Isocyanides have long proved themselves to be irreplaceable building blocks in modern organic chemistry. The unique features of the isocyano group make isocyanides particularly useful for the synthesis of a number of important classes of nitrogen heterocycles, such as pyrroles, indoles, and quinolines. Several cocyclizations of isocyanides via zwitterions and radical intermediates as well as transition-metal-catalyzed syntheses of different types of heterocycles have recently been developed. Methods starting from isocyanides often have distinct advantages over alternative approaches to the same heterocycles because of their enhanced convergence, the great simplicity of most of the operations with them, and the great variety of isocyanides readily available for use. Isocyanides have also been used in some enantioselective syntheses of chiral heterocyclic compounds, including natural products as well as precursors thereof.

Metallo aldimines. Masked acyl carbanion

Isocyanides in the Synthesis of Nitrogen Heterocycles

Synthetic methods using α-heterosubstituted organometallics

Synthesis and chemistry of acyl silanes

New horizons in carbonyl chemistry: reagents for nucleophilic acylation

α-Alkali-metalated isocyanides, which can be obtained from isocyanides and bases, can be used for nucleophilic introduction of (masked) α-aminoalkyl groups. Intramolecular ring-closure may then follow if a nucleophile combines at the electron sextet of the isocyanide carbon. Treatment of α-alkali-metalated isocyanides with electrophilic agents permits rapid and efficient synthesis of, inter alia, 2- and 3-amino alcohols, straight-chain, branched, and β-functional α-amino acids, olefins, vinyl isocyanides, and of a large number of mainly five-, but also six- and seven-membered aza-, diaza-, oxa-aza-, and thia-aza heterocycles.

Metallo aldimines. Masked acyl carbanion

Citations

Isocyanides in the Synthesis of Nitrogen Heterocycles

Synthetic methods using α-heterosubstituted organometallics

Synthesis and chemistry of acyl silanes

New horizons in carbonyl chemistry: reagents for nucleophilic acylation

α-Metalated Isocyanides in Organic Synthesis. New synthetic methods (6)

Related Papers (5)

Lithium Aldimines. A New Synthetic Intermediate

New access to 2,3-disubstituted quinolines through cyclization of o-alkynylisocyanobenzenes

Carbonyl Olefination with α‐Metalated Isocyanides

Generation and synthetic applications of 2-lithio-1,3-dithianes

Recent developments in isocyanide based multicomponent reactions in applied chemistry