Organometallics and Renewables

Table of Contents

1. Frontmatter

2. Olefin Metathesis of Renewable Platform Chemicals

   Lucas Montero de Espinosa, Michael A. R. Meier

   Abstract

   Olefinic double bonds are often found in the structure of natural compounds. This makes olefin metathesis a powerful tool for their transformation into valuable renewable platform chemicals and, in some cases, directly for targeted chemical products. Natural products display many different structures and functional groups, which in some cases challenge catalyst performance. In this respect, new catalysts with improved performance are constantly developed providing new application possibilities. This chapter covers the research performed in the field of olefin metathesis with renewable chemicals, starting from the early days of this chemical reaction to the present situation. Special attention is given to renewables naturally containing double bonds, like oleochemicals or terpenes. On the other hand, the introduction of double bonds in the structure of non-olefinic renewables, such as carbohydrates, amino acids, or peptides, and their use as olefin metathesis substrates are discussed. This chapter is subdivided in two main parts covering the synthesis of platform chemicals and the synthesis of polymers, respectively.

3. Pd-Catalyzed Telomerization of 1,3-Dienes with Multifunctional Renewable Substrates: Versatile Routes for the Valorization of Biomass-Derived Platform Molecules

   Pieter C. A. Bruijnincx, Robin Jastrzebski, Peter J. C. Hausoul, Robertus J. M. Klein Gebbink, Bert M. Weckhuysen

   Abstract

   The dimerization of 1,3-dienes (e.g. butadiene) with the addition of a protic nucleophile (e.g. methanol) yields 2,7-octadienyl ethers in the so-called telomerization reaction. This reaction is most efficiently catalyzed by homogeneous palladium complexes. The field has experienced a renaissance in recent years as many of the platform molecules that can be renewably obtained from biomass are well-suited to act as multifunctional nucleophiles in this reaction. In addition, the process adheres to many of the principles of green chemistry, given that the reaction is 100% atom efficient and produces little waste. The telomerization reaction thus provides a versatile route for the production of valuable bulk and specialty chemicals that are (at least partly) green and renewable. The use of various multifunctional substrates that can be obtained from biomass is covered in this review, as well as mechanistic aspects of the telomerization reaction.

4. Hydroformylation and Related Reactions of Renewable Resources

   A. Behr, A. J. Vorholt

   Abstract

   Today, the increasing global population and the rising consumption of fossil resources for energy and material use are important issues for research activities in the field of transformation of renewable resources. In petrochemistry, well-established reactions like hydroformylation are performed in multiton plants all over the world and are important examples for processing new resources beyond fossil feedstocks. This chapter deals with the application of three important reactions with carbon monoxide, specifically hydroformylation, hydroaminomethylation, and hydroesterification with renewables which have a C–C-double bond in the starting material. In these reactions, unsaturated oleocompounds and a variety of terpenes can be employed because of their naturally available double bonds.

5. Catalytic Oxidation and Deoxygenation of Renewables with Rhenium Complexes

   Ties J. Korstanje, Robertus J. M. Klein Gebbink

   Abstract

   Transformation of renewables has received major research interest in recent years, opening up completely new research areas, in particular in the field of oxidation and deoxygenation. For the oxidation reaction, rhenium complexes, in particular methyltrioxorhenium, are well known for their potential as catalysts, but they are also potent catalysts for the deoxygenation reaction. The application of organometallic rhenium complexes in both the oxidation and deoxygenation reactions using a broad range of substrates derived from renewable resources, such as terpenes, oils, fats, lignin, and sugar alcohols, is reviewed in this chapter.

6. Recent Developments in Catalytic Activation of Renewable Resources for Polymer Synthesis

   Antoine Buchard, Clare M. Bakewell, Jonathan Weiner, Charlotte K. Williams

   Abstract

   This review describes the application of organometallic and inorganic complexes as initiators and catalysts for polymerizations using renewable resources. It focuses on the ring-opening polymerization of lactide and the alternating copolymerization of carbon dioxide and epoxides. For lactide ring-opening polymerization, a general background to the reaction mechanism, kinetics, stereochemical control and polymerization control is presented. This is followed by reviews of the use of groups 3 and 13 complexes as initiators. Group 3 complexes show excellent rates, amongst the fastest reported for this polymerization, and in some cases stereocontrol. The group 13 complexes have good precedent for stereocontrol; recent advances using heavier group 13 elements, In and Ga, are highlighted. For the alternating copolymerization, an overview of the reaction kinetics, mechanism and control is presented. Recent advances in the use of catalyst operating at low pressure and dinuclear catalysts are presented.

7. Backmatter