Complete Field Guide to Asymmetric BINOL-Phosphate Derived Brønsted Acid and Metal Catalysis: History and Classification by Mode of Activation; Brønsted Acidity, Hydrogen Bonding, Ion Pairing, and Metal Phosphates

Multicomponent reactions: advanced tools for sustainable organic synthesis

Nitrogen containing compounds are of great importance because of their interesting and diverse biological activities. The construction of the C–N bond is of significant importance as it opens avenues for the introduction of nitrogen in organic molecules. Despite significant advancements in this field, the construction of the C–N bond is still a major challenge for organic chemists, due to the involvement of harsh reaction conditions or the use of expensive catalysts in many cases. Thus, it is a challenge to develop alternative, milder and cheaper methodologies for the construction of C–N bonds. Herein, we have selected some prime literature reports that may serve this purpose.

C–N bond forming cross-coupling reactions: an overview

As valuable C1 building blocks, isocyanides represent an important class of reactive species and synthons. During the past decades, exhaustive efforts have been devoted to the discovery of highly efficient reactions involving isocyanide on the basis of the development of the Passerini and Ugi reactions. Several types of reactions involving isocyanides have been reported, such as nucleophilic attack, electrophilic addition, imidoylation reactions, and oxidation etc. In this review, recent progress in isocyanide insertion chemistry is presented. Among all isocyanide insertions, two catalytic systems have been developed, that is, Lewis (Bronsted) acid-catalyzed isocyanide insertions and transition-metal-enabled isocyanide insertions, respectively. This review is hence written in the sequence of Lewis (Bronsted) acid-catalyzed isocyanide insertion and transitional metal-enabled isocyanide insertion, where isocyanide insertion into heteroatom–hydrogen bonds, carbon–halogen bonds, carbon–hydrogen bonds, and metal carbenes are summarized.

Recent advances in isocyanide insertion chemistry

Metal-mediated and metal-catalyzed reactions of isocyanides.

Isocyanides have been important building blocks in organic synthesis since the discovery of the Ugi reaction and related isocyanide-based multicomponent reactions. In the past decade isocyanides have found a new application as versatile C1 building blocks in palladium catalysis. Palladium-catalyzed reactions involving isocyanide insertion offer a vast potential for the synthesis of nitrogen-containing fine chemicals. This Minireview discusses all the achievements in this emerging field.

Palladium-catalyzed migratory insertion of isocyanides: an emerging platform in cross-coupling chemistry.

The importance of palladium-catalyzed cross coupling reactions in contemporary organic synthesis is undisputed and underlined by the Nobel Prize for Chemistry in 2010. In addition to the highly efficient cross coupling reactions for single C-C bond construction, palladium-catalyzed cascade processes involving multiple bond formations have emerged in recent years as valuable tools for the rapid synthesis of complex molecular scaffolds. This review presents an overview of the most relevant developments in this field, with a focus on the generation of diverse poly- and heterocyclic scaffolds. The generally well understood reactivity of palladium has allowed the discovery of many intriguing novel cascade processes, and the creativity of the synthetic community will undoubtedly lead to many more discoveries in the future. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Recent Advances in Palladium-Catalyzed Cascade Cyclizations

O(2) in, H(2)O out: Various diamines and related bisnucleophiles readily undergo oxidative isocyanide insertion with Pd(OAc)(2) (1 mol %) as the catalyst and O(2) as the terminal oxidant to give a diverse array of medicinally relevant N heterocycles. The utility of this highly sustainable method is demonstrated by a formal synthesis of the antihistamines astemizole and norastemizole.

Sustainable Synthesis of Diverse Privileged Heterocycles by Palladium‐Catalyzed Aerobic Oxidative Isocyanide Insertion

Palladium-catalyzed synthesis of 4-aminophthalazin-1(2H)-ones by isocyanide insertion.

Multiple applications of isothioureas as fine chemicals (or their precursors) are known, but a general sustainable method for their synthesis was hitherto unavailable We report a novel general approach towards S-alkyl and S-aryl isothioureas through a copper(I)-catalyzed three-component reaction between amines, isocyanides, and thiosulfonates The formal synthesis of a superpotent sweetener further illustrates the applicability of our method

Tjoestil Vlaar

Papers

Palladium-catalyzed migratory insertion of isocyanides: an emerging platform in cross-coupling chemistry.

Recent Advances in Palladium-Catalyzed Cascade Cyclizations

Sustainable Synthesis of Diverse Privileged Heterocycles by Palladium‐Catalyzed Aerobic Oxidative Isocyanide Insertion

Palladium-catalyzed synthesis of 4-aminophthalazin-1(2H)-ones by isocyanide insertion.

Sustainable Three‐Component Synthesis of Isothioureas from Isocyanides, Thiosulfonates, and Amines