。
The dissertation consists of three parts:(1) Enantioselective Henry reaction of isatin and nitromethene; (2) Enantioselective Michael addition of nitromethane to indolylidene-cyanoacetic acetate; (3) Enantioselective Michael addition of ketones to alkylidenemalononitriles.
Since 1910, the first organocatalytic cyanohydrin reaction in the presence of quinine/quinidine was proceeded by Bredig's method with low enantioselectivity (<10%ee). However, this kind of catalysts has arisen chemists'strong interests, and they broadened the application areas of different organocatalysts. Until 2000, the passion of organocatalytic research was pushed to the climax contributing to the excellent work of List, Barbas III, MacMillan et. al. Considering the advantages of organocatalysis, especially without metal contained, chemists would like to apply it on medicine and natural products'synthesis. And a mount of good results have been achieved.
Cinchona Alkaloids are very useful in asymmetric catalysis. In this dissertation, we used three of them, cuprine, quinine thiourea, and amino quinine, to catalyze Henry reaction and Michael addition with high enantioselectivity. Enantioselective Henry reaction of isatin and nitromethene was performed at-15℃in DMA, catalyzed by cuprine (10mol%) with 10mol% PhCOOH as additive. The chiral product could be obtained with 99% yield and 92%ee, and after the further treatment by CH2Cl2, enantioselectivity was raised up to 99%ee. The addition product could be transformed into (+)-Dioxibrassinin with two steps or (-)-S-Spirobrassinin with an additional step, the later is natural cruciferous phytoalexins.
The enantioselective Michael reaction of nitromethane to indolylidene-cyanoacetic acetate 3-8, catalyzed by quinine thiourea without solvent at -10℃, was the second topic research. The product could be obtained with high yield (99%) and high enantioselectivity (88%ee). After the reduction of -NO2 into -NH2, the addition product 3-10b could be transformed into spiro[oxindole] amide compound 3-11 whose crystal structure helped us determine the stereo-configuration of product 3-10.
The third topic was about enantioselective Michael addition of ketones to alkylidenemalononitriles 4-6 which was catalyzed by amino quinine with high yield (92-95%) and high ee value (92%ee). The enantioselectivity would become better (95%ee) if the three-component "one pot" addition of isatin, malononitrile, and acetone was reacted under the same condition. As we found that the addition of (R)-BNPH as additive could increase the ee value greatly from 75% to 92%. Then cycloaddition of chiral product 4-7a with NaBH4 occurred to give the corresponding spiro dihydropyran compounds 4-8a.
Additionally, The stero-structures of new compounds were determined by X-ray tests, followed by nuclear magnetic resonance spectroscopy (1H and 13C), high performance mass spectrometry, optical rotation, and melting point.
引文
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