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Metal-catalyzed electrochemical diazidation of alkenes

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Science  11 Aug 2017:
Vol. 357, Issue 6351, pp. 575-579
DOI: 10.1126/science.aan6206

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A charged approach to forming C–N bonds

Adjacent carbon-nitrogen bonds often appear in chemical compounds of pharmaceutical interest. Fu et al. developed a versatile method to form these bonds by pairing manganese catalysis with electrochemical azide oxidation in the presence of olefins. A major advantage of the electrochemical approach is the tunable precision of its oxidizing power, which leaves other sensitive substituents such as alcohols and aldehydes intact. The reaction proceeded over several hours at room temperature, forming hydrogen at the counter electrode as a benign by-product.

Science, this issue p. 575

Abstract

Vicinal diamines are a common structural motif in bioactive natural products, therapeutic agents, and molecular catalysts, motivating the continuing development of efficient, selective, and sustainable technologies for their preparation. We report an operationally simple and environmentally friendly protocol that converts alkenes and sodium azide—both readily available feedstocks—to 1,2-diazides. Powered by electricity and catalyzed by Earth-abundant manganese, this transformation proceeds under mild conditions and exhibits exceptional substrate generality and functional group compatibility. Using standard protocols, the resultant 1,2-diazides can be smoothly reduced to vicinal diamines in a single step, with high chemoselectivity. Mechanistic studies are consistent with metal-mediated azidyl radical transfer as the predominant pathway, enabling dual carbon-nitrogen bond formation.

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