Additions to Alkenes, Alkynes, and Carbonyl Compounds
E-Book, Englisch, 610 Seiten, PDF, Format (B × H): 170 mm x 240 mm
ISBN: 978-3-13-176521-5
Verlag: Thieme
Format: PDF
Kopierschutz: Adobe DRM (»Systemvoraussetzungen)
Synthesis critically reviews the state of the art of a wide variety of reactions
by which one carbon atom is added to an organic molecule, forming a C-C bond. In
spite of the numerous classic reactions of this kind, there has been enormous
progress in recent years, especially for those reactions involving catalytic
methods. Introduction of substituted methyl groups is a major challenge and only
very recently the first catalysts have been discovered that enable the
introduction of fluoromethyl groups in aromatics.
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Weitere Infos & Material
1.1 Addition to Alkenes1.1.1 Hydroformylation of Alkenes1.1.2 Asymmetric Hydroformylation of Alkenes1.1.3 Tandem Hydroformylation of Alkenes1.1.4 Nonconventional Reaction Media: Hydroformylation, Carbonylation, and Hydroxycarbonylation of Alkenes1.1.5 Hydroformylation of Alkenes: Industrial Applications1.1.6 Carbonylation of Alkenes1.1.7 Cyclopropanation of Alkenes with C-11.1.8 Addition of Carbon Dioxide to Alkenes and Other Unsaturated Hydrocarbons1.1.9 Hydrocyanations of Alkenes1.1.10 Stereoselective Conjugate Addition of Methyl and Cyanide1.1.11 Enantioselective Conjugate Addition of Nitromethane1.2 Addition to Alkynes1.2.1 Carbonylation of Alkynes1.3 Addition to Carbonyl Compounds and Derivatives1.3.1 Stereoselective (Nucleophilic) Methylation of Ketones and Aldehydes1.3.2 Cyanation of Ketones, Aldehydes, and Imines1.3.3 Stereoselective Addition of Nitromethane
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....
