Horn Alissa, Dussault Patrick H
Department of Chemistry, University of Nebraska-Lincoln Lincoln NE 68588-0304 USA
RSC Adv. 2020 Dec 16;10(72):44408-44429. doi: 10.1039/d0ra09088c. eCollection 2020 Dec 9.
Copper-promoted azide/alkyne cycloadditions (CuAAC) are explored as a tool for modular introduction of peroxides onto molecules and nanomaterials. Dialkyl peroxide-substituted alkynes undergo Cu(i)-promoted reaction with azides in either organic or biphasic media to furnish peroxide-substituted 1,2,3-triazoles. Heterolytic fragmentation of the peroxide to an aldehyde, a side reaction that appears to be related to the formation of the triazole, can be suppressed by use of excess alkyne, the presence of triethylsilane, or by use of iodoalkyne substrates. Complementary reactions of simple alkynes with azido-substituted peroxides are much less efficient. Click reactions of alkynyl peroxyacetals are also reported; reductive fragmentation can be minimized by increasing the distance between the peroxyacetal and the alkyne. The strategy enables modular introduction of dialkyl peroxides and peroxyacetals onto gold nanoparticles, the first such process to be reported.
铜促进的叠氮化物/炔烃环加成反应（CuAAC）被作为一种将过氧化物模块化引入分子和纳米材料的工具进行探索。过氧化二烷基取代的炔烃在有机或双相介质中与叠氮化物发生铜（I）促进的反应，以提供过氧化物取代的1,2,3 - 三唑。通过使用过量的炔烃、三乙基硅烷的存在或使用碘代炔烃底物，可以抑制过氧化物向醛的异裂碎片化，这是一种似乎与三唑形成有关的副反应。简单炔烃与叠氮基取代的过氧化物的互补反应效率要低得多。还报道了炔基过氧缩醛的点击反应；通过增加过氧缩醛与炔烃之间的距离，可以将还原碎片化最小化。该策略能够将过氧化二烷基和过氧缩醛模块化引入金纳米颗粒，这是首次报道的此类过程。
