School of Chemistry, Trinity Biomedical Sciences Institute, Trinity College Dublin, The University of Dublin, 152-160 Pearse Street, Dublin 2, Ireland.
Chem Soc Rev. 2021 Apr 7;50(7):4730-4789. doi: 10.1039/c7cs00719a. Epub 2021 Feb 24.
Porphyrins feature prominently in nature, be it as enzymatic cofactors, electron and exciton shuffles, as photoactive dyes, or as signaling substances. Their involvement in the generation, storage and use of oxygen is pivotal to life, while their photochemical properties are central to the biochemical functioning of plants. When complexed to metals, porphyrins can engage in a multitude of contemporary applications ranging from solar energy generation to serving as catalysts for important chemical reactions. They are also able to function as useful theranostic agents, and as novel materials for a wide range of applications. As such, they are widely considered to be highly valuable molecules, and it almost goes without saying that synthetic organic chemistry has dramatically underpinned all the key advances made, by providing reliable access to them. In fact, strategies for the synthesis of functionalized porphyrins have now reached a state of refinement where pretty well any desired porphyrin can successfully be synthesized with the approaches that are available, including a cornucopia of related macrocycle-modified porphyrinoids. In this review, we are going to illustrate the development of this exciting field by discussing a number of classic syntheses of porphyrins. Our coverage will encompass the natural protoporphyrins and chlorophylls, while also covering general strategies for the synthesis of unsymmetrical porphyrins and chlorins. Various industrial syntheses of porphyrins will also be discussed, as will other routes of great practical importance, and avenues to key porphyrinoids with modified macrocycles. A range of selected examples of contemporary functionalization reactions will be highlighted. The various key syntheses will be described and analyzed from a traditional mechanistic organic chemistry perspective to help student readers, and those who are new to this area. The aim will be to allow readers to mechanistically appreciate and understand how many of these fascinating ring-systems are built and further functionalized.
卟啉在自然界中扮演着重要的角色，无论是作为酶的辅助因子、电子和激子转移、光活性染料，还是作为信号物质。它们在氧气的产生、储存和利用中起着关键作用，而它们的光化学性质则是植物生化功能的核心。当与金属络合时，卟啉可以参与从太阳能发电到作为重要化学反应催化剂的多种现代应用。它们还可以作为有用的治疗诊断剂和各种应用的新型材料。因此，它们被广泛认为是非常有价值的分子，而且几乎可以说，合成有机化学通过提供可靠的获取途径，为所有关键进展提供了巨大的支持。事实上，功能化卟啉的合成策略已经达到了一种精细化的状态，几乎任何所需的卟啉都可以通过现有的方法成功合成，包括丰富的相关大环修饰卟啉类。在这篇综述中，我们将通过讨论一些经典的卟啉合成来展示这个令人兴奋的领域的发展。我们的报道将涵盖天然原卟啉和叶绿素，同时还将涵盖不对称卟啉和叶绿素的一般合成策略。还将讨论各种工业合成卟啉的方法，以及其他具有实际重要性的途径，以及具有修饰大环的关键卟啉类途径。还将讨论各种其他重要的途径，以及具有修饰大环的关键卟啉类途径。将突出展示一些当代功能化反应的选定实例。将从传统的有机化学机制观点来描述和分析各种关键合成，以帮助学生读者和该领域的新手。目的是让读者从机制上欣赏和理解这些迷人的环系是如何构建和进一步功能化的。
