Reactions of Arylsulfonate Electrophiles with NMe4 F: Mechanistic Insight, Reactivity, and Scope

The Journal of Organic Chemistry
Sydonie D SchimlerMelanie S Sanford

Abstract

This paper describes a detailed study of the deoxyfluorination of aryl fluorosulfonates with tetramethylammonium fluoride (NMe4F) and ultimately identifies other sulfonate electrophiles that participate in this transformation. 19F NMR spectroscopic monitoring of the deoxyfluorination of aryl fluorosulfonates revealed the rapid formation of diaryl sulfates under the reaction conditions. These intermediates can proceed to fluorinated products; however, diaryl sulfate derivatives bearing electron-donating substituents react very slowly with NMe4F. Based on these findings, aryl triflate and aryl nonaflate derivatives were explored, since these cannot react to form diaryl sulfates. Aryl triflates were found to be particularly effective electrophiles for deoxyfluorination with NMe4F, and certain derivatives (i.e., those bearing electron-neutral/donating substituents) afforded higher yields than their aryl fluorosulfonate counterparts. Computational studies implicate a similar mechanism for deoxyfluorination of all the sulfonate electrophiles.

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Apr 13, 2019·Chemistry : a European Journal·Athanasios MarkosPetr Beier
Aug 1, 2019·Chemical Society Reviews·A S BarrowJ E Moses
Jan 18, 2020·Science·Oriol PlanasJosep Cornella
Feb 20, 2021·The Journal of Organic Chemistry·Cynthia M HongDanielle M Schultz
May 25, 2021·Organic Letters·María T Morales-ColónMelanie S Sanford
Jul 29, 2021·Chemical Communications : Chem Comm·Xiu WangJinbo Hu
Aug 29, 2020·Chemical Reviews·Zihang Qiu, Chao-Jun Li
Jun 27, 2020·Organic Letters·Young-Do KwonJoong-Hyun Chun
Nov 3, 2021·The Journal of Organic Chemistry·Holly McErlainAndrew Sutherland

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