Current Organic Synthesis ( IF 1.7 ) Pub Date : 2020-07-31 , DOI: 10.2174/1570179417666200212111049 Tegene T Tole 1 , Johannes H L Jordaan , Hermanus C M Vosloo
Background: 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).
Objective: 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.
Conclusion: 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.
中文翻译:
α-吡啶基醇,α,α'-吡啶二醇,α-联吡啶醇和α,α'-联吡啶二醇作为朝向重要有机分子和过渡金属配合物的结构基元。
背景:在过去的三十年中,吡啶醇的制备和使用显示出令人难以置信的增长。吡啶基醇杂配体的重要性质是其强碱性,这主要是由于缺乏相应阴离子的共振稳定性所致。这种强碱性的阴离子性质使它们具有在金属中心之间架桥而不是仅以末端方式结合到一个金属中心的高能力。由于它们与过渡金属共价(与氧)和半不稳定配位(通过氮)相互作用的能力,因此需要它们作为配体。
目的:本文综述了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序在重要有机分子制备中的广泛应用。它们的强碱性阴离子性质。
结论:从综述中可以清楚地看出,除了它们在均相和不对称催化反应中的合成用途外,还制备了冠醚,环状和无环醚,配位硼酸酯(硼酸酯),吡啶基膦配体,吡啶基亚磷酸酯吡啶基-次膦基配体是吡啶基醇的另一广泛应用领域。除上述应用外,它们还用于建模酶和某些治疗剂的作用方式。它们的强碱性阴离子性质使其在过渡金属簇络合物的合成中具有很高的能力,使其能够在金属中心之间架桥,而不是仅以末端方式结合至一个金属中心。