In recent years, the olefin metathesis reaction has attracted widespread attention as a versatile carbon−carbon bond-forming method. Many new applications have become possible because of major advances in catalyst design. State-of-the-art ruthenium catalysts are not only highly active but also compatible with most functional groups and easy to use. This Account traces the ideas and discoveries that were instrumental in the development of these catalysts, with particular emphasis on (PCy3)2Cl2RuCHPh and its derivatives. The discussion includes an analysis of trends in catalyst activity, a description of catalysts coordinated with N-heterocyclic carbene ligands, and an overview of ongoing work to improve the activity, stability, and selectivity of this family of L2X2RuCHR complexes.

http://web4.uwindsor.ca/users/j/jlichaa/reference.nsf/0/10ff8b04ff3a317885256d88005720f6/$FILE/acr-2001-34-18-metath-grubbs.pdf

The Development of L2X2RuCHR Olefin Metathesis Catalysts: An Organometallic Success Story

The advent of well-defined catalysts for olefin metathesis which combine high activity, durability, and excellent tolerance towards polar functional groups has revolutionized the field. The past decade has seen the rapid embrace of these reagents as tools for advanced organic and polymer chemistry and the success of this development is witnessed by a plethora of elegant applications to the synthesis of natural and nonnatural products. This review article provides an overview of these developments and intends to familiarize the reader with some very recent advances which hold the promise to expand the scope of the reaction even further. Moreover, the positive impact of metathesis on the fundamental logic of retrosynthetic planning is demonstrated by means of typical examples. Finally, it will be shown that metathesis is by no means restricted to alkenes as substrates, and some comments on metathesis reactions following unconventional mechanistic pathways will also be presented.

Olefin Metathesis and Beyond

Living ring-opening metathesis polymerization

Homogeneous Metathesis Polymerization by Well-Defined Group VI and Group VIII Transition-Metal Alkylidenes: Fundamentals and Applications in the Preparation of Advanced Materials.

Recent Advances in Transition-Metal-Catalyzed Functionalization of Unstrained Carbon–Carbon Bonds

Alkene metathesis: new developments in catalyst design and application

Direct Observation of Orthogonal Orientation of an Aromatic Ring Attached to the Carbene Carbon in Fischer Carbene Complexes in Solution: Diastereotopicity of Benzyl Protons as a Stereochemical Probe†

Solution and solid state conformation of Fischer carbene complexes vis-à-vis conformation of aryl carboxamides: complexation of the aromatic ring by tricarbonylchromium makes a difference

Current research in alkene metathesis has two significant strands of development. One pertains to rapid progress in catalyst development which permits far greater tolerance of organic functional groups. This includes synthesis of new, structurally defined, catalytically active molecules, some of them even performing in aqueous environment. The second aspect is a consequence of the first one. Not only polyfunctional polymeric materials are obtainable as a result of “living” ring-opening metathetic polymerisation of structurally complex monomers, but alkene metathesis provided an efficient ring-closing strategy for use in synthesizing intricate structural patterns of important organic molecules. In this review, the information is classified in terms of type of catalysis — homogeneous or heterogeneous. Each type is subdivided according to the metal used, so that a reactivity pattern might emerge to guide future developments.

K. N. Jayaprakash

Papers

Alkene metathesis: new developments in catalyst design and application

Direct Observation of Orthogonal Orientation of an Aromatic Ring Attached to the Carbene Carbon in Fischer Carbene Complexes in Solution: Diastereotopicity of Benzyl Protons as a Stereochemical Probe†

Solution and solid state conformation of Fischer carbene complexes vis-à-vis conformation of aryl carboxamides: complexation of the aromatic ring by tricarbonylchromium makes a difference

Alkene Metathesis: New Developments in Catalyst Design and Application