非均相酸碱催化剂协同催化Aldol反应
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摘要
酸碱协同作用普遍存在于酶和抗体的催化过程中。生物催化剂的这个特点激励着化学工作者不断追求合成新的酸碱双功能或多功能催化剂。这类催化剂具有催化活性和立体选择性高、反应条件温和、无需引入金属等优点。从实际应用的角度考虑,为了降低成本,则希望这些多功能分子,尤其是那些需要多步合成才能得到的催化剂能够被固载,以便于回收、重复使用和方便产品纯化。不对称aldol反应是最常见的C-C键形成的反应之一,广泛应用于合成天然或非天然产物。本文以酸碱双功能化的有机-无机介孔材料为基础,以aldol反应为模型反应,系统研究了酸碱基团的类型、空间位阻、相对位置以及不同载体对催化性能的影响。主要研究内容包括:
通过后接枝的方法将大位阻有机碱TBD(1,5,7-triazabicyclo[4.4.0]dec-5-ene,碱性与KOH相当)固载于Al-MCM-41分子筛表面,合成了一种新型的含有骨架酸性位和表面碱性位的双功能介孔催化剂。因为空间位阻的影响,骨架上的酸性中心和表面的碱性中心避免了相互中和,实现了“性质相反试剂”在同一体系内的和平共存。酸碱活性中心在表面的分布克服了彼此之间距离的限制,不会因为距离太近而相互中和。这种酸碱双功能催化剂能够有效协同催化丙酮与对硝基苯甲醛的aldol反应。
使用接枝的方法将含有脲和氨基的有机双功能分子负载于介孔材料表面,合成了既有酸性中心又有碱性中心的双功能多相催化剂。研究发现,不同类型活性基团和它们的相对位置都会对催化活性产生很大影响。在aldol反应中,双功能催化剂的酸性基团(脲)与碱性基团(伯胺)处于一个合适的位置具有最好的催化活性。
将烷基化的手性环己二胺使用后接枝的方法固载到多孔材料表面,通过质子酸的加入,得到了一种具有伯胺和弱质子酸的双功能多相介孔催化剂。这类双功能催化剂可以有效的催化丙酮与对硝基苯甲醛的不对称aldol反应。碱性中心的空间位阻对催化剂的对映体选择性影响较小,而酸性中心的空间位阻对于底物的手性诱导是至关重要的。将手性环己二胺通过共价键分别固载在不同孔径的分子筛孔道内,得到了一系列有机-无机混合催化剂。因为纳米孔的孔道限制效应,适当的孔径可以提高催化剂在不对称aldol反应中的对映体选择性,其中,以大孔径SBA-15分子筛为载体时,所得产物的对映体过量值最高。
Acid-base cooperativity is commonly invoked in enzymatic and catalytic antibody catalysis.This paradigm of biological catalysis has inspired the synthesis of bifunctional catalysts with superior activity and selectivity,including enantioselectivity.Small molecular bifunctional organocatalyst imitated enzyme,especially with L-proline and its derivatives has attracted extensive research activities and experienced a huge development.The main advantages of these catalysts are that the reaction can be performed with excellent stereoselectivity under mild conditions.From a practical point of view,it would be desirable to have the catalyst immobilized so that its recovery,reuse and product purification can be facilitated in order to reduce costs,especially when the catalyst is obtained after several synthetic steps.The direct catalytic asymmetric aldol reaction is a highly versatile and powerful C-C bond forming reaction and has been widely used in constructing natural and nonnatural products.
In this dissertation,we demonstrate the synthesis of bifunctional mesoporous catalysts containing an acidic site in the framework and a basic site on the porous surface by postgrafting of 1,5,7-triazabicyclo[4.4.0]dec-5-ene(TBD,a sterically hindered organic base with comparable strength to KOH) onto Al-MCM-41 molecular sieve.Al-MCM-41 usually has relatively weaker Brφnsted acid sites and stronger Lewis acid sites.Because of the space hindrance between the acidic sites in the framework and the immobilized TBD base sites, they can cohabit independently without mutual destruction.Therefore,a cooperative catalysis originated from the acidic and basic sites of the bifunctional heterogeneous catalyst shows an acid-base cooperativity in catalyzing the aldol condensation of acetone and various aldehydes to selectively giveβ-hydroxycarbonyl compounds.
The binary catalyst system,consisting of the double hydrogen-bonding of urea as acidic center and primary amine of phenylene diamine as basic center within same a molecule,can effectively catalyze the aldol reaction of actone with p-nitrobenzaldehyde.We have demonstrated that a general acid group,urea,can activate substrates in cooperation with a general base group,primary amine,to catalyze aldol reaction that involve carbonyl activation. By fine-tuning the relative position and proper spatial arrangement of different cooperative functional groups,the functional catalysts could effectively catalyze in the aldol reaction of actone with p-nitrobenzaldehyde catalyzed by bifunctional solid catalyst.The high TOF value indicates a genuine and superior catalytic performance in comparison with those of other bifunctional catalysts between different molecules.
