硫脲手性有机催化剂的设计合成及反应研究探讨
摘要
对硫脲有机小分子催化剂的研究越来越多,由于其结构中含有N-H基团易于与多种底物(如羰基,硝基等)形成分子间氢键从而实现良好的催化活性及手性控制。随着对硫脲催化剂研究的进一步深入,发现双功能化手性硫脲催化剂在催化不对称Michael加成等反应时,得到较为满意的产率和对映体过量值。本论文设计合成了以便宜、易得的天然L-(+)-酒石酸为原料,经酯化,成环,格氏反应,氯代,叠氮化,还原,等7步反应获得了(Ⅰ、Ⅱ、Ⅲ)三个新的以TADDAMIN为骨架的手性伯胺-硫脲催化剂。及以(4R,5S)-5-(胺基-二苯基-甲基)-2,2-二甲基-α,α-二苯基-1,3-二氧戊环-4-甲醇)为骨架的硫脲催化剂(Ⅳ),及以1,2-环己二胺(DACH)为骨架一端和脯氨酸以酰胺键连接,另一端形成硫脲的催化剂的设计与合成Ⅵ。同时还合成了一种已报道的硫脲-叔胺催化剂Ⅴ。尝试了它们在催化β-硝基苯乙烯与丙二酸二乙酯,β-硝基苯乙烯与酮的Michael加成反应,肉桂酸酯与硝基甲烷Michael加成反应,査尔酮与硝基甲烷的Michael加成反应,催化剂Ⅴ催化査尔酮与对甲氧基苯胺的aza-Michael加成反应,体系中加入适量的DIPEA有催化活性,而且有旋光。缺点是产率低只有百分之十左右,还需要继续选择合适的体系,如换用其它溶剂,改用其它碱催化希望结果会更好。催化剂Ⅵ催化对硝基苯甲醛与丙酮的aldol反应,有催化活性,还需进一步研究。同时,需要再尝试新的反应体系。并研究催化剂的结构、溶剂效应、温度、催化剂用量及反应底物类型对立体选择性的影响,以筛选适合的催化剂和优化反应条件。
In recent years, more and more scholars come to study on asymmetric organic reaction catalyzed by small organic molecule catalysts containing thiourea group(s). Rely on the structures containing N-H groups is apt to form dual Intermolecular hydrogen bonds with multiple substrates to achieve good catalytic activity and control of chiral.studies on and applications of asymmetric organic reaction catalyzed by thiourea catalysts have been regarded as one of the most remarkable fields in catalytic asymmetric reactions .Since 1998 the Jacobsen research team's pioneering work, had many applies with the amino acid skeleton connected urea/thiourea chiral catalyst in many kinds of asymmetrical reaction and has realized the very good Stereoselectivity. With the development of small organic molecule catalysts, Chemists began to simulate the structure and characteristics of enzymes which have multi- activation center and these activation centers compose suitable spatial structure and urge catalytic reaction to become more efficient. Receives the enzyme the structure inspiration, in 2003, Takemoto research team's proposed for the first time the single molecular double activation concept, and designed and synthesized bifunctional thiourea-tertiary amine catalyst, introduced other activating group during introduction thiourea groups and introduction another activation in another end (chiral amine) to form double functionalization double activation catalyst, enhances reaction activity and stereo selective greatly. Hereafter a series of includes each kind of chiral skeleton's bifunctional thiourea catalyst to report one after another by each research team that and obtained the widespread application in a series of asymmetrical catalytic reaction.
The paper divided into three parts, the paper first part summarized the research development which was asymmetrical catalyzes, particularly thiourea catalyst and bifunctional thiourea catalyst, in was asymmetrical catalyzes the research development. The second part is the catalyst design and the synthesis. Third part of catalytic reaction discussion use synthesis catalyst (Ⅰ、Ⅱ、Ⅲ、Ⅳ、Ⅴ、Ⅵ) attempts some common substrates the asymmetrical Michael addition reaction.
The paper first part summarized the research development of asymmetrical catalyzes. Include: study the importance of asymmetric synthesis、Asymmetric synthesis asymmetric catalysis is the ultimate goal、Separate Of Asymmetric catalysis and advantage of small organic molecules catalysis、Develop of asymmetric organic catalytic、the Mechanism of small Organic molecule catalytic、classification of Organic small molecule catalyst and typical catalyst small organic molecules、Typical small organic molecules catalyst a number of reactions. Second part was chiral thiourea organic small molecule catalyst research and application.
