Isonitrile Syntheses

Abstract

In spite of the large number of reactions which involve the formation of isonitriles, the only preparative routes to these compounds, until recently, were the classical isonitrile syntheses discovered about one hundred years ago by Gautier and Hofmann. These methods are not generally applicable, and give satisfactory yield$ only in exceptional cases. Isonitriles have recently become readily available by the elimination of water from N-substituted formamides, using acyl halides of Group IV-VI elements in the presence of bases as dehydrating agents. A dehydrating system with a particularly wide range of application consists of phosgene with tertiary amines. This system generally provides the easiest and most productive route to isonitriles, particularly where large quantities (> 1 mole) are to be prepared.

The sulfocyanic theory on the origin of life: towards a critical reappraisal of an autotrophic theory

“…Isothiocyanic acid (HNCS) has been detected in the interstellar medium (Irvine 1998). The reaction of isothiocyanic acid with isonitriles can lead to triazines (Ugi et al 1965).…”

Azide Chemistry – An Inorganic Perspective, Part II[‡][3+2]‐Cycloaddition Reactions of Metal Azides and Related Systems

“…[36b] Only one isocyano function of the diisocyanide bis(2-isocyanoethyl)carbonate [509] 3, 4, chapter 1.1.1); in the former case, the unreacted CN group acts as a base towards a second complex molecule leading to partially associated products with loss of phosphine. Another type of isocyanide carrying a functional group able to act as a ligand is 2-isocyanoethyl(diphenyl)phosphine.…”

Base-catalyzed cyclization of Ugi-adducts to substituted indolyl based γ-lactams

“…The Ugi four component condensation reaction is one of the distinguished MCRs, involving the condensation of aldehydes, amines, carboxylic acids, and isocyanides to form the corresponding diamide adducts [9][10][11][12]. Some modifications such as post-condensation cyclization (PCC) have been made to the Ugi-4CC reaction in order to synthesize complex heterocycles by extending reactions on Ugi adducts.…”