Synthetic and mechanistic aspects of sulfonyl migrations. Issue 14 (10th February 2020)

• Record Type: Journal Article
• Authors: Flynn, Aaran J.; Ford, Alan; Maguire, Anita R.
• Is Part Of: Organic & biomolecular chemistry. Volume 18:Issue 14(2020)
• Page Start: 2549
• Page End: 2610
• Publication Date: 2020-02-10
• Subjects: Chemistry, Organic -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1039/c9ob02587a
• Languages: English
• ISSNs: 1477-0520

Abstract

Abstract : Sulfonyl migrations, frequently described as 'unusual' or 'unexpected', from the last 20 years, including 1, 2-, 1, 3-, 1, 4-, 1, 5-, 1, 6- and 1, 7-sulfonyl shifts, through either radical or polar processes, either inter- or intramolecularly are reviewed. Abstract : Over the past 20 years reports of sulfonyl migrations have appeared, frequently described as 'unusual' and 'unexpected'. This comprehensive review compiles, for the first time, sulfonyl migrations reported over the last 20 years including formal 1, 2-, 1, 3-, 1, 4-, 1, 5-, 1, 6- and 1, 7-sulfonyl shifts, occurring through either radical or polar processes, either inter- or intramolecularly. Discussion of the sulfonyl migrations is structured according to reaction type, i.e. nitrogen–carbon, nitrogen–oxygen, nitrogen–nitrogen, oxygen–carbon (including anionic and non-anionic thia-Fries rearrangements), oxygen–oxygen and carbon–carbon migrations. Discussion of the underlying mechanisms for the migrations is included, with particular attention afforded to the principal techniques utilised for their elucidation, namely isotopic-labelling, crossover experiments, density functional theory calculations and electron paramagnetic resonance spectroscopy amongst others.