Third, dual-function thiourea catalyst of organic catalytic asymmetric organic reactions is reviewed. Include: thiourea - tertiary type of organic bifunctional thiourea catalyst thiourea - Base Bifunctional Cinchona Thiourea-based organic catalyst, thiourea - primary amine bifunctional catalysts of the organic thiourea, thiourea - Chung bifunctional organic amine thiourea catalyst for disulfide of thiourea-based bifunctional thiourea organic catalyst, organic bifunctional thiourea catalyst for catalytic asymmetric Friedel-Crafts alkylation reaction of organic bifunctional thiourea catalyst for asymmetric Henry Reaction (Nitro aldol reaction), dual function of the organic thiourea other asymmetric catalytic reactions
The second part is the catalyst design and the synthesis. The design synthesized L-(+)- tartaric acid which by the small advantage, easy to result in is a raw material, after the esterification, ring closing reaction , grignard reaction , Chloro-Substituted, azide substitution,reduction and so on 7 step reactions has obtained (Ⅰ,Ⅱ,Ⅲ) three new by TADDAMIN ((4S,5S) - 2,2- dimethyl–α,α,α',α'- four benzyl - 1,3- dioxolane - 4,5- dimethylamine) are skeleton's chiral primary amine - thiourea catalysts. Take ((4R,5S) - 5- (amidogen - diphenyl - methyl) - 2,2- dimethyl -α,α, - diphenyl - 1,3- dioxolane - 4- methyl alcohol) as skeleton's thiourea catalyst (Ⅳ). And take (R,R)-1,2- diaminocyclohexane (DACH) as Chiral skeleton one end bonding with the proline by amide linkage, other end forms the thiourea the catalyst (Ⅵ) .Simultaneously also synthesized one kind already the thiourea - tertiary amine catalyst which reported (Ⅴ).
The third part of catalytic reaction discussion, has attempted them in the catalyzedβ-Nitrostyrene and diethyl malonate,β-Nitrostyrene and Ketone Michael addition reaction, Cinnamate and nitromethane Michael addition reaction, Chalcone and nitromethane Michael addition reaction, Chalcone and p-Methoxyaniline aza-Michael addition reaction. But the catalyst does not have catalytic effect through the catalyst structure's analysis, we speculated that catalysts has not catalytic effect possibly is because take TADDAMIN as skeleton's catalysts and the diaminocyclohexane (DACH) skeleton's catalysts, compares among the TADDAMIN skeleton chiral carbon and the amine group also some carbon atom, the cause chiral center and the primary amine group and the thiourea groups space length is too big, when activates the substrate the two lack some kind of synergism. Need to try a new reaction system. And studies the catalyst the structure, the solvent effect, the temperature, the catalyst amount used and the reaction substrate type to the stereoselective influence, selects the suitable catalyst and the optimized reaction condition.
Catalyst (Ⅵ) catalyzes 4-Nnitrobenzaldhyde and acetone aldol reaction. CatalystⅥcatalyzed 4-Nnitrobenzaldhyde and acetone aldol reaction has the catalytic activity possibly is because the catalyst includes the proline groups and bases. Compare CatalystⅥcatalyzed 4-Nnitrobenzaldhyde and acetone aldol reaction with L-Proline catalyzes 4-Nnitrobenzaldhyde and acetone aldol reaction the merit is the catalystⅥSoluble relative L-Proline has the improvement, the shortcoming is yield only then 22%, but literature [15] report L-Proline (30 mol%) catalyzes yield reach 68%, but also needs to continue to choose the appropriate system.
In recent years, more and more scholars come to study on asymmetric organic reaction catalyzed by small organic molecule catalysts containing thiourea group(s). Rely on the structures containing N-H groups is apt to form dual Intermolecular hydrogen bonds with multiple substrates to achieve good catalytic activity and control of chiral.studies on and applications of asymmetric organic reaction catalyzed by thiourea catalysts have been regarded as one of the most remarkable fields in catalytic asymmetric reactions .Since 1998 the Jacobsen research team's pioneering work, had many applies with the amino acid skeleton connected urea/thiourea chiral catalyst in many kinds of asymmetrical reaction and has realized the very good Stereoselectivity. With the development of small organic molecule catalysts, Chemists began to simulate the structure and characteristics of enzymes which have multi- activation center and these activation centers compose suitable spatial structure and urge catalytic reaction to become more efficient. Receives the enzyme the structure inspiration, in 2003, Takemoto research team's proposed for the first time the single molecular double activation concept, and designed and synthesized bifunctional thiourea-tertiary amine catalyst, introduced other activating group during introduction thiourea groups and introduction another activation in another end (chiral amine) to form double functionalization double activation catalyst, enhances reaction activity and stereo selective greatly. Hereafter a series of includes each kind of chiral skeleton's bifunctional thiourea catalyst to report one after another by each research team that and obtained the widespread application in a series of asymmetrical catalytic reaction.
