Iron Nitrate-Mediated Selective Synthesis of 3-Acyl-1,2,4-oxadiazoles from Alkynes and Nitriles: The Dual Roles of Iron Nitrate.
Qilong BianCunluo WuJiangpei YuanZuodong ShiTao DingYongwei HuangHao XuYuanqing XuPublished in: The Journal of organic chemistry (2020)
A direct strategy for the selective synthesis of 3-acyl-1,2,4-oxadiazoles from alkynes and nitriles has been developed under iron(III) nitrate-mediated conditions. The mechanism includes three sequential procedures: iron(III) nitrate-mediated nitration of alkynes leads to α-nitroketones, dehydration of α-nitroketones provides the nitrile oxides, and 1,3-dipolar cycloaddition of nitrile oxides with nitriles produces 3-acyl-1,2,4-oxadiazoles under iron-mediated conditions. Iron(III) nitrate plays dual roles in the nitration of alkynes and the activation of nitriles, while the formation of pyrimidine/isoxazole byproducts can be efficiently inhibited.