Abstracts

1.1.1 Hydroformylation of Alkenes

R. P.J. Bronger, P. C.J. Kamer, and D. Vogt

Hydroformylation of alkenes is a mild and clean method for the functionalization of hydrocarbons and has grown to be among the most important homogeneously catalyzed reactions in industry. It is a 100% atom-economic reaction to prepare aldehydes that are important synthons for organic synthesis, and has wide functional group compatibility.

In this review the focus is on the effects of various catalysts on the selective hydroformylation of both functionalized and unfunctionalized alkenes to produce high-value aldehydes. In particular, rhodium catalysts have undergone a remarkable development, while cobalt catalysts have remained more or less unchanged over the years, and palladium has recently been recognized as a suitable transition metal for hydroformylation.

Keywords: hydroformylation homogeneous catalysis aldehydes phosphorus ligands ligand design rhodium cobalt palladium platinum

1.1.2 Asymmetric Hydroformylation of Alkenes

C. Godard, B. F. Perandones, and C. Claver

Asymmetric hydroformylation is a very promising catalytic reaction that produces chiral aldehydes from inexpensive feedstocks (alkenes and syngas) in a single step under essentially neutral reaction conditions. Asymmetric hydroformylation offers a great potential for the fine chemical industry since enantiomerically pure or enriched aldehydes can be obtained through hydroformylation of a variety of substrates using the appropriate chiral-phosphorus-modified rhodium catalyst. This chapter presents the successful transformations of benchmark and specific substrates, organized according to the substitution pattern.

Keywords: asymmetric catalysis hydroformylation rhodium chirality phosphorus ligands aldehydes

1.1.3 Tandem Hydroformylation of Alkenes

I. Fleischer and E. Mejía

This overview encompasses the most recent developments in the field of tandem hydroformylation reactions up to late 2012. The combination of the hydroformylation of alkenes and a subsequent transformation of the corresponding aldehydes gives access to a broad range of functionalities, relevant for both academy and industry. The chapter is subdivided according to the type of functionalization following the hydroformylation step.

Keywords: acetalization aldehydes aldol reaction alkenes amines C-C bonds carbon-heteroatom bonds homogeneous catalysis hydroformylation metal carbonyl complexes rhodium catalysts tandem reactions domino reactions Wittig reaction reductive amination

1.1.4 Nonconventional Reaction Media: Hydroformylation, Carbonylation, and Hydroxycarbonylation of Alkenes

A. Mortreux, M. Sauthier, E. Monflier, and S. Tilloy

This chapter focuses on catalytic reactions involving the use of carbon monoxide and alkenes together with tertiary substrates such as hydrogen, alcohols, amines, or water where the catalyst recovery and recycling has been emphasized via the use of biphasic media. These atom-economical catalytic reactions result in the synthesis of aldehydes, esters, amines, and carboxylic acids, as well as polyketones, where the activity and regioselectivity concerns have been addressed.

Keywords: hydroformylation hydroesterification carbonylation hydroxycarbonylation carbon monoxide biphasic catalysis ionic liquid water-soluble ligands phosphines cyclodextrins recycling regioselectivity

1.1.5 Hydroformylation of Alkenes: Industrial Applications

J. G. de Vries

Alkenes can be converted into aldehydes using a highly atom-efficient hydroformylation reaction in which carbon monoxide and hydrogen are added across the double bond. In this chapter industrial hydroformylation processes are described. Catalysts are based on cobalt with or without trialkylphosphine ligands, or rhodium with triarylphosphine ligands or monodentate or bidentate triaryl phosphite ligands. The products are raw materials for plasticizers and solvents.

