Simões Mário M Q, Cavaleiro José A S, Ferreira Vitor F
Department of Chemistry & LAQV-REQUIMTE, University of Aveiro, 3810-193 Aveiro, Portugal.
Departamento de Tecnologia Farmacêutica Química, Universidade Federal Fluminense, Niterói 24241-002, RJ, Brazil.
Molecules. 2023 Sep 18;28(18):6683. doi: 10.3390/molecules28186683.
Diazo compounds are organic substances that are often used as precursors in organic synthesis like cyclization reactions, olefinations, cyclopropanations, cyclopropenations, rearrangements, and carbene or metallocarbene insertions into C-H, N-H, O-H, S-H, and Si-H bonds. Typically, reactions from diazo compounds are catalyzed by transition metals with various ligands that modulate the capacity and selectivity of the catalyst. These ligands can modify and enhance chemoselectivity in the substrate, regioselectivity and enantioselectivity by reflecting these preferences in the products. Porphyrins have been used as catalysts in several important reactions for organic synthesis and also in several medicinal applications. In the chemistry of diazo compounds, porphyrins are very efficient as catalysts when complexed with low-cost metals (e.g., Fe and Co) and, therefore, in recent years, this has been the subject of significant research. This review will summarize the advances in the studies involving the field of diazo compounds catalyzed by metalloporphyrins (M-Porph, M = Fe, Ru, Os, Co, Rh, Ir) in the last five years to provide a clear overview and possible opportunities for future applications. Also, at the end of this review, the properties of artificial metalloenzymes and hemoproteins as biocatalysts for a broad range of applications, namely those concerning carbene-transfer reactions, will be considered.
重氮化合物是一类有机物质，常用于有机合成中的前体，如环化反应、烯化反应、环丙烷化反应、环丙烯化反应、重排反应以及卡宾或金属卡宾插入C-H、N-H、O-H、S-H和Si-H键的反应。通常，重氮化合物的反应由过渡金属与各种配体催化，这些配体可调节催化剂的活性和选择性。这些配体可以通过在产物中反映这些偏好来改变和提高底物的化学选择性、区域选择性和对映选择性。卟啉已被用作有机合成中几个重要反应的催化剂，也用于一些医学应用。在重氮化合物化学中，卟啉与低成本金属（如铁和钴）络合时作为催化剂非常有效，因此，近年来这一直是大量研究的主题。本综述将总结过去五年中金属卟啉（M-Porph，M = Fe、Ru、Os、Co、Rh、Ir）催化重氮化合物领域的研究进展，以提供清晰的概述和未来应用的可能机会。此外，在本综述结尾，还将考虑人工金属酶和血红蛋白作为广泛应用的生物催化剂的性质，即那些与卡宾转移反应有关的性质。
