手性布朗斯特酸催化硝基烯烃不对称傅克烷基化反应研究
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摘要
傅克烷基化反应是对芳香化合物衍生化的最为有效的方法之一,而不对称傅克烷基化反应则提供了合成手性芳基衍生物的直接途径。本论文主要研究了手性布朗斯特酸催化硝基烯烃的不对称傅克反应,分为以下四部分。
第一部分,阐述了不对称催化反应的重要性并综述了近年来有机小分子催化的不对称傅克烷基化反应的进展。
第二部分,设计并合成了一类基于樟脑骨架的新型硫脲催化剂,并对其催化硝基烯烃的不对称傅克烷基化反应进行了研究,实现了吲哚与硝基烯烃的不对称傅克烷基化反应。
第三部分,研究了手性磷酸催化的硝基烯烃与4,7-二氢吲哚的不对称傅克烷基化反应。在低催化剂量(0.5mol%)条件下,实现了手性磷酸催化4,7-二氢吲哚与硝基烯烃反应并以高产率和优秀对映选择性(最高可以达97%ee)得到加成产物,反应均能在2小时内反应完全。此外,还实现了高对映选择性一锅法合成2位取代的吲哚衍生物,为合成2位取代的吲哚衍生物提供了一种高效简便的合成方法。
第四部分工作,发现在5mol%手性磷酸催化下,也能高效的实现吡咯同硝基烯烃的不对称傅克烷基化反应,并对该反应进行了初步研究。
Friedel-Crafts alkylation is one of the most efficient methods for the derivatization of aromatic compounds. Asymmetric Friedel-Crafts alkylation reaction provides direct access to the enantiopure aromatic derivatives. This dissertation is focused on the asymmetric Friedel-Crafts reactions with nitroolefins catalyzed by chiral Br(?)nsted acids. This dissertation consisted of four parts.
In part one, the recent progress in organocatalytic asymmetric Friedel-Crafts reactions is reviewed.
In part two, a class of novel chiral thioures involving camphor framework was designed and synthesized. Their applications in asymmetric Friedel-Crafts reactions of indoles with nitroolefins were studied.
In part three, asymmetric Friedel-Crafts reaction of 4,7-dihydroindoles with nitroolefins was studied. Highly efficient Friedel-Crafts reaction of 4,7-dihydroindoles with nitroolefins by a chiral phosphoric acid was realized. With 0.5 mol% of the catalyst, the reactions were complete in 2 hours at rt to afford the 2-substituted 4,7-dihydroindoles with up to 97% ee. In addition, the 2-substituted indole derivatives could be obtained in one-pot with high enantioselectivities, providing an efficient and simple way to synthesized 2-substituted indole derivatives.
In part four, with 5 mol% of the chiral phosphoric acid, high enantioselectivities of 2-substituted pyrrole could also be obtained via the Friedel-Crafts reaction. The asymmetric Friedel-Crafts reactions of pyrroles with nitroolefins by chiral phosphoric acid is currently undergoing in the lab.
第一部分,阐述了不对称催化反应的重要性并综述了近年来有机小分子催化的不对称傅克烷基化反应的进展。
第二部分,设计并合成了一类基于樟脑骨架的新型硫脲催化剂,并对其催化硝基烯烃的不对称傅克烷基化反应进行了研究,实现了吲哚与硝基烯烃的不对称傅克烷基化反应。
第三部分,研究了手性磷酸催化的硝基烯烃与4,7-二氢吲哚的不对称傅克烷基化反应。在低催化剂量(0.5mol%)条件下,实现了手性磷酸催化4,7-二氢吲哚与硝基烯烃反应并以高产率和优秀对映选择性(最高可以达97%ee)得到加成产物,反应均能在2小时内反应完全。此外,还实现了高对映选择性一锅法合成2位取代的吲哚衍生物,为合成2位取代的吲哚衍生物提供了一种高效简便的合成方法。
第四部分工作,发现在5mol%手性磷酸催化下,也能高效的实现吡咯同硝基烯烃的不对称傅克烷基化反应,并对该反应进行了初步研究。
Friedel-Crafts alkylation is one of the most efficient methods for the derivatization of aromatic compounds. Asymmetric Friedel-Crafts alkylation reaction provides direct access to the enantiopure aromatic derivatives. This dissertation is focused on the asymmetric Friedel-Crafts reactions with nitroolefins catalyzed by chiral Br(?)nsted acids. This dissertation consisted of four parts.
In part one, the recent progress in organocatalytic asymmetric Friedel-Crafts reactions is reviewed.
In part two, a class of novel chiral thioures involving camphor framework was designed and synthesized. Their applications in asymmetric Friedel-Crafts reactions of indoles with nitroolefins were studied.
In part three, asymmetric Friedel-Crafts reaction of 4,7-dihydroindoles with nitroolefins was studied. Highly efficient Friedel-Crafts reaction of 4,7-dihydroindoles with nitroolefins by a chiral phosphoric acid was realized. With 0.5 mol% of the catalyst, the reactions were complete in 2 hours at rt to afford the 2-substituted 4,7-dihydroindoles with up to 97% ee. In addition, the 2-substituted indole derivatives could be obtained in one-pot with high enantioselectivities, providing an efficient and simple way to synthesized 2-substituted indole derivatives.
In part four, with 5 mol% of the chiral phosphoric acid, high enantioselectivities of 2-substituted pyrrole could also be obtained via the Friedel-Crafts reaction. The asymmetric Friedel-Crafts reactions of pyrroles with nitroolefins by chiral phosphoric acid is currently undergoing in the lab.
引文
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