Transition‐Metal‐Catalyzed Cross‐Coupling and Sequential Reactions of Azides with Isocyanides

Abstract

Transition-metal-catalyzed cross-coupling reaction of azides with isocyanides, as a new type of nitrene transformation, has become an expeditious method to prepare carbodiimides. Considering the compatibility of this coupling process with other systems, transition-metal-catalyzed sequential reactions have become more popular in recent years. These remarkable advances not only involve many interesting reaction processes, but also provide useful strategies for the construction of nitrogen-containing structures, such as guanidines, amidines, isoureas, and heterocyclic compounds. This review will present a comprehensive picture of the development of transition-metal-catalyzed coupling process of azides with isocyanides and their applications in the preparation of nitrogen-containing compounds. Catalytic coupling reactions followed by nucleophilic additions will be briefly introduced here. Most recent advances in catalytic cascade reactions involving a coupling process will be highlighted and make up the main part of this review. 1. strates 4.1. Pd-Catalyzed Cascade Reactions 4.2. Rh-Catalyzed Cascade Reactions 4.3. Co-Catalyzed Cascade Reactions 5. Conclusions

1,3-diene-based AIEgens: Stereoselective synthesis and applications

“…The synthesis of 1,3-dienes via the reaction between alkenes and alkenes represents the most common approach. This strategy includes various methodologies, including the Heck reaction, 13 oxidative coupling, 14 and reductive coupling. 15 Three main strategies are used to regulate the geometry of double bonds: (1) The selective use of alkene substrates with specific configurations, (2) the control of β-H elimination through steric effects, and (3) the selective activation of vinyl C–H bonds.…”

Visible-light-induced synthesis of 2,4-disubstituted quinolines from o-vinylaryl isocyanides and oxime esters

“…As one of the most significant constituents in organic synthesis, isocyanides are capable of undergoing extensive transformations due to their unique terminal carbon center. 10 Transition-metal catalyzed isocyanide insertion reactions provide an effective pathway for the synthesis of nitrogen-containing fine chemicals by using isocyanides as C 1 building blocks. 11 Besides, isocyanide-based multicomponent reactions (Scheme 1a), such as the Ugi reaction, are useful for constructing complex molecules without tedious steps.…”

Selective 1,2-insertion of carbodiimides and substrate-divergent silyl group migration at 1-metallacyclobuta-2,3-dienes

“…13 Products of simple coordination of carbodiimides to a metal centre were isolated 13 a and proposed as intermediates in reactions involving these as substrates 14 or products. 15 Metal catalysed functionalisation of carbodiimides such as guanylation 16 or metathesis 17 was reported in the past, involving aza-metallacycles as key-intermediates. In general, aza-metallacycles are an interesting class of organometallic compounds with great potential for the construction of nitrogen containing cyclic and acyclic structures.…”