Medium Rings Bearing Bitriazolyls: Easily Accessible Structures with Superior Performance as Cu Catalyst Ligands
Medium Rings Bearing Bitriazolyls: Easily Accessible Structures with Superior Performance as Cu Catalyst Ligands
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含有联三唑基的中环：易于接近的结构，具有作为铜催化剂配体的卓越性能
DOI：
10.1021/acs.joc.8b01899
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发表时间：
2018
期刊：
影响因子：
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通讯作者：
Lihe Zhang
中科院分区：
文献类型：
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作者：
Lingjun Li;Shenlong Huang;Tongpeng Shang;Bo Zhang;Yuanyang Guo;Gongming Zhu;Demin Zhou;Guisheng Zhang;Anlian Zhu;Lihe Zhang
由于其独特的性质，结构新颖且易于获得的介质环的开发在制药工业和学术研究中具有重大意义。然而，由于中环支架的刚性骨架和大角度应变，合成中环支架非常困难。本文设计、合成了一类新的含双三唑基的中环化合物（MRBTs），并将其作为Cu（I）催化点击反应的新型骨架配体，用于蛋白质的定点修饰。其中一个MRBTs，3aa，表现出高达55 000的周转数（TON）和显着的加速效应（kobs = 1.95 M-1 s-1），是铜催化的炔和叠氮化物环加成反应中最有效的配体之一。与难以获得其他已知的中等环不同，这些7-12元MRBT可以从结构不同的线性末端二炔和叠氮化物以简单的一步方式制备。因此，独特的可访问性和有趣的属性意味着其广泛的应用前景。
Benefiting from their unique properties, the development of structurally novel and easily accessible medium rings is of significant interest in the pharmaceutical industry and academic research. However, synthetic access to medium-ring scaffolds is very difficult due to their rigid skeleton and large-angle strains. In this paper, a new class of medium rings bearing bitriazolyls (MRBTs) was designed, synthesized, identified as a promising new skeleton ligand for the Cu(I)-catalyzed click reaction, and used in site-special modification of protein. One of the MRBTs, 3aa, exhibited a turnover number (TON) as high as 55 000 and dramatic accelerating effects (kobs = 1.95 M–1 s–1) and ranked among the most efficient ligands for copper-catalyzed alkyne and azide cycloaddition. Unlike the difficult access to other known medium rings, these 7–12-membered MRBTs can be prepared in straightforward, one-step manner from structurally diverse linear terminal diynes and azides. The unique accessibility and intriguing properties therefore imply their broad application perspectives.