Special Issue "Olefin Metathesis and Its Application"

Guest Editor
Dr. Anna G. Wenzel
Joint Science Department, Claremont McKenna, Pitzer and Scripps Colleges, Claremont, California 91711, USA
E-Mail: awenzel@jsd.claremont.edu
Interests: asymmetric catalysis; organometallic cemistry; organic synthesis

Dear Colleagues,

The reliable and efficient generation of carbon-carbon bonds underpins the foundation of chemical synthesis. Of these, olefin metathesis has risen to the forefront of the methods utilized for the preparation of alkenes. Catalyst developments in the past 25 years have dramatically increased the accessibility of this reaction for general use, with many catalysts now being commercially available. In addition, significant progress has been made in understanding the catalyst and substrate structural features, their interactions, and experimental conditions crucial to reaction selectivity. This has led to numerous applications of olefin metathesis in both academia and industry. In particular, cross-metathesis, ring-closing metathesis, enyne metathesis, ring-rearrangement metathesis, as well as tandem processes, remain highly active areas of investigation.

Despite the progress that has been achieved, many challenges remain, principally with regard to catalyst stability and control. The issue of control manifests itself in a myriad of ways, be it regiochemical or stereochemical. For example, the issue of olefin diastereocontrol in metathesis remains a significant challenge due to the thermodynamic nature of the reaction. Additionally, the pursuit of substrate control, while maintaining high catalyst turnover numbers in the face of steric and electronic impediments, remains a significant goal of catalyst design. Fortunately, recent years have seen many elegant solutions towards progress in overcoming these hurdles.

This Special Issue on olefin metathesis will offer an attractive forum to present recent results in olefin metathesis pertaining to catalyst development, broadened substrate scope and/or stereocontrol, as well as the application of olefin metathesis to synthesis. I strongly encourage authors to submit papers for Molecules’ Special Issue on Olefin Metathesis. I believe that the topics covered will thoroughly convey the expanding potential and applicability of this versatile reaction.

Dr. Anna G. Wenzel
Guest Editor

Submission

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• olefin metathesis
• ruthenium
• molybdenum
• transition metal
• alkylidene
• catalytic

Type of Paper: Review
Title: Dimerization, isomerization, and Metathesis of Ethene on Nickel Ion Loaded on Silica
Author: Masakazu Iwamoto
Affiliation: Chemical Resources Laboratory, Tokyo Institute of Technology, 4259-R1-5 Nagatsuta, Midori-ku, Yokohama 226-8503, Japan;
E-Mail: iwamoto@res.titech.ac.jp
Abstract: The increment in propene production is one of the significant objectives to be achieved in the present petroleum chemistry. Especially the one-path conversion of ethene to propene (ETP reaction, 3C2H4 à2C3H6) is the most desired process. In our efforts, the specific acid catalysis of mesoporous silica was combined with the catalysis of nickel ion, which could turn the new type of ETP reaction into reality. The one-path conversion of ethene was 68% and the propene selectivity was 48% with 43% of butenes in a continuous gas-flow system at 673 K and an atmospheric pressure. The reactivity of lower olefins and the dependences of the ETP reaction on the contact time and the partial pressure of ethene followed the reaction mechanism consisting of dimerization of ethene to 1-butene, isomerization of 1-butene to 2-, and metathesis of 2-butene and ETP. The Ni-loaded mesoporous silica catalysts were characterized mainly by EXAFS and TPR techniques. The local structures of the nickel species active for the ETP reaction were very similar to that of layered nickel silicate, while those on the inert catalysts were the same as that of NiO particles.

Type of Paper: Review
Authors: Giuseppe Vasapollo and Giuseppe Mele
Affiliation: Dipartimento di Ingegneria dell'Innovazione, Università di Lecce, Via Arnesano, 73100 Lecce, Italy; E-Mail: giuseppe.vasapollo@unisalento.it (G.V.)
Title: Olefin Metathesis of Natural and Hybrid Compounds
Abstract: Olefin metathesis has been used in several areas of synthetic organic chemistry including organometallic and polymer chemistry, synthesis of small  molecule. Such reaction has been applied to Cardanol, for the preparation hybrid materials. The long chain attached to the meta position of the phenolic ring of cardanol confers to all derivatives particular properties (good solubility, interesting physical properties) but also allowed to prepare new cardanol hybrid materials with porphyrins, phthalocyanines and fullerenes. The aim of this review is to show  that metathesis reaction can be applied to cardanol and to show also that the chemistry of cardanol is a stimulating area of academic and industrial research.

Type of Paper: Review
Title: Studies of Ruthenium Olefin Metathesis Catalysts and Their Catalytic Activity in Metathesis Reactions by Mass Spectrometry
Author: Haoyang Wang
Affiliation: Shanghai Institute of Organic Chemistry, CAS Lingling Road 345, 200032 Shanghai, China
Abstract: The general concepts, features and applications of mass spectrometry for  studying the Ru-olefin metathesis catalysts and their catalytic activity in metathesis  reactions are reviewed. At the same time, the advantages of mass spectrometry in  studying of Ru-olefin metathesis catalysts and their catalytic reactions allow chemists to characterize Ru-olefin metathesis catalysts, probe the metathesis reaction mechanisms, intercept/characterize transient reactive intermediates in solution and even study on decomposition process and products of Ru-Carbene catalysts. Important information from mass spectrometric studies of Ru-olefin metathesis catalysts and their applications in chemistry of olefin metathesis are summarized.
Keywords: Ru-catalyzed olefin metathesis catalysts; reaction mechanism; mass spectrometry; decomposition reaction

Type of Paper: Article
Title: Development of a New and Convenient Method for the Preparation of Ring-Closing Metathesis Catalysts
Author: Yann Schrodi
Affiliation: Department of Chemistry and Biochemistry, California State University Northridge, Northridge, California 91330, USA; E-Mail: yann.schrodi@csun.edu.
Abstract: We have previously reported on the preparation of a new ruthenium phenylindenylidene complex by a one-step method based on organic precursor 1a (Scheme 1).  This new complex possesses catalytic activity in ring-closing metathesis comparable to that of related highly active commercial olefin metathesis catalysts.1  Herein, we describe the reaction of several other organic precursors (1b-d, see below) with different ruthenium starting materials (e.g., RuCl2(p-cymene)(PCy3) and RuCl2(PPh3)3).  The influence of the organic precursor’s properties on the formation of ruthenium phenylindenylidene complexes and on their olefin metathesis activity are discussed.