The paper divided into three parts, the paper first part summarized the research development which was asymmetrical catalyzes, particularly thiourea catalyst and bifunctional thiourea catalyst, in was asymmetrical catalyzes the research development. The second part is the catalyst design and the synthesis. Third part of catalytic reaction discussion use synthesis catalyst (Ⅰ、Ⅱ、Ⅲ、Ⅳ、Ⅴ、Ⅵ) attempts some common substrates the asymmetrical Michael addition reaction.
The paper first part summarized the research development of asymmetrical catalyzes. Include: study the importance of asymmetric synthesis、Asymmetric synthesis asymmetric catalysis is the ultimate goal、Separate Of Asymmetric catalysis and advantage of small organic molecules catalysis、Develop of asymmetric organic catalytic、the Mechanism of small Organic molecule catalytic、classification of Organic small molecule catalyst and typical catalyst small organic molecules、Typical small organic molecules catalyst a number of reactions. Second part was chiral thiourea organic small molecule catalyst research and application.
Third, dual-function thiourea catalyst of organic catalytic asymmetric organic reactions is reviewed. Include: thiourea - tertiary type of organic bifunctional thiourea catalyst thiourea - Base Bifunctional Cinchona Thiourea-based organic catalyst, thiourea - primary amine bifunctional catalysts of the organic thiourea, thiourea - Chung bifunctional organic amine thiourea catalyst for disulfide of thiourea-based bifunctional thiourea organic catalyst, organic bifunctional thiourea catalyst for catalytic asymmetric Friedel-Crafts alkylation reaction of organic bifunctional thiourea catalyst for asymmetric Henry Reaction (Nitro aldol reaction), dual function of the organic thiourea other asymmetric catalytic reactions
The second part is the catalyst design and the synthesis. The design synthesized L-(+)- tartaric acid which by the small advantage, easy to result in is a raw material, after the esterification, ring closing reaction , grignard reaction , Chloro-Substituted, azide substitution,reduction and so on 7 step reactions has obtained (Ⅰ,Ⅱ,Ⅲ) three new by TADDAMIN ((4S,5S) - 2,2- dimethyl–α,α,α',α'- four benzyl - 1,3- dioxolane - 4,5- dimethylamine) are skeleton's chiral primary amine - thiourea catalysts. Take ((4R,5S) - 5- (amidogen - diphenyl - methyl) - 2,2- dimethyl -α,α, - diphenyl - 1,3- dioxolane - 4- methyl alcohol) as skeleton's thiourea catalyst (Ⅳ). And take (R,R)-1,2- diaminocyclohexane (DACH) as Chiral skeleton one end bonding with the proline by amide linkage, other end forms the thiourea the catalyst (Ⅵ) .Simultaneously also synthesized one kind already the thiourea - tertiary amine catalyst which reported (Ⅴ).
The third part of catalytic reaction discussion, has attempted them in the catalyzedβ-Nitrostyrene and diethyl malonate,β-Nitrostyrene and Ketone Michael addition reaction, Cinnamate and nitromethane Michael addition reaction, Chalcone and nitromethane Michael addition reaction, Chalcone and p-Methoxyaniline aza-Michael addition reaction. But the catalyst does not have catalytic effect through the catalyst structure's analysis, we speculated that catalysts has not catalytic effect possibly is because take TADDAMIN as skeleton's catalysts and the diaminocyclohexane (DACH) skeleton's catalysts, compares among the TADDAMIN skeleton chiral carbon and the amine group also some carbon atom, the cause chiral center and the primary amine group and the thiourea groups space length is too big, when activates the substrate the two lack some kind of synergism. Need to try a new reaction system. And studies the catalyst the structure, the solvent effect, the temperature, the catalyst amount used and the reaction substrate type to the stereoselective influence, selects the suitable catalyst and the optimized reaction condition.
Catalyst (Ⅵ) catalyzes 4-Nnitrobenzaldhyde and acetone aldol reaction. CatalystⅥcatalyzed 4-Nnitrobenzaldhyde and acetone aldol reaction has the catalytic activity possibly is because the catalyst includes the proline groups and bases. Compare CatalystⅥcatalyzed 4-Nnitrobenzaldhyde and acetone aldol reaction with L-Proline catalyzes 4-Nnitrobenzaldhyde and acetone aldol reaction the merit is the catalystⅥSoluble relative L-Proline has the improvement, the shortcoming is yield only then 22%, but literature [15] report L-Proline (30 mol%) catalyzes yield reach 68%, but also needs to continue to choose the appropriate system.
引文
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