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TitleModern Solvents in Organic Synthesis
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LanguageEnglish
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Total Pages205
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Page 2

Organic reactions using water as solvent are reviewed with a focus on pericyclic reactions, car-
bonyl additions, stoichiometric organometallic reactions, oxidations and reductions which
show an unusual outcome in terms of reactivity and selectivity compared with those perfor-
med in organic solvent. The advantages of using water as a solvent are discussed and related
to the hydrophobic effects and the hydrogen-bonding ability of water with a special emphasis
on its very high cohesive energy density which strongly favors organic reactions having a
negative activation volume.

Keywords. Water, Solvents, Organic synthesis, Reactivity, Friendly processes.

1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2

2 The Unique Properties of Liquid Water and Aqueous

Solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3

3 Origin of the Reactivity in Water . . . . . . . . . . . . . . . . . 5

4 Pericyclic Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . 7

4.1 Diels-Alder Reactions . . . . . . . . . . . . . . . . . . . . . . . . . 7
4.1.1 The Effect of Water and Additives on Chemical Reactivity . . . . . 7
4.1.2 The Effect of Water and Additives on Selectivity . . . . . . . . . . . 12
4.2 Hetero-Diels-Alder Reactions . . . . . . . . . . . . . . . . . . . . . 14
4.2.1 Aza-Diels-Alder Reactions . . . . . . . . . . . . . . . . . . . . . . . 14

Page 103

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