Ring-closing metathesis (RCM) is a widely used variation of olefin metathesis in organic chemistry for the synthesis of various unsaturated rings via the intramolecular metathesis of two terminal alkenes, which forms the cycloalkene as the E- or Z- isomers and volatile ethylene.
The most commonly synthesized ring sizes are between 5-7 atoms; however, reported syntheses include 45- up to 90- membered macroheterocycles. These reactions are metal-catalyzed and proceed through a metallacyclobutane intermediate. It was first published by Dider Villemin in 1980 describing the synthesis of an Exaltolide precursor, and later become popularized by Robert H. Grubbs and Richard R. Schrock, who shared the Nobel Prize in Chemistry, along with Yves Chauvin, in 2005 for their combined work in olefin metathesis. RCM is a favorite among organic chemists due to its synthetic utility in the formation of rings, which were previously difficult to access efficiently, and broad substrate scope. Since the only major by-product is ethylene, these reactions may also be considered atom economic, an increasingly important concern in the development of green chemistry.
There are several reviews published on ring-closing metathesis.
The first example of ring-closing metathesis was reported by Dider Villemin in 1980 when he synthesized an Exaltolide precursor using a WCl6/Me4Sn catalyzed metathesis cyclization in 60-65% yield depending on ring size (A). In the following months, Jiro Tsuji reported a similar metathesis reaction describing the preparation of a macrolide catalyzed by WCl6 and dimethyltitanocene (Cp2TiMe2) in a modest 17.9% yield (B). Tsuji describes the olefin metathesis reaction as “...potentially useful in organic synthesis” and addresses the need for the development of a more versatile catalyst to tolerate various functional groups.
In 1987, Siegfried Warwel and Hans Kaitker published a synthesis of symmetric macrocycles through a cross-metathesis dimerization of starting cycloolefins to afford C14, C18, and C20 dienes in 58-74% yield, as well as C16 in 30% yield, using Re2O7 on Al2O3 and Me4Sn for catalyst activation.
This page is automatically generated and may contain information that is not correct, complete, up-to-date, or relevant to your search query. The same applies to every other page on this website. Please make sure to verify the information with EPFL's official sources.
This course on homogeneous catalysis provide a detailed understanding of how these catalysts work at a mechanistic level and give examples of catalyst design for important reactions (hydrogenation, ol
A persistent carbene (also known as stable carbene) is a type of carbene demonstrating particular stability. The best-known examples and by far largest subgroup are the N-heterocyclic carbenes (NHC) (sometimes called Arduengo carbenes), for example diaminocarbenes with the general formula (R2N)2C:, where the four R moieties are typically alkyl and aryl groups. The groups can be linked to give heterocyclic carbenes, such as those derived from imidazole, imidazoline, thiazole or triazole.
Delves into the role of computational chemistry in enhancing Olefin Metathesis, emphasizing theory's predictive power and the Nobel Prize-winning contributions of Chauvin, Grubbs, and Schrock.
Nitrogen-containing compounds are an important class of molecules in medicinal chemistry, chemical biology, biochemistry, material sciences or environmental sciences. Organic nitrogen occurs in many forms, ranging from small building blocks such as urea, a ...
EPFL2022
In a recent study, a new procedure for Z-selective olefin synthesis by reductive coupling of alkyl iodides with terminal alkynes in the presence of iron salts is described. This transformation is representative of many newly developed synthetic routes thro ...
We report the use of photocatalysis for the homolytic ring-opening of carbonyl cyclopropanes. In contrast to previous studies, our approach does not require a metal cocatalyst or a strong reductant. The carbonyl cyclopropanes can be employed for both [2σ + ...