摘要
氧化偶联反应是指通过氧化剂作用下氧化切断化学键,然后实现官能团化,从而构建新的碳-碳键和碳-杂原子键等化学键的的方法和技术。氧化偶联反应的反应条件为中性,切断的化学键包括碳-氢键以及杂原子-氢键等。其中碳-氢键氧化切断的氧化偶联反应已成为有机化学研究的热点领域。其原因是碳-氢键氧化切断直接官能团可以避免使用预先官能团化的反应物,原子经济性高,对环境友好。因此,通过碳-氢键氧化切断的氧化偶联反应对构建天然产物和先导药物骨架,或对药物先导化合物直接修饰,实现活性化合物的多样性合成以及药物分子的高通量筛选无疑具有重要意义和研究价值。
铜催化剂是一种价廉易得的催化剂,已广泛应用于有机合成中。使用铜催化剂来催化氧化偶联反应即是有机合成研究热点也是最具挑战性领域之一。在铜催化剂催化氧化偶联反应研究中,如何提高铜催化剂的催化活性成为该研究的关键。
本论文主要研究了铜催化酮或酸氧化偶联反应及苯并异吡喃环化反应。本论文主要包括如下内容:
(1)首先对近年来铜催化氧化偶联反应的研究进展进行了详细评述。主要从构建不同化学键方面进行综合评述,包括三方面:(i)铜催化氧化偶联反应构建碳-碳键的研究进展;(ii)铜催化氧化偶联反应构建碳-氮键的研究进展;(iii)铜催化氧化偶联反应构建碳-氧键和其它化学键的研究进展。主要集中对铜催化氧化偶联反应的研究内容和机理进行了描述和探讨。
(2)发现了一种高效的铜催化酮与TEMPO的α-羟胺化反应,合成出一些天产物和药物的基本骨架部分的2-芳氧基2-(2,2,6,6-四甲基哌啶-1-氧化物)乙酮化合物,产率中等到高。值得指出的是,使用的铜包铁催化剂(Cu/Fe)可以回收重复使用多次,仍具有好的催化活性。该方法是一种新的铜催化酮的α-羟胺化反应。产物,2-芳氧基2-(2,2,6,6-四甲基哌啶-1-氧化物)乙酮化合物,很容易转化为芳基二羰基化合物,该二羰基化合物同样是一种重要的有机合成砌块,例如合成脱氧酮糖酸类化合物。
(3)以铜为催化剂,在DABCO配体和TBHP氧化剂的协助下,实现了酸与甲酰胺或乙酰胺的氧化酰胺化反应。该反应适合酸的范围广,包括烷基酸、芳基酸、a,β-不饱和酸和氨基酸等。最为重要的是,该方法使用甲酰胺或乙酰胺作为氨基来源,与酸反应合成一系列新的酰胺,为有机合成和工业原料的酰胺的合成提供了一种新途径。
(4)建立了一种Lewis酸催化的环化反应合成苯并环庚[b]吲哚化合物。该方法是一类构建七元碳环的新策略,反应中使用铜催化剂,两分子的苯并异毗喃为反应底物。还尝试了将产物苯并环庚[b]吲哚化合物应用于荧光材料,发现苯并环庚[b]吲哚化合物可以作为一些金属离子例如汞离子的荧光探针。
(5)砜官能团是许多有机材料、活性分子和药物的重要骨架,也是有机合成的重要中间体。发现了一种新的简单的反应,即在碱作用下酮与1,2-二苯基砜乙烷的亲核取代反应,合成出1-芳基-4-苯基砜基丁-1-酮化合物。该方法是一类新型的合成官能团化砜化合物反应,使用商业化1,2-二苯基砜乙烷产品替代烯基砜作为砜官能团的来源,从而将羰基化合物底物拓宽到普通酮化合物。
The oxidative coupling reaction includes the oxidative cleavage of chemical bonds by oxidants, followed by functionalization to construct various chemical bonds, such as new carbon-carbon bonds and carbon-heteroatom bonds. The oxidative coupling reactions are generally used to cleave the carbon-carbon bonds and carbon-heteroatom bonds under neutral reaction conditions. Particularly, the oxidative coupling reactions through the carbon-hydrogen bond cleavage are the hot-topic in organic synthesis because they do not need per-functionalization substrates with high atom-economy and benign-environment. For these reasons, the utilizations of the oxidative coupling reactions in the synthesis of natual products and lead drug frameworks are high desirable.
