钯催化的吲哚与炔的偶联反应和有机碘试剂作用下对乙酰苯胺乙酰氧化和醚化反应的研究
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摘要
芳香族化合物其在化工和医药中都有着广泛的应用,特别是吲哚和乙酰苯胺类化合物。合成该类化合物的传统反应一般需要特定的催化剂并且是在苛刻的条件下进行的,对环保和经济上都很有局限性;并且有许多的目标化合物需要用好几步才能得到,这样要消耗大量的原料。在最近的二十几年里,交叉偶联反应和氧化反应逐渐成为合成芳香族化合物的重要方法。这些新型的反应使芳香族化合物在直接官能团化方面有了很大的进展,极大的改进了传统合成工艺。通过有机碘试剂氧化作用下的偶联反应来合成芳香类化合物也成为一个新的研究热点。而最近的全合成研究中也大都采用了新型的有机合成策略。鉴于环保,经济以及原子经济性的需求,研究高效、低毒、便宜和环保的新型反应有着重要的意义。
本论文包括三部分,一是在钯催化下的吲哚与炔类化合物直接偶联反应的研究;二是有机碘试剂(PIFA)作用下对乙酰苯胺的乙酰氧化和醚化反应的研究。三是生物碱Sieboldine A和Alopecuridine的全合成骨架模型反应的研究。
报道了以一种高效的Pd催化剂来直接对吲哚进行C-3炔基化的反应。该反应在吲哚未做任何保护和活化的前提下,在比较温和的实验条件下合成了高选择性、高产率的偶联产物。
研究了由乙酰苯胺出发在无任何金属催化剂以及金属氧化剂的存在下,在BF3·OEt2参与下用三氟醋酸碘苯(PIFA)对乙酰苯胺直接进行乙酰氧化和醚化反应,在温和的实验条件下得到高选择性,高产率的目标化合物。并且可以广泛的拓展底物范围:应用同一个反应体系与醇进行醚化反应,也能得到高选择性、高产率的醚化产物。此外,该反应的原子经济性较高,反应体系毒性小,能体现对环境比较友好的特性。
研究了生物碱Sieboldine A和Alopecuridine的骨架模型反应。在对生物碱Sieboldine A和Alopecuridine的全合成研究中将苯环转化成三个并环是非常具有挑战性的,是该全合成的关键。我们采用了设计辅助模型,然后通过尝试不同反应条件将苯环直接转化成三个并环的方式。
Cross-coupling reaction is one the important reactions in organic chemistry. It finds wide applications in chemical engineering and medical syntheses. It is very limited for the traditional synthesis methods due to its specific catalyst and exigent parameter . To meet the requirement of the environmental and economical protection, the study on a high efficiency, low toxic, low price and environmental benign reaction system is of impending importance. Study the new cross-coupling reactions It is a new trend in organic chemistry and a challenging project in the green process for the chemical engineering.
The paper contains three parts, one is Palladium-catalyzed direct C-3 alkynylation of indoles. One is Direct Acetoxylation and Etherification of Anilides using Phenyliodine Bis(trifluoroacetate) (PIFA). The third part is total synthesis of the model molecule of Sieboldine A and Alopecuridine.
Firstly,the direct Palladium-catalyzed coupling reaction of indoles with alkynyl bromide has been developed to produce corresponding 3-alkynylindoles with high regioselectivity and in good to excellent yields under mild conditions.
Secondly, the acetoxylation and etherification of anilides induced by organoiodine(III) oxidant were reported. In the presence of phenyliodine(III) bis(trifluoroacetate) (PIFA) and BF3·OEt2, the reaction of anilides with AcOH or MeOH at the room temperature gave the para-acetoxylated and para-methoxylated products with high regioselectivity in good to excellent yields.
Thirdly, we studied the total synthesis of the model molecule of Sieboldine A and Alopecuridine. We introduced a new model molecule to study the key step of the total synthesis of Sieboldine A and Alopecuridine. And we experimented many different reactions under different conditions.
本论文包括三部分,一是在钯催化下的吲哚与炔类化合物直接偶联反应的研究;二是有机碘试剂(PIFA)作用下对乙酰苯胺的乙酰氧化和醚化反应的研究。三是生物碱Sieboldine A和Alopecuridine的全合成骨架模型反应的研究。
报道了以一种高效的Pd催化剂来直接对吲哚进行C-3炔基化的反应。该反应在吲哚未做任何保护和活化的前提下,在比较温和的实验条件下合成了高选择性、高产率的偶联产物。
研究了由乙酰苯胺出发在无任何金属催化剂以及金属氧化剂的存在下,在BF3·OEt2参与下用三氟醋酸碘苯(PIFA)对乙酰苯胺直接进行乙酰氧化和醚化反应,在温和的实验条件下得到高选择性,高产率的目标化合物。并且可以广泛的拓展底物范围:应用同一个反应体系与醇进行醚化反应,也能得到高选择性、高产率的醚化产物。此外,该反应的原子经济性较高,反应体系毒性小,能体现对环境比较友好的特性。
研究了生物碱Sieboldine A和Alopecuridine的骨架模型反应。在对生物碱Sieboldine A和Alopecuridine的全合成研究中将苯环转化成三个并环是非常具有挑战性的,是该全合成的关键。我们采用了设计辅助模型,然后通过尝试不同反应条件将苯环直接转化成三个并环的方式。
Cross-coupling reaction is one the important reactions in organic chemistry. It finds wide applications in chemical engineering and medical syntheses. It is very limited for the traditional synthesis methods due to its specific catalyst and exigent parameter . To meet the requirement of the environmental and economical protection, the study on a high efficiency, low toxic, low price and environmental benign reaction system is of impending importance. Study the new cross-coupling reactions It is a new trend in organic chemistry and a challenging project in the green process for the chemical engineering.
The paper contains three parts, one is Palladium-catalyzed direct C-3 alkynylation of indoles. One is Direct Acetoxylation and Etherification of Anilides using Phenyliodine Bis(trifluoroacetate) (PIFA). The third part is total synthesis of the model molecule of Sieboldine A and Alopecuridine.
Firstly,the direct Palladium-catalyzed coupling reaction of indoles with alkynyl bromide has been developed to produce corresponding 3-alkynylindoles with high regioselectivity and in good to excellent yields under mild conditions.
Secondly, the acetoxylation and etherification of anilides induced by organoiodine(III) oxidant were reported. In the presence of phenyliodine(III) bis(trifluoroacetate) (PIFA) and BF3·OEt2, the reaction of anilides with AcOH or MeOH at the room temperature gave the para-acetoxylated and para-methoxylated products with high regioselectivity in good to excellent yields.
Thirdly, we studied the total synthesis of the model molecule of Sieboldine A and Alopecuridine. We introduced a new model molecule to study the key step of the total synthesis of Sieboldine A and Alopecuridine. And we experimented many different reactions under different conditions.
引文
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