金配合物催化炔基官能化促发的不对称串联环化反应
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摘要
杂环骨架广泛存在于一些具有生物活性的天然产物、医药及其它一些功能分子中。因此,杂环化合物的合成在有机合成中占有非常重要的地位。而串联反应从简单分子出发,经过“一锅”多步化学反应合成结构复杂的分子,操作简便、合成效率高,因此受到越来越多的关注。近些年,金配合物作为一类新型有效的催化剂,可以催化多种化学反应。尤其是作为π-路易斯酸广泛应用于活化碳-碳三键继而使其发生一系列亲核加成反应,在催化化学及有机合成化学领域中日渐重要而获得高度关注。
本文研究了金配合物催化烯炔醇环化异构形成的氧杂环状双烯中间体,既可作为双烯体与贫电子亲双烯体进行常规Diels-Alder反应,也可作为亲双烯体与a,p-不饱和羰基化合物进行氧杂Diels-Alder反应。其中常规Diels-Alder反应的可以优良的收率“一锅”合成一类氧杂[2,2,2]多环化合物,此类化合物不易通过传统的化学方法制备；而氧杂Diels-Alder反应的可产生二氢吡喃并γ-内酯类双环化合物,另外,使用手性铜配合物与金配合物协同催化串联环化异构-氧杂Diels-Alder反应,可高对映选择性地合成二氢吡喃并γ-内酯类双环化合物。
通过手性金配合物催化2-炔基苯硼酸的环化异构-胺化串联反应,立体选择性地合成了一种具有C-N手性轴的新型阻旋异构体。用(R)-BINAP(AuCl)2和AgNTf2催化2-炔基苯硼酸和偶氮二羧酸酯的不对称环化异构-胺化串联反应,以最高88%的收率和91%ee的对映选择性合成了一系列含有B-O杂芳环的阻旋异构体。此串联反应底物适用范围广,产物的轴手性在室温下相对稳定。通过X-射线单晶衍射分析确定了此类化合物的结构,并借助振动圆二色谱(VCD)技术确定了其绝对构型。
Heterocyclic structural skeletons are prevalent in biologically active natural products, Pharmaceuticals, organic materials and numerous functional molecules. Therefore, the development of new synthetic methods to directly access heterocycles is of greatly synthetic importance. Cascade or domino reactions, because they are able to build up structurally complex molecules from relatively simpler substrates, have received increasing attention. In recent years, the gold catalysis has allowed a variety of cascade reactions, some of which were capable of efficiently accessing structurally complex heterocycles. Most importantly, the gold complexes, as strong π-Lewis acids, are able to catalyze the addition of nucleophiles to carbon-carbon triple bond very efficiently and have drawn more attention.
The1,3-butadiene derivatives, generated from the cycloisomerization of enyne alcohols catalyzed by an appropriate gold complex, was able to participate in either the Diels-Alder reaction as dienes or the inverse-electron-demand hetero-Diels-Alder reaction as dieneophiles. The oxa-bridged [2,2,2] multiply cyclic compounds, which would be difficult to be accessed by a traditional transformation, have been obtained by the cascade cycloisomerization-Diels-Alder reaction in one-pot. In addition, the dihydropyrano-y-lactone derivatives could be accessed by the cycloisomerization-hetero-Diels-Alder reaction. Besides, the asymmetric synthesis of dihydropyrano-y-lactone derivatives was achieved with high enantioselectivity by using copper complex in combination with the gold complex.
We have established a chiral gold (I) complex-catalyzed enantioselective cycloisomerization-amination csacde of2-(alkynyl)phenyl boronic acids with diazenes, leading to a family of unprecedented chiral molecules, heteroaryl atropisomers involving B-O bond. The atropisomers were obtained in up to89%yield and up to91%ee by using (R)-BINAP(AuNTf2)2as catalyst generated in situ from (R)-BINAP(AuCl)2and AgNTf2. The protocol tolerated a wide scope of substrates bearing various functional groups and the chirality of such atropisomers is relatively stable at room temperature.The structure was determined by X-ray diffraction and the configuration of the novel chiral C-N axis was tentatively assigned by vibrational circular dichroism (VCD) calculation.
本文研究了金配合物催化烯炔醇环化异构形成的氧杂环状双烯中间体,既可作为双烯体与贫电子亲双烯体进行常规Diels-Alder反应,也可作为亲双烯体与a,p-不饱和羰基化合物进行氧杂Diels-Alder反应。其中常规Diels-Alder反应的可以优良的收率“一锅”合成一类氧杂[2,2,2]多环化合物,此类化合物不易通过传统的化学方法制备；而氧杂Diels-Alder反应的可产生二氢吡喃并γ-内酯类双环化合物,另外,使用手性铜配合物与金配合物协同催化串联环化异构-氧杂Diels-Alder反应,可高对映选择性地合成二氢吡喃并γ-内酯类双环化合物。
通过手性金配合物催化2-炔基苯硼酸的环化异构-胺化串联反应,立体选择性地合成了一种具有C-N手性轴的新型阻旋异构体。用(R)-BINAP(AuCl)2和AgNTf2催化2-炔基苯硼酸和偶氮二羧酸酯的不对称环化异构-胺化串联反应,以最高88%的收率和91%ee的对映选择性合成了一系列含有B-O杂芳环的阻旋异构体。此串联反应底物适用范围广,产物的轴手性在室温下相对稳定。通过X-射线单晶衍射分析确定了此类化合物的结构,并借助振动圆二色谱(VCD)技术确定了其绝对构型。
Heterocyclic structural skeletons are prevalent in biologically active natural products, Pharmaceuticals, organic materials and numerous functional molecules. Therefore, the development of new synthetic methods to directly access heterocycles is of greatly synthetic importance. Cascade or domino reactions, because they are able to build up structurally complex molecules from relatively simpler substrates, have received increasing attention. In recent years, the gold catalysis has allowed a variety of cascade reactions, some of which were capable of efficiently accessing structurally complex heterocycles. Most importantly, the gold complexes, as strong π-Lewis acids, are able to catalyze the addition of nucleophiles to carbon-carbon triple bond very efficiently and have drawn more attention.
The1,3-butadiene derivatives, generated from the cycloisomerization of enyne alcohols catalyzed by an appropriate gold complex, was able to participate in either the Diels-Alder reaction as dienes or the inverse-electron-demand hetero-Diels-Alder reaction as dieneophiles. The oxa-bridged [2,2,2] multiply cyclic compounds, which would be difficult to be accessed by a traditional transformation, have been obtained by the cascade cycloisomerization-Diels-Alder reaction in one-pot. In addition, the dihydropyrano-y-lactone derivatives could be accessed by the cycloisomerization-hetero-Diels-Alder reaction. Besides, the asymmetric synthesis of dihydropyrano-y-lactone derivatives was achieved with high enantioselectivity by using copper complex in combination with the gold complex.
We have established a chiral gold (I) complex-catalyzed enantioselective cycloisomerization-amination csacde of2-(alkynyl)phenyl boronic acids with diazenes, leading to a family of unprecedented chiral molecules, heteroaryl atropisomers involving B-O bond. The atropisomers were obtained in up to89%yield and up to91%ee by using (R)-BINAP(AuNTf2)2as catalyst generated in situ from (R)-BINAP(AuCl)2and AgNTf2. The protocol tolerated a wide scope of substrates bearing various functional groups and the chirality of such atropisomers is relatively stable at room temperature.The structure was determined by X-ray diffraction and the configuration of the novel chiral C-N axis was tentatively assigned by vibrational circular dichroism (VCD) calculation.
引文
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