Copper catalysts, expensive catalysts, are widely used in organic synthesis. Recently, copper-catalyzed oxidative coupling reactions have been one of the the most important and challenging areas in organic synthesis. Among these reactions, the key is how to improve the catalytic activities of copper catalysts.
The dissertation mainly studies on the copper-catalyzed oxidative coupling reactions of ketones or acids and annulation of isochromenes. The contents of this dissertation are as following:
(1) Recent progress in the copper-catalyzed oxidative coupling reactions has been described in detail. Three parts on the construction of chemical bonds are discussed in this chapter, including:(i) Advances in the construction of the carbon-carbon bonds by copper-catalyzed oxidative coupling reactions,(ii) advances in the construction of the carbon-nitrogen bonds by copper-catalyzed oxidative coupling reactions, and (iii) advances in the construction of the carbon-oxygen bonds and the other chemical bonds by copper-catalyzed oxidative coupling reactions. We focus on the results and the mechanisms of the copper-catalyzed oxidative coupling reactions.
(2) An efficient copper-catalyzed α-aminoxylation of ketones with TEMPO was presented for the synthesis of2-aryloxy-1-aryl-2-(2,2,6,6-tetramethylpiperidin-1-yloxy)ethanones, fundamental structural units that are found in natural products and pharmaceutical agents, in moderate to excellent yields. It is noteworthy that the Cu/Fe catalyst can be recovered and reusable several times with highly catalytic activity, and this method is the first example for the Cu-catalyzed oxyamination reaction of ketones with TEMPO. Importantly, the products,2-aryloxy-1-aryl-2-(2,2,6,6-tetramethyl-piperidin-1-yloxy)ethanones, can readily deliver aryl glyoxylates, which play an important role in biological processes as useful intermediates in the synthesis of some natural products, such as the3-deoxy-2-ulosonic acids and their derivatives.
(3) A new, general copper-catalyzed amidation of acids with formamides or acetamide to selective synthesize new amides with the aid of DAB CO ligand and TBHP oxidation is presented. This method has high compatibility with a wide range of acids, including alkyl acids, aryl acids, α,β-unsaturated acids and amino acids. Importantly, this method allows the use of various formamides and an acetamide as the amine resources for amidation with acids leading to new amide products, which open a new door to use acids for the direct synthesis of amides, a class of fundamental chemicals in organic synthesis and chemical industries.
(4) A novel Lewis acid-catalyzed annulation reaction has been established for the synthesis of benzocyclohepta[b]indoles. This method represents a new annulation strategy to a seven-membered carbocyclic ring system from two3-(1H-isochromen-1-yl)-1H-indole molecules using Cu(OTf)2catalyst; moreover, the products, benzocyclohepta[b]indoles, can be used as the rapid mercuric ion colorimetric detection reagents.
(5) Sulfones are important units found in organic materials, bioactive molecules and pharmaceuticals, as well as widely serve as valuable intermediates in synthetic chemistry. A new, simple base-mediated nucleophilic replacement reaction of1,2-bis(phenylsulfonyl)ethane with ketones has been developed for the synthesis of1-aryl-4-(phenylsulfonyl)butan-1-ones. This method represents the first example of preparing new functionalized sulfones using commercial available1,2-bis(phenylsulfonyl)ethane instead of vinyl sulfones as the sulfone resource, and expands the scope to common ketones.
引文
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[99]Tang R.-Y., Li J.-H. PdC12-Cataylzed Domino Reactions of 2-Alkynylbenzaldehydes with Indoles:Synthesis of Fluorescent 5H-Benzo[b]carbazol-6-yl Ketones, Chem. Eur. J.2010,16 (16),4733-4738.
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