Keywords: alcohols aldehydes alkenes carbonyl complexes cobalt catalysts diols hydroformylation isomerization rhodium catalysts phosphine oxides phosphines phosphites

1.1.6 Carbonylation of Alkenes

M. L. Clarke and J. A. Fuentes

This chapter provides a concise overview of metal-catalyzed additions to alkenes that involve carbon monoxide and another nucleophilic species, such as water or an alcohol. This is an important area of research in terms of several commodity chemical targets, with many papers devoted to the evolution and mechanistic interrogation of catalysts that are viable for industry. This chapter demonstrates that this class of reaction is synthetically useful for a wide range of possible target molecules. Such reactions include the formation of carboxylic acids, including the "profen" family of drugs by hydroxycarbonylation of vinylarenes, in which it is now possible to control both regioselectivity and, to a lesser degree, enantioselectivity. The alkoxycarbonylation of alkenes primarily refers to what is more strictly a hydroalkoxycarbonylation, where hydride and carbon monoxide are added across an alkene and then terminated with an alcohol. Both intermolecular and intramolecular variants of this reaction are discussed. Other variants of alkene carbonylation are those where a nucleophile attacks an alkene, with the other terminus being functionalized with a carboxylic acid derivative derived from carbon monoxide. A few examples are highlighted with typical experimental procedures that should aid the nonspecialist in conducting these reactions.

Keywords: alkoxycarbonylation hydroalkoxycarbonylation hydroesterification hydroxycarbonylation hydrocarbonylation cyclization asymmetric synthesis carbon monoxide carboxylic acids carboxylic acid esters chiral phosphines large-scale processes atom efficiency green chemistry

1.1.7 Cyclopropanation of Alkenes with C-1

T. R. Belderrain and M. C. Nicasio

Cyclopropanation of alkenes is a direct route for the synthesis of cyclopropanes. This can be achieved by various methodologies. Specifically, this chapter is intended to provide an overview of the use of one-carbon reagents in cyclopropanation; thus, only synthetic methodologies regarding the use of methylene-transfer reagents are discussed.

Keywords: alkenes cyclopropanes diazomethane carbenes transition-metal catalysis dihalomethanes zinc reagents ylides

1.1.8 Addition of Carbon Dioxide to Alkenes and Other Unsaturated Hydrocarbons

J. Takaya and N. Iwasawa

Various transition-metal complexes promote C-C bond-forming reactions of carbon dioxide with acyclic unsaturated hydrocarbons including alkenes, alkynes, 1,3-dienes, and allenes. These reactions provide efficient methods for the synthesis of carboxylic acids and their derivatives.

Keywords: carbon dioxide carboxylic acids esters lactones pyrones C-C bond formation transition metals alkenes 1,3-dienes alkynes allenes

1.1.9 Hydrocyanation of Alkenes

M. E. Tauchert

Hydrocyanation of alkenes is an atom-economical reaction to install a functionalized C-1 building block into a molecule. The reaction can be run to yield either the linear or the branched nitrile product. Branched nitriles can be produced in moderate to good enantiomeric excess. A detailed overview of the mechanism of nickel-catalyzed hydrocyanation is provided to help assess the scope and limitations of this reaction.

Keywords: styrene vinylarenes dienes hydrocyanation alkenes nitriles nickel palladium

1.1.10 Stereoselective Conjugate Addition of Methyl and Cyanide

B. Goldfuss

Conjugate additions of methyl and cyanide nucleophiles to Michael acceptors are powerful methods for stereoselective homologation. New ligands and a variety of copper sources today enable highly enantioselective nucleophilic 1,4-methylations. Besides Grignard reagents, methylzinc reagents and trimethylaluminum are well established as nucleophilic methyl sources. Enantioselective cyanations of alkenes, aldehydes, or imines can be accomplished with metal catalysts (e.g., based on nickel, aluminum, or titanium) or organocatalysts, mostly employing silyl cyanides or acetone cyanohydrin as the cyanide source.

Keywords: copper catalysts methyl Grignard reagents methylaluminum reagents cyanide asymmetric catalysis asymmetric synthesis conjugate addition C-C bonds carbon-heteroatom bonds Michael acceptors nucleophilic addition

1.1.11 Enantioselective Conjugate Addition of Nitromethane

R. Ballini and M....