Abstract
The stereoselective transformation of 2-thioamides to 2-thio-3-chloroacrylamidesand the investigation of the scope of this transformation, includingextension to ester and nitrile derivatives, is described. Thesehighly functionalised acrylamide derivatives are synthetically versatile,and their reactivity has been investigated in a wide range of transformations,including chemoselective oxidation to the racemic sulfoxide or sulfone,and enantioselective and -diastereoselective oxidationto the sulfoxides. The 2-thio-3-chloroacrylamides were found tobe very effective Michael acceptors in nucleophilic addition/substitutionreactions, dienophiles in Diels-Alder cycloadditions, anddipolarophiles in 1,3-dipolar cycloadditions. The level of oxidationat sulfur was found to strongly influence the reactivity. This accountsummarises synthetic and mechanistic aspects of the research programmefocussed on the synthesis and reactivity of 2-thio-3-chloroacrylamidesin our research group over the past decade. 1 Introduction - Discovery of 2-Thio-2-chloroacrylamides andInitial Observations 2 Synthesis of the β-Chloroacrylamides and Investigationof their Mechanistic Pathway 3 Extension of the Methodology to β-Haloacrylamides, β-Acrylates,and β-Acrylonitriles 4 Oxidation of the β-Chloroacrylamides 4.1 Chemoselective Sulfur Oxidation 4.2 Enantioselective Sulfur Oxidation 4.3 Diastereoselective Sulfur Oxidation 5 Nucleophilic Addition/Substitution Reactions of the β--Chloroacrylamides 5.1 Addition of Carbon Nucleophiles 5.2 Addition of Nitrogen Nucleophiles 5.3 Addition of Oxygen Nucleophiles 5.4 Addition of Sulfur and Selenium Nucleophiles 5.5 Summary of Nucleophilic Additions 6 Reactivity of the β-Chloroacrylamides in Diels-Alder -CycloadditionReactions 6.1 Cycloadditions with Cyclopentadiene 6.2 Cycloadditions with 2,3-Dimethyl-1,3-butadiene 6.3 Summary of Diels-Alder Cycloadditions 7 Reactivity of the β-Chloroacrylamides in 1,3-Dipolar -CycloadditionReactions 7.1 Cycloadditions with Diazoalkanes 7.2 Cycloadditions with Nitrile Oxides and Nitrones 8 Conclusion
Published Version
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