Reactions of Aldehydes and Ketones and Their Derivatives

This Chapter Contains Sections titled: Formation and Reactions of Acetals and Related Species Reactions of Glucosides Reactions of Ketenes and Related Cumulenes Formation and Reactions of Nitrogen Derivatives Imines: Synthesis, and General and Iminium Chemistry Mannich, Mannich-type, and Nitro-Mannich Reactions Other ‘Name’ Reactions of Imines Stereoselective Hydrogenation of Imines, and Other Reductive Processes Stereoselective Allyl-, Aryl-, Alkenyl-, and Alkynyl-ations of Imines Other Stereoselective Reactions of Imines Other Reactions of Imines Oximes Hydrazones and Related Species CC Bond Formation and Fission: Aldol and Related Reactions Reviews of Aldols, and General Reviews of Asymmetric Catalysis Asymmetric Aldols The Mukaiyama Aldol The Morita–Baylis–Hillman Reaction Other Aldol-type Reactions Allylation and Related Reactions Alkynylations The Benzoin and Stetter Reactions The Michael Addition Miscellaneous Condensations Other Addition Reactions Addition of Organozincs Arylations, and Addition of Other Organometallics, Including Grignards The Wittig and Other Olefinations Hydrosilylation, Hydrophosphonylation, Hydroboration, and Hydroacylation Formation of Cyanohydrins, Cyanosilylation, and other Cyanations α-Aminations and Related Reactions Enolization, Reactions of Enolates, and Related Reactions α-Halogenation, α-Alkylation, and Other α-Substitutions Oxidation and Reduction of Carbonyl Compounds Oxidation of Aldehydes to Acids Other Oxidations and Oxidative Processes Reduction Reactions Miscellaneous Cyclizations Other Reactions References This chapter discusses the reactions of aldehydes and ketones and their derivatives. Several papers deal with the conversion of aldehydes to carboxylic acids, or oxidation to the acid level, such as anhydride or nitrile formation. Direct Mannich-type reactions generating both alpha- and beta-amino esters from a range of carbonyl compounds and aldimines have been described. Second-order Moller-Plesset perturbation theory has been employed to investigate their reactivity, with pericyclic reactions giving rise to five-membered cyclic carbene intermediates, leading-through subsequent hydrogen transfers-to pyrazoles and imidazoles. Several asymmetric transfer hydrogenations were carried out on ketones in formic acid/triethylamine, using ruthenium catalysts. A review examines the current understanding of enantioselective reduction of prochiral aromatic ketones by Noyori and Nayari-Ikariya bifunctional catalysts, two of the bestbehaved catalytic systems: they deliver up to 99.9% ee with very low catalyst loading of ca. 10-5 mol%.