Organic Synthesis in Water

The use of water as a medium for promoting organic reactions has, for the most part, been non-existent, despite the fact that water has served, and continues to serve, as the solvent in which the vast majority of biochemical processes take place. Chemists have only recently come to appreciate the enormous potential that water holds for those engaged in synthetic organic and organometallic chemistry, in part because of water's unique enthalpic and entropic properties. In this volume, an international team of authors, each taking advantage of the unique properties of water for carrying out organic transformations, is brought together in order to provide a timely and concise overview of current research. The chapters focus on the practical use of water in synthetic organic chemistry, with special emphasis on Diels-Alder reactions, Claisen rearrangements, organometallic chemistry, transition-metal catalysis, oxida tions and reductions. I am grateful to my colleagues, J. Auge, I. Beletskaya, A. Cheprakov, F. Fringuelli, J. Gajewski, P. Gamer, S. Kobayashi, A. Lubineau, D. Parker, O. Piermatti, F. Pizzo and Y. Queneau, for participating in this venture. Their knowledge and experience have been invaluable in putting this volume together.

Klappentext

The use of water as a medium for promoting organic reactions has been rather neglected in the development of organic synthesis, despite the fact that it is the solvent in which almost all biochemical processes take place. Chemists have only recently started to appreciate the enormous potential water has to offer in the development of new synthetic reactions and strategies, where it can offer benefits in both unique chemistry and reduced environmental impact. In this new book, the editor, well known for his contribution to the development of water as a useful medium in synthetic organic chemistry, has assembled an international team of authors, themselves at the forefront of research into the use of the unique properties of water carrying out organic transformations, to provide a timely and concise overview of current research. By focusing on the practical use of water in synthetic organic chemistry, and with the concern for the use of solvents in organic chemistry, professional chemists, particularly those involved in industrial research and development, will find this book an essential guide to the current state of the art, and a useful starting point in their own research. Academic chemists, including postgraduate and advanced undergraduate students, will find this book an invaluable guide to this exciting and important area of chemistry.

Inhalt
1 Diels-Alder reactions in aqueous media.- 1.1 Introduction.- 1.2 The effect of water on Diels-Alder reactivity.- 1.3 Regioselectivity and endo/exo-selectivity.- 1.4 Diastereofacial selectivity.- 1.5 Synthetic applications.- 1.6 Intramolecular cycloadditions.- References.- 2 Hetero Diels-Alder reactions.- 2.1 Introduction.- 2.2 Aza Diels-Alder reactions in aqueous media.- 2.3 Synthetic exploitation of the aqueous aza Diels-Alder reaction.- 2.4 Retro aza Diels-Alder reactions in aqueous media.- 3.- References.- 3 Claisen rearrangements in aqueous solution.- 3.1 Introduction.- 3.2 Aromatic Claisen rearrangement.- 3.3 Aliphatic Claisen rearrangement.- 3.4 Synthetic exploitation of aqueous Claisen rearrangements.- 3.5 Water as a solvent.- 3.6 Multiparameter correlation-factor analyses.- 3.7 Other developments in Claisen rearrangements in aqueous solution.- 3.8 Summary.- Acknowledgements.- References.- 4 Carbonyl additions and organometallic chemistry in water.- 4.1 Introduction.- 4.2 Barbier-type alkylation reactions.- 4.3 Conjugate 1,4-additions.- 4.4 Cross-aldol and Reformatsky-type reactions.- 4.5 Pinacol coupling reactions.- 4.6 Miscellaneous reactions.- References.- 5 Aqueous transition-metal catalysis.- 5.1 Trends in aqueous transition-metal catalysis.- 5.2 Palladium-catalyzed cross-coupling reactions.- 5.3 Heck reaction.- 5.4 Carbonylation.- 5.5 Hydroformylation.- 5.6 Hydrogenation.- 5.7 Other reactions.- References.- 6 Oxidations and reductions in water.- 6.1 Oxidations in water: introduction.- 6.2 Oxidation of carbon-hydrogen bonds.- 6.3 Oxidation of carbon-carbon double bonds.- 6.4 Other oxidations.- 6.5 Reductions in water: introduction.- 6.6 Reduction of carbon-carbon double and triple bonds.- 6.7 Reduction of carbonyl and nitro functionalities.- 6.8 Other reductions.- References.- 7 Base-catalyzed aldol- and Michael-type condensations in aqueous media.- 7.1 Introduction.- 7.2 Claisen-Schmidt reaction.- 7.3 Vinylogous aldol reaction.- 7.4 Knoevenagel reaction.- 7.5 Tollens reaction.- 7.6 Weiss-Cook reaction.- 7.7 Michael reaction.- References.- 8 Water-stable rare-earth Lewis-add catalysis in aqueous and organic solvents.- 8.1 Introduction.- 8.2 Aldol reactions.- 8.3 Allylation reactions.- 8.4 Diels-Alder reactions.- 8.5 Mannich-type reactions.- 8.6 Imino Diels-Alder reactions: synthesis of pyridine and quinoline derivatives.- 8.7 Asymmetric aza Diels-Alder reactions: synthesis of tetrahydroquinoline derivatives using a chiral lanthanide Lewis acid as catalyst.- 8.8 Micellar systems.- Acknowledgements.- References.