Radical Mechanism of Isocyanide-Alkyne Cycloaddition
by Multicatalysis of Ag<sub>2</sub>CO<sub>3</sub>, Solvent, and Substrate
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Abstract
A combined DFT and experimental study
was performed to reveal the
mechanism of isocyanide-alkyne cycloaddition. Our results indicate
that the mechanism of this valuable reaction is an unexpected multicatalyzed
radical process. Ag<sub>2</sub>CO<sub>3</sub> is the pivotal catalyst,
serving as base for the deprotonation of isocyanide and oxidant to
initiate the initial isocyanide radical formation. After the cycloaddition
between isocyanide radical and silver-acetylide, substrate (isocyanide)
and solvent (dioxane) replace the role of Ag<sub>2</sub>CO<sub>3</sub>. They act as a radical shuttle to regenerate isocyanide radical
for the next catalytic cycle, simultaneously completing the protonation.
Furthermore, the bulk solvent effect significantly increases the reactivity
by decreasing the activation barriers through the whole reaction,
serving as solvent as well as catalyst