Synthesis of 1H-Pyrazol-5-yl-pyridin-2-yl-[1,2,4]triazinyl Soft-Lewis Basic Complexants via Metal and Oxidant Free [3+2] Dipolar Cycloaddition of Terminal Ethynyl Pyridines with Tosylhydrazides

Soft-Lewis basic complexants that facilitate chemoselective separation of the minor actinides from the lanthanides are critical to the closure of the nuclear fuel cycle. Complexants that modulate covalent orbital interactions with relevant metals of interest can facilitate desired outcomes in liquid-liquid separation, allowing for further transmutative processes that decrease issues related with storage of spent nuclear fuel from energy and weapons production. Synthesis of previously unexplored scaffolds seeks to improve performance over benchmark complexants. In the current work, an intermolecular, thermally initiated, and DBU-assisted [3 + 2] cycloaddition of 3-(6-ethynyl-pyridin-2-yl)-5,6-diphenyl-[1,2,4]triazine dipolarophiles with structurally diverse 4-methylbenzenesulfono-hydrazides afforded 21 yet-to-be reported examples in 42-68% yield and modest regioselectivity for the desired regioisomer. Preparation of requisite starting materials, method definition, dipole and dipolarophile scope, ten-fold scale-up reaction, and downstream functional group interconversion are reported herein.