We demonstrate the synthesis of bifunctional mesoporous catalysts containing a simple chiral primary-tertiary diamine/Brφnsted acid conjugates in combination with on the porous surface by postgrafting of chiral trans-N,N-dialkylated diaminocyclohexanes onto mesoporous materials.The bifunctional catalysts can catalyze effectively the asymmetric aldol reaction of acetone with various aldehydes.A confinement effect originating from mesoporous was observed in this reaction.The organic-inorganic hybrid catalysts were synthesized by covalent anchoring of chiral diamine in the nanopores of MCM-41 and SBA-15.Modified SBA-15 catalyst obtained higher ee value than that obtained for the same catalysts anchored on the silica gel and MCM-41.Because of the confinement effect of the nanopores,the enantioselectivity increase with increasing of nanopore size in the asymmetric aldol reaction.
通过后接枝的方法将大位阻有机碱TBD(1,5,7-triazabicyclo[4.4.0]dec-5-ene,碱性与KOH相当)固载于Al-MCM-41分子筛表面,合成了一种新型的含有骨架酸性位和表面碱性位的双功能介孔催化剂。因为空间位阻的影响,骨架上的酸性中心和表面的碱性中心避免了相互中和,实现了“性质相反试剂”在同一体系内的和平共存。酸碱活性中心在表面的分布克服了彼此之间距离的限制,不会因为距离太近而相互中和。这种酸碱双功能催化剂能够有效协同催化丙酮与对硝基苯甲醛的aldol反应。
使用接枝的方法将含有脲和氨基的有机双功能分子负载于介孔材料表面,合成了既有酸性中心又有碱性中心的双功能多相催化剂。研究发现,不同类型活性基团和它们的相对位置都会对催化活性产生很大影响。在aldol反应中,双功能催化剂的酸性基团(脲)与碱性基团(伯胺)处于一个合适的位置具有最好的催化活性。
将烷基化的手性环己二胺使用后接枝的方法固载到多孔材料表面,通过质子酸的加入,得到了一种具有伯胺和弱质子酸的双功能多相介孔催化剂。这类双功能催化剂可以有效的催化丙酮与对硝基苯甲醛的不对称aldol反应。碱性中心的空间位阻对催化剂的对映体选择性影响较小,而酸性中心的空间位阻对于底物的手性诱导是至关重要的。将手性环己二胺通过共价键分别固载在不同孔径的分子筛孔道内,得到了一系列有机-无机混合催化剂。因为纳米孔的孔道限制效应,适当的孔径可以提高催化剂在不对称aldol反应中的对映体选择性,其中,以大孔径SBA-15分子筛为载体时,所得产物的对映体过量值最高。
Acid-base cooperativity is commonly invoked in enzymatic and catalytic antibody catalysis.This paradigm of biological catalysis has inspired the synthesis of bifunctional catalysts with superior activity and selectivity,including enantioselectivity.Small molecular bifunctional organocatalyst imitated enzyme,especially with L-proline and its derivatives has attracted extensive research activities and experienced a huge development.The main advantages of these catalysts are that the reaction can be performed with excellent stereoselectivity under mild conditions.From a practical point of view,it would be desirable to have the catalyst immobilized so that its recovery,reuse and product purification can be facilitated in order to reduce costs,especially when the catalyst is obtained after several synthetic steps.The direct catalytic asymmetric aldol reaction is a highly versatile and powerful C-C bond forming reaction and has been widely used in constructing natural and nonnatural products.
In this dissertation,we demonstrate the synthesis of bifunctional mesoporous catalysts containing an acidic site in the framework and a basic site on the porous surface by postgrafting of 1,5,7-triazabicyclo[4.4.0]dec-5-ene(TBD,a sterically hindered organic base with comparable strength to KOH) onto Al-MCM-41 molecular sieve.Al-MCM-41 usually has relatively weaker Brφnsted acid sites and stronger Lewis acid sites.Because of the space hindrance between the acidic sites in the framework and the immobilized TBD base sites, they can cohabit independently without mutual destruction.Therefore,a cooperative catalysis originated from the acidic and basic sites of the bifunctional heterogeneous catalyst shows an acid-base cooperativity in catalyzing the aldol condensation of acetone and various aldehydes to selectively giveβ-hydroxycarbonyl compounds.
The binary catalyst system,consisting of the double hydrogen-bonding of urea as acidic center and primary amine of phenylene diamine as basic center within same a molecule,can effectively catalyze the aldol reaction of actone with p-nitrobenzaldehyde.We have demonstrated that a general acid group,urea,can activate substrates in cooperation with a general base group,primary amine,to catalyze aldol reaction that involve carbonyl activation. By fine-tuning the relative position and proper spatial arrangement of different cooperative functional groups,the functional catalysts could effectively catalyze in the aldol reaction of actone with p-nitrobenzaldehyde catalyzed by bifunctional solid catalyst.The high TOF value indicates a genuine and superior catalytic performance in comparison with those of other bifunctional catalysts between different molecules.
We demonstrate the synthesis of bifunctional mesoporous catalysts containing a simple chiral primary-tertiary diamine/Brφnsted acid conjugates in combination with on the porous surface by postgrafting of chiral trans-N,N-dialkylated diaminocyclohexanes onto mesoporous materials.The bifunctional catalysts can catalyze effectively the asymmetric aldol reaction of acetone with various aldehydes.A confinement effect originating from mesoporous was observed in this reaction.The organic-inorganic hybrid catalysts were synthesized by covalent anchoring of chiral diamine in the nanopores of MCM-41 and SBA-15.Modified SBA-15 catalyst obtained higher ee value than that obtained for the same catalysts anchored on the silica gel and MCM-41.Because of the confinement effect of the nanopores,the enantioselectivity increase with increasing of nanopore size in the asymmetric aldol reaction.
引文
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