Hydroxy(organosulfonyloxy)iodoarenes in Organic Synthesis

In Part I of this Account, the utility of hydroxy(sulfonyloxy)iodobenzenes, PhI(OH)OSO2R, and closely related sulfonyloxyiodinanes for the oxysulfonylation, aryliodination, and oxidation of organic molecules is reviewed. Not only is the work from the research groups of the principal authors covered, but also that of other major researchers in the field. These hypervalent iodine reagents have been employed for the preparation of α-sulfonyloxy carbonyl compounds (ketones, esters, lactones), vic-ditosyloxyalkanes, 1,4-disulfonyloxyalkenes, tosyloxylactones, bislactones, ketolactones, isoflavones, and alkynyl- and vinyliodonium salts. The functionalization of cubanes, the direct conversion of carboxamides to alkylammonium tosylates and various oxidative rearrangements are also described. Some underlying and unifying mechanistic interpretations are presented with particular emphasis on the stereo- and regiochemistry attending the aforementioned transformations. In Part II one of the authors (GFK) documents the role of serendipity in a number of discoveries achieved by his group in this area. Part 1. Hydroxy(organosulfonyloxy)iodoarenes in Organic Synthesis (R. M. Moriarty, R. K. Vaid, G. F. Koser) 1. Introduction 2. Synthesis and Structure of Hydroxy(organosulfonyloxy)-iodoarenes 3. Synthesis of vic-Ditosyloxyalkanes, vic-Dimesyloxyalkanes and vic-Bistrifloxyalkanes from Alkenes 4. Synthesis of 1,4-Ditosyloxyalkenes and 1,4-Bistrifloxyalkenes from Conjugated Dienes 5. Intramolecular Participation of Nucleophilic Functional Groups in the Oxidation of Alkenes with Hydroxy(tosyloxy)-iodobenzene 5.1. Participation of the Carboxyl Group: Synthesis of Tosyloxylactones and Bislactones 5.2. Participation of the Hydroxyl Group 5.3. Participation of Carbamate Nitrogen 6. Reactions of Allenes with Hydroxy(tosyloxy)iodobenzene 7. Synthesis of 1-Alkynyl- and 1-Alkenyliodonium Salts from Alkynes 8. Oxidative Rearrangement of Alkynes to Esters 9. Ligand Transfer and Oxidative Displacement Reactions of Iodoarenes and Iodoalkanes with Sulfonyloxyiodinanes: Synthesis of Sulfonyloxycubanes and -homocubanes 10. Synthesis of α-Sulfonyloxy Ketones and α-Sulfonyloxy β-Dicarbonyl Compounds 11. Synthesis of α-Substituted Ketones, Thiazoles, and Selenazoles 12. Intramolecular Participation of the Carboxyl Group in the Oxidation of Ketones with Hydroxy(tosyloxy)iodobenzene: Synthesis of Oxolactones 13. Oxidative Rearrangement of Aryl Ketones to Esters 14. Synthesis of Isoflavones and 2,3-Dimethoxy-3-hydroxy-flavanones 15. Reactions of Chalcones with Hydroxy(tosyloxy)iodobenzene 16. Synthesis of Sulfonyloxy Esters and Lactones 17. Hydroxy(tosyloxy)iodobenzene as a Hofmann Reagent: Synthesis of Amines from Carboxamides 18. Oxidation of Sulfides 19. Oxidative Cleavage of Glycols 20. Oxidation of Hydroquinones 21. Synthesis of Diaryl- and Aryl(heteroaryl)iodonium Salts 22. Synthesis and Reactivity of Hydroxy(sulfonyloxy)iodopentafluorobenzenes 23. Conclusion Part II. Recollections on the Role of Serendipity in Our Researches on Hydroxy(tosyloxy)iodo benzene (G. F. Koser) 24. Why Hydroxy(tosyloxy)iodobenzene? 25. Mood Indigo and the Ligand-Transfer Reaction 26. Will We Ever Be Able to Predict the Behavior of Hydroxy-(tosyloxy)iodobenzene? 27. Is Hydroxy(tosyloxy)iodobenzene Soluble in Anything? 28. Make Sure that You Attend Seminars 29. Read the Literature. Even "Me Too" Research Can Be Fruitful