Recent advances in isocyanide chemistry

Mechanism of [2 + 1] Cycloadditions of Hydrogen Isocyanide to Alkynes: Molecular Orbital and Density Functional Theory Study

“…The cyanide−isocyanide isomerization has often been employed as an initial step in numerous preparative methods . Isocyanides usually react with a wide range of substrates, including nucleophiles, electrophiles, and radicals, under various experimental conditions, giving rise to different primary imine adducts . The mechanism and, in particular, the stereospecificity of these addition reactions have been investigated in details. − Owing to the presence of a monocoordinated carbon atom having an electron lone pair, isocyanides are also well suited as 1,1-dipolar partners in different types of cycloaddition whose primary cycloadducts undergo further rearrangements and/or ring expansions .…”

Synthesis and characterization of functionalized dihydropyrimidinones via one-pot isocyanide-based three-component reaction of N-formyl urea and dialkyl ACETYLENEDICARBOXYLATES

“…On the basis of the well-established chemistry of isocyanides [24,25], nucleophilic addition of alkyl isocyanide 1 to dialkyl acetylenedicarboxylate 2 leads to zwitterion 5 which is protonated by NH acid to give 6. This intermediate is attacked by anion 7 to produce ketenimine 8.…”

Silica Nanoparticles from Rice Husk Ash: A Green Catalyst for the One-Pot Three-Component Synthesis of Benzo[<i>B</i>]Furan Derivatives

“…Although we have not established the mechanism of the reaction in an experimental manner, a plausible reaction sequence that accounts for the formation of ( 7) is shown in Scheme 2. Thus condensation of 2-hydroxybenzaldehyde derivative (2) and secondary amine (1) would give the iminium ion intermediate (3), which would react with the alkyl isocyanide (4) to afford intermediate (5). The ionic intermediate ( 5) would cyclize into benzofuran (6).…”

“…Of pivotal importance in this area are the isocyanide-based MCRs such as the versatile Ugi and Passerini reactions [1][2][3][4]. The ability of isonitriles to undergo facile addition with a nucleophile and an electrophile under mild conditions makes them useful reactants for the development of novel MCRs [2,5]. Isocyanides [6], regarded for many years as compounds with unpleasant odor and very few chemical and pharmaceutical applications, are now looked upon as useful synthons with interesting chemical properties.…”