Tole Tegene T, Jordaan Johannes H L, Vosloo Hermanus C M
Research Focus Area for Chemical Resource Beneficiation, Catalysis and Synthesis Research Group, North-West University, Hoffmann Street, 2531 Potchefstroom, South Africa.
Curr Org Synth. 2020;17(5):344-366. doi: 10.2174/1570179417666200212111049.
The preparation and use of pyridinyl alcohols as ligands showed incredible increment in the past three decades. Important property of pyridinyl alcoholato ligands is their strong basicity, which is mainly due to the lack of resonance stabilization of the corresponding anion. This strongly basic anionic nature gives them high ability to make bridges between metal centers rather than to bind to only one metal center in a terminal fashion. They are needed as ligands due to their ability to interact with transition metals both covalently (with oxygen) and hemilabile coordination (through nitrogen).
The review focuses on the wide application of α-pyridinyl alcohols, α,α'-pyridine diols, α- bipyridinyl alcohols, and α,α'-bipyridine diols as structure motifs in the preparation of important organic molecules which is due to their strongly basic anionic nature.
It is clear from the review that in addition to their synthetic utility in the homogeneous and asymmetric catalytic reactions, the preparation of the crown ethers, cyclic and acyclic ethers, coordinated borates (boronic esters), pyridinyl-phosphine ligands, pyridinyl-phosphite ligands, and pyridinyl-phosphinite ligands is the other broad area of application of pyridinyl alcohols. In addition to the aforementioned applications they are used for modeling mode of action of enzymes and some therapeutic agents. Their strongly basic anionic nature gives them high ability to make bridges between metal centers rather than to bind to only one metal center in a terminal fashion in the synthesis of transition metal cluster complexes. Not least numbers of single molecule magnets that can be used as storage of high density information were the result of transition metal complexes of pyridinyl alcoholato ligands.
在过去三十年中，吡啶醇作为配体的制备和应用呈现出惊人的增长。吡啶醇配体的重要特性是其强碱性，这主要归因于相应阴离子缺乏共振稳定作用。这种强碱性阴离子性质赋予它们在金属中心之间形成桥连的高能力，而不是以端基方式仅与一个金属中心结合。由于它们能够与过渡金属以共价方式（通过氧）和半不稳定配位方式（通过氮）相互作用，因此需要它们作为配体。
本综述重点关注α - 吡啶醇、α,α'-吡啶二醇、α - 联吡啶醇和α,α'-联吡啶二醇作为结构基元在重要有机分子制备中的广泛应用，这归因于它们的强碱性阴离子性质。
从综述中可以清楚地看出，除了在均相和不对称催化反应中的合成效用外，吡啶醇在冠醚、环状和非环状醚、配位硼酸盐（硼酸酯）、吡啶基 - 膦配体、吡啶基亚磷酸酯配体和吡啶基次膦酸酯配体制备中的应用也是另一个广泛领域。除了上述应用外，它们还用于模拟酶和一些治疗剂的作用模式。在过渡金属簇配合物的合成中，它们的强碱性阴离子性质赋予它们在金属中心之间形成桥连的高能力，而不是以端基方式仅与一个金属中心结合。吡啶醇配体的过渡金属配合物产生了大量可用于高密度信息存储的单分子磁体。
