The chemistry of heterocyclic carbenes has experienced a rapid development over the last years. In addition to the imidazolin-2-ylidenes, a large number of cyclic diaminocarbenes with different ring sizes have been described. Aside from diaminocarbenes, P-heterocyclic carbenes, and derivatives with only one, or even no heteroatom within the carbene ring are known. New methods for the synthesis of complexes with N-heterocyclic carbene ligands such as the oxidative addition or the metal atom template controlled cyclization of β-functionalized isocyanides have been developed recently. This review summarizes the new developments regarding the synthesis of N-heterocyclic carbenes and their metal complexes.

Heterocyclic Carbenes: Synthesis and Coordination Chemistry

In the investigation of efficient chemical transformations, the carbon-carbon bond-forming reactions play an outstanding role. In this context, organocatalytic processes have achieved considerable attention. 1 Beside their facile reaction course, selectivity, and environmental friendliness, new synthetic strategies are made possible. Particularly, the inversion of the classical reactivity (Umpolung) opens up new synthetic pathways. 2 In nature, the coenzyme thiamine (vitamin B1), a natural thiazolium salt, utilizes a catalytic variant of this concept in biochemical processes as nucleophilic acylations. 3 The catalytically active species is a nucleophilic carbene. 4

Organocatalysis by N-Heterocyclic Carbenes

The fascinating story of olefin (or alkene) metathesis (eq
1) began almost five decades ago, when Anderson and
Merckling reported the first carbon-carbon double-bond
rearrangement reaction in the titanium-catalyzed polymerization of norbornene. Nine years later, Banks and Bailey reported “a new disproportionation reaction . . . in which olefins are converted to homologues of shorter and longer carbon chains...”. In 1967, Calderon and co-workers named this metal-catalyzed redistribution of carbon-carbon double bonds olefin metathesis, from the Greek word “μeτάθeση”, which means change of position. These contributions have since served as the foundation for an amazing research field, and olefin metathesis currently represents a powerful transformation in chemical synthesis, attracting a vast amount of interest both in industry and academia.

https://core.ac.uk/download/pdf/4884240.pdf

Ruthenium-based heterocyclic carbene-coordinated olefin metathesis catalysts.

This critical review discusses historical and contemporary research in the field of transition metal-catalyzed carbon–hydrogen (C–H) bond activation through the lens of stereoselectivity. Research concerning both diastereoselectivity and enantioselectivity in C–H activation processes is examined, and the application of concepts in this area for the development of novel carbon–carbon and carbon–heteroatom bond-forming reactions is described. Throughout this review, an emphasis is placed on reactions that are (or may soon become) relevant in the realm of organic synthesis (221 references).

Transition metal-catalyzed C–H activation reactions: diastereoselectivity and enantioselectivity

Modern synthetic methods have revolutionized polymer chemistry through the development of new and powerful strategies for the controlled synthesis of complex polymer architectures. 1-5 Many of these developments were spawned by new classes of transition metal catalysts for the synthesis of new polyolefin microstructures, 5 the design of highly efficient families of “living” polymerization strategies for the synthesis of block, graft, and star polymers, 6-12 controlled methods for the synthesis of dendritic macromolecules, 3,13,14

Organocatalytic ring-opening polymerization.

The coenzyme thiamine (vitamin B1), a natural thiazolium salt, is involved in many enzymatic catalyses. Since it has been proposed that the catalytically active species of these reactions is a nucleophilic carbene, many chemists have tried to perform enzyme mimetic asymmetric carbene catalysis. After a long and difficult search, stable carbenes are finally isolated, characterized, and in the chemist's hands. The experiments of decades have finally resulted in successful enantioselective benzoin condensations and enantioselective intramolecular Stetter reactions as important examples of carbene catalyzed asymmetric nucleophilic acylation processes.

Nucleophilic carbenes in asymmetric organocatalysis.

Asymmetric intramolecular crossed-benzoin reactions by N-heterocyclic carbene catalysis.

The title compound 1,3,4-triphenyl-4,5-dihydro-1H-1,2,4-triazol-5-ylidene has been prepared in quantitative yield from the corresponding 5-methoxytriazoline precursor by simple thermal decomposition in vacuo via α-elimination of methanol. The carbene is a stable solid in the absence of oxygen and moisture, and shows the typical reactivity of nucleophilic Wanzlick-type carbenes.

Tim Balensiefer

Papers

Nucleophilic carbenes in asymmetric organocatalysis.

Asymmetric intramolecular crossed-benzoin reactions by N-heterocyclic carbene catalysis.

Preparation and Application of 1,3,4-Triphenyl-4,5-dihydro-1H-1,2,4-triazol-5-ylidene, A Stable Carbene

Preparation and Application of 1,3,4‐Triphenyl‐4,5‐dihydro‐1H‐1,2,4‐triazol‐5‐ylidene, a Stable Carbene.

Nucleophilic N‐Heterocyclic Carbenes in Asymmetric Organocatalysis