Issue 7, 2023

Sulfur(iv) reagents for the SuFEx-based synthesis of substituted sulfamate esters

Abstract

Sulfur(VI) fluoride exchange chemistry has been reported to be effective at synthesizing valuable sulfur(VI) functionalities through sequential nucleophilic additions, yet oxygen-based nucleophiles are limited in this approach to phenolic derivatives. Herein, we report a new sulfur(IV) fluoride exchange strategy to access synthetically challenging substituted sulfamate esters from alkyl alcohols and amines. We also report the development of a non-gaseous, sulfur(IV) fluoride exchange reagent, N-methylimidazolium sulfinyl fluoride hexafluorophosphate (MISF). By leveraging the reactivity of the sulfur(IV) center of this novel reagent, the sequential addition of alcohols and amines to MISF followed by oxidation afforded the desired substituted sulfamates in 40–83% yields after two steps. This new strategy expands the scope of SuFEx chemistry by increasing the accessibility of underdeveloped –S(O)F intermediates for future explorations.

Graphical abstract: Sulfur(iv) reagents for the SuFEx-based synthesis of substituted sulfamate esters

Supplementary files

Article information

Article type
Edge Article
Submitted
26 Oct 2022
Accepted
19 Jan 2023
First published
20 Jan 2023
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2023,14, 1775-1780

Sulfur(IV) reagents for the SuFEx-based synthesis of substituted sulfamate esters

K. T. Downey, J. Y. Mo, J. Lai, B. J. Thomson and G. M. Sammis, Chem. Sci., 2023, 14, 1775 DOI: 10.1039/D2SC05945B

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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