Unravelling the labyrinth of palladium-catalysed reactions involving isocyanides

Abstract

Isocyanides possess a rich history in the world of synthetic chemistry. Recently the scope of this already versatile class of reagent has been expanded into its use in palladium-catalysed cascade sequences. The scope of this type of reaction is explored in depth and this tutorial review focuses on its various applications in chemical synthesis, and the wide range of systems that can be efficiently prepared using this strategy are documented.

Characterization of Cu-ligand bonds in tris-pyrazolylmethane isocyanide copper(I) complexes based upon combined X-ray diffraction and theoretical study

“…Metal-involving reactions of such versatile substrates as isocyanides attract significant attention, which is collaterally reflected in a large number of reviews and books published in this field [1][2][3][4][5][6][7][8]. Among various metal centers that promote conversion of RNC species, copper(I) plays a remarkable role insofar as this labile metal center provides efficient cyclization of isocyanides to various heterocyclic systems (for recent examples see [9][10][11][12][13][14]).…”

Synthesis of 6‐Alkylated Phenanthridine Derivatives Using Photoredox Neutral Somophilic Isocyanide Insertion

“…[1] Isocyanides are isoelectronic with carbon monoxide, and thus it is not surprising that isocyanides can undergo insertion reactions (also named imidoylative reactions) [2] to provide N-containing heterocycles which are ubiquitous in pharmaceuticals and biologically active molecules. [2][3][4] As depicted in Scheme 1 a, palladium-catalyzed isocyanide insertion and somophilic isocyanide insertion represent two typical strategies currently reported for isocyanide insertion reactions.…”

“…[1] Isocyanides are isoelectronic with carbon monoxide, and thus it is not surprising that isocyanides can undergo insertion reactions (also named imidoylative reactions) [2] to provide N-containing heterocycles which are ubiquitous in pharmaceuticals and biologically active molecules. [2][3][4] As depicted in Scheme 1 a, palladium-catalyzed isocyanide insertion and somophilic isocyanide insertion represent two typical strategies currently reported for isocyanide insertion reactions. While the palladium-catalyzed isocyanide insertions often require high reaction temperatures and have the tendency to undergo multiple consecutive insertions, [5] the use of isocyanides as somophiles for insertion reactions holds promise for practical synthetic applications under mild reaction conditions.…”

“…We then turned our attention to explore the scope of alkylating reagents (2). A series of 6-alkylated phenanthridine derivatives were prepared as shown in Table 3.…”

Synergy Effects in the Chemical Synthesis and Extensions of Multicomponent Reactions (MCRs)—The Low Energy Way to Ultra-Short Syntheses of Tailor-Made Molecules

“…Even though MCRs normally run without catalysts, there are special applications for both various transition metal catalysts [79,118,[139][140][141][142][143][144][145][146] and organic catalysts [79,[147][148][149][150].…”