The Use of Thiocarbonyl Compounds in Carbon-Carbon Bond Forming Reactions

Patrick Metzner

doi:10.1055/s-1992-26330

Synthesis 1992; 1992(12): 1185-1199
DOI: 10.1055/s-1992-26330

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The Use of Thiocarbonyl Compounds in Carbon-Carbon Bond Forming Reactions

Patrick Metzner^*

^*Laboratoire de Chimie des Composés Thio-Organiques (Unité Associée au CNRS), ISMRA, 6 Boulevard du Maréchal Juin, F-14050 Caen, France

Abstract

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The behavior of thioaldehydes, thioketones, thiono esterts (O-alkyl thioates) and dithio esters (S-alkyl dithioates) has been reviewed. Specific properties of thiocarbonyl compounds have been shown: Michael addition reaction of enethiolates, thiophilic addition of nucleophiles, easy thio-Claisen rearrangement, [4+2] cycloaddition with dienes and rich dipolarophile chemistry. 1. Introduction 2. Nucleophilic Reactions in Basic Medium 2.1. Generation of Enethiolates 2.2. Aldol Reaction 2.3. Wittig-Horner Reaction 2.4. Michael Addition 2.5. Opening of Epoxides 2.6. Sulfur Alkylation 3. Reactions with Nucleophiles 3.1. Thiophilic Versus Carbophilic Addition of Grignard Reagents and Alkyllithiums 3.2. Unsaturated Thiocarbonyl Compounds as Michael Acceptors 3.3. Claisen Condensation and Other Reactions with Enolates 3.4. Reactions with Sulfur and Phosphorus Ylides 4. Pericyclic Reactions 4.1. [2.3] Sigmatropic Rearrangements 4.2. The Thio-Claisen Rearrangement 4.3. Other [3.3] Sigmatropic Rearrangements 4.4. Diels-Alder Addition Reaction 4.4.1. Thiocarbonyl Compounds as Dienophiles 4.4.2. Thiocarbonyl Compounds as Dienes 4.5. Ene Reaction 4.6. [2+2] Cycloadditions 4.7. Dipolar Cycloadditions 4.7.1. Diazoalkanes and Generation of Thiocarbonyl Ylides 4.7.2. Cycloaddition with Nitrile Oxides, Imines and Sulfides, Nitrones, Nitronates, Azomethine Imines and Ylides 5. Conclusion

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