Thiophosgene in Organic Synthesis

The synthetic utility of thiophosgene has recently been widely explored. Besides use in the classical preparations of isothiocyanates, thiocarbamates,thiocarbonates, and thioureas, it can also be successfully used in the synthesis of nitriles, alkenes, thietanes, a wide variety of thioxo-substituted heterocyclic compounds, and inorganic complexes. Thiophosgene is a readily available chemical but can also be conveniently prepared in the laboratory by reductive dechlorination of trichloromethanesulfenyl chloride. The present survey of the literature on thiophosgene is intended to encourage better use of the reagent in future organic syntheses. 1. Introduction 2. Synthesis of Thiophosgene 3. Reactions at a Nitrogen Centre 3.1. Reactions with Primary Amines 3.2. Reactions with Amides 3.3. Reactions with Secondary Amines 3.4. Reactions with Tertiary Amines 3.5. Reactions with Imines 3.6. Reactions with Hydrazines 3.7. Reactions with Diazo Compounds and Azides 4. Reactions at an Oxygen Centre 4.1. Reactions with Alcohols 4.2. Reactions with Phenols 4.3. Reactions with Thiolactones 4.4. Reactions with Oximes 5. Reactions at a Sulfur Centre 5.1. Reactions with Thiols 5.2. Reactions with Dithiolactone Derivatives 6. Reactions at a Carbon Centre 7. Reactions with Organometallic and Inorganic Compounds 8. Miscellaneous Reactions 9. Conclusions