Renaissance of Organic Synthesis Using Isocyanides

Abstract

New reactions using old functionality, isocyanides, are described. By using isocyanides in place of carbon monoxide, transformations otherwise difficult to achieve, such as GaCl 3 -catalyzed [4 + 1] cycloaddition and TfOH-catalyzed insertion into a CO bond of acetals, are realized. In addition, isocyanides are exploited as a key component in transition-metal-catalyzed CH bond activation and borylation reactions.

Palladium(0)-Catalyzed Benzylic C(<i>sp</i>³)–H Functionalization for the Concise Synthesis of Heterocycles and Its Applications

“…We initially focused on a cascade reaction involving a combination of benzylic C(sp 3 )-H functionalization with Pd-catalyzed isocyanide insertion [81][82][83][84][85][86] for the synthesis of indole derivatives, which are an important class of nitrogen-containing heterocycles in the pharmaceutical sciences. Several other groups had previously reported concise methods for the synthesis of carbo-and heterocyclic systems through isocyanide insertion and C(sp 2 )-H activation steps.…”

Organocatalytic activation of isocyanides: N-heterocyclic carbene-catalyzed enaminone synthesis from ketones

“…1 Because the terminal carbon of isocyanide can act as both a nucleophile and the carbene center, control of its reactivity is key to developing novel transformations. In many cases, the isocyanide group can act as a mild nucleophile, meaning that it undergoes electrophilic activation in the presence of an electrophilic compound.…”

Catalytic Isonitrile Insertions and Condensations Initiated by RNC–X Complexation

“…[3] The synthesis of isonitriles has blossomed because isonitriles provide a rapid entry into drug-like molecules, heterocycles, [4] and diverse molecular scaffolds. [5] …”

“…[7] Dramatic progress in Ugi, Passerini, and related multicomponent additions has recently been reviewed. [1–3] …”