Palladium in Heterocyclic Chemistry
Palladium in Heterocyclic Chemistry
复制标题
DOI：
10.1055/s-2002-19789
复制
发表时间：
2004-08
期刊：
影响因子：
--
通讯作者：
P. Stevenson
中科院分区：
文献类型：
--
作者：
P. Stevenson
第一章是一个很好的帐户钯催化反应，现在普遍采用的有机合成。这些反应包括氧化偶联、交叉偶联反应、Heck反应、羰基化和胺化。在每种情况下的反应机理进行了详细讨论，概述了这些程序的范围和局限性。对于需要钯0的每个反应类别，尝试描述如何从钯II盐前体产生钯0。这是一个经常在研究论文中被掩盖的主题，我觉得像这样的小接触使化学更吸引那些正在考虑使用钯化学的神秘新手。有很多小块的教条提供，这有助于合理化的多样性化学稍后描述。将卤代乙烯氧化加成的容易性等同于SNAr置换的容易性的类比特别有帮助，这在某种程度上合理化了为什么杂环化合物的行为与碳环如此不同，并允许在随后的章节中确定区域选择性的强大预测工具。各种交叉偶联反应根岸，铃木和斯蒂尔的条件进行了严格的比较和对比，作者给出了一个很好的想法，哪些额外的官能团将生存的条件。决定什么使一个良好的转移基团在交叉耦合的因素进行了讨论，并有许多例子，更困难的交叉耦合反应涉及的烷基基团在整个文本。关于赫克反应的介绍部分非常出色。鉴于Heck反应通常不产生手性中心，我认为提供的关于新兴不对称Heck反应的背景信息比给出的一段更有价值。钯化学的10个杂环类，即吡咯，吲哚，吡啶，噻吩，呋喃，噻唑，oxaozoles，咪唑，吡嗪，和嘧啶都涵盖在自己的章节。每一章都有相同的风格，一个天然存在的杂环的介绍，然后是一个合成的活性杂环化合物的清单，并简要描述了它们的药用特性。新的palladiumcatalyzed路线，这些杂环在适当的情况下，和钯介导的化学这些杂环遵循相同的顺序作为第1章介绍的基本化学。这种风格是合乎逻辑的，它是非常容易找到一个特定的杂环所需的反应，但确实有缺点，如果一个人读这本书从封面到封面，你会发展的感觉'似曾相识'在后面的章节。在每一章中，还包括了制造钯介导反应的底物的化学过程，使人们能够充分评估该方法的全部可行性，而无需查阅原始文献。非常自由地使用图表，包含基本的实验条件，是一个优点，我希望这些方案将征求化学家的浏览，寻找一些先例，他们正在考虑的化学是可能的。在整本书中有许多杂芳基赫克反应的例子，一个反应，它已经迅速从一个好奇心发展到现在的合成非常有用的程序。在每一章的结尾都有一个广泛的参考文献清单，涵盖了直到1999年，其中仅吲哚一章就有近500篇参考文献。
Chapter 1 is an excellent account of palladium-catalysed reactions that are now commonly employed in organic synthesis. These reactions include oxidative coupling, cross coupling reactions, Heck reactions, carbonylation, and amination. In each case the mechanism of the reaction was discussed in detail outlining the scope and limitations of these procedures. For each reaction class for which palladium 0 was required an attempt was made to describe how this was generated from the palladium II salt precursor. This is a subject which is often glossed over in research papers and little touches like this I feel make the chemistry more appealing to the mystified novice who is contemplating employing palladium chemistry. There are lots of little pieces of dogma provided which help rationalise the diverse chemistry later described. The analogy of equating ease of oxidative addition of vinyl halides to that of SNAr displacement was particularly helpful and this goes some way to rationalising why heterocyclic compounds behave so differently from carbocycles and allows a powerful predictive tool for determining regioselectivity in subsequent chapters. The conditions for the various cross coupling reactions Negishi, Suzuki, and Stille are critically compared and contrasted and the authors gave a good idea of which additional functional groups would survive the conditions. The factors which determine what makes a good transfer group in cross couplings is discussed and there are many examples of the more difficult cross coupling reactions involving that of alkyl groups throughout the text. The introductory section on the Heck reaction was excellent. Given that the Heck reaction normally does not produce chiral centres, I felt that the background information provided on the emerging asymmetric Heck reaction merited more than the one paragraph it was given. The palladium chemistry of ten heterocylic classes namely pyrroles, indoles, pyridines, thiophens, furans, thiazoles, oxaozoles, imidazoles, pyrazines, and pyrimidines are each covered in their own chapter. Each chapter has the same style, an introduction with naturally occurring heterocyles followed by a listing of synthetic pharmacologically active heterocylic compounds with a brief description of their medicinal properties. New palladiumcatalysed routes to these heterocycles are given where appropriate, and the palladium-mediated chemistry of these heterocycles follows the same order as the basic chemistry introduced in chapter 1. This style is logical, it is extremely easy to find a desired reaction of a particular heterocycle, but does have the disadvantage that if one reads the book from cover to cover you will develop a feeling of ‘déjà vu’ in the later chapters. In each chapter the chemistry for making the substrates for the palladium-mediated reactions is also included allowing one to fully evaluate the full feasibility of the approach without going to the original literature. The very liberal use of diagrams, containing basic experimental conditions, is a strong point and I expect these schemes will solicit browsing from chemists looking for some precedent that the chemistry they are contemplating is possible. Throughout the book there are many examples of the heteroaryl Heck reaction, a reaction, which has rapidly evolved from being a curiosity to a now synthetically very useful procedure. At the end of each chapter there is an extensive list of references covering up to and including the year 1999 with nearly 500 references alone for the indole chapter.