含环辛烷核的羟烷基-1,2,3-三唑的立体选择性及其在 CuAAC 催化中的应用,Catalysts

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含环辛烷核的羟烷基-1,2,3-三唑的立体选择性及其在 CuAAC 催化中的应用
Catalysts ( IF 3.8 ) Pub Date : 2023-05-03 , DOI: 10.3390/catal13050835
Olga V. Ryzhikova ₁ , Kseniya N. Sedenkova ₁ , Sergey V. Kositov ₁ , Victor A. Tafeenko ₁ , Yuri K. Grishin ₁ , Elena B. Averina ₁

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带有附加官能团的 1,2,3-三唑已作为配体应用于广泛反应的催化、用于各种实际用途的过渡金属络合物的合成以及金属基药物的设计。加速 CuAAC 反应的三唑基配体，如 TBTA 和 TTTA，如今常用于有机合成，寻找结构不太复杂的新型配体是一项重要任务。在目前的工作中，一系列含有环辛烷核的羟烷基三唑通过叠氮醇或二叠氮二醇与苯乙炔的现成单个非对映异构体的环加成反应合成。所获得的羟烷基三唑被探测为苄基叠氮与乙炔的 CuAAC 反应的配体，以及 1-[(4-苯基-1H-1,2, 3-triazol-1-yl)methyl]cyclooctanol 被证明可以作为这些过程的有效配体。上述三唑与CuCl2的络盐很容易得到。根据X射线衍射分析数据，该配合物含有两个三唑分子，其中只有三唑环的N1原子作为配位中心。这种分子结构与 1-[(4-phenyl-1H-1,2,3-triazol-1-yl)methyl]cyclooctanol 在 CuAAC 反应中作为配体的效率密切相关：它能够配位铜离子和同时，它形成了一个足够不稳定的复合物，不会从催化循环中去除铜离子。该复合物包含两个三唑分子，其中只有三唑环的 N1 原子充当配位中心。这种分子结构与 1-[(4-phenyl-1H-1,2,3-triazol-1-yl)methyl]cyclooctanol 在 CuAAC 反应中作为配体的效率密切相关：它能够配位铜离子和同时，它形成了一个足够不稳定的复合物，不会从催化循环中去除铜离子。该复合物包含两个三唑分子，其中只有三唑环的 N1 原子充当配位中心。这种分子结构与 1-[(4-phenyl-1H-1,2,3-triazol-1-yl)methyl]cyclooctanol 在 CuAAC 反应中作为配体的效率密切相关：它能够配位铜离子和同时，它形成了一个足够不稳定的复合物，不会从催化循环中去除铜离子。

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Stereoselective Approach to Hydroxyalkyl-1,2,3-Triazoles Containing Cyclooctane Core and Their Use for CuAAC Catalysis

1,2,3-Triazoles bearing additional functional groups have found applications as the ligands in catalysis of a broad scope of reactions, synthesis of transition metals complexes for various practicable purposes, and design of metal-based drugs. Triazolyl ligands accelerating CuAAC reactions, such as TBTA and TTTA, are nowadays commonly used in organic synthesis, and the search for novel ligands with a less complicated structure represents an important task. In the present work a series of hydroxyalkyltriazoles, containing a cyclooctane core, were synthesized via cycloaddition of readily available individual diastereomers of azidoalcohols or diazidodiols with phenylacetylene. The obtained hydroxyalkyltriazoles were probed as ligands for CuAAC reactions of benzyl azide with acetylenes, and 1-[(4-phenyl-1H-1,2,3-triazol-1-yl)methyl]cyclooctanol was demonstrated to act as an effective ligand for these processes. The complex salt of the abovementioned triazole and CuCl2 was readily obtained. According to X-ray diffraction analysis data, the complex contained two molecules of triazole, in which only N1-atoms of the triazole ring acted as coordination centers. Such a molecular structure correlates well with the efficiency of 1-[(4-phenyl-1H-1,2,3-triazol-1-yl)methyl]cyclooctanol as a ligand in CuAAC reactions: it is able to coordinate copper ions and, at the same time, it forms a sufficiently labile complex to not withdraw copper ions from the catalytic cycle.

更新日期：2023-05-03

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