Issue 18, 2022

Sulfur(iv)-mediated umpolung α-heterofunctionalization of 2-oxazolines


The α-umpolung of carbonyl compounds significantly expands the boundaries of traditional carbonyl chemistry. Despite various umpolung methods available today, reversing the inherent reactivity of carbonyls still remains a substantial challenge. In this article, we report the first use of sulfonium salts, in lieu of well-established hypervalent iodines, for the carbonyl umpolung event. The protocol enables the incorporation of a wide variety of heteroatom nucleophiles into the α-carbon of 2-oxazolines. The success of this investigation hinges on the following factors: (1) the use of sulfoxides, which are abundant, structurally diverse and tunable, and easily accessible, ensures the identification of a superior oxidant namely phenoxathiin sulfoxide for the umpolung reaction; (2) the “assembly/deprotonation” protocol previously developed for rearrangement reactions in our laboratory was successfully applied here for the construction of α-umpoled 2-oxazolines.

Graphical abstract: Sulfur(iv)-mediated umpolung α-heterofunctionalization of 2-oxazolines

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Article information

Article type
Edge Article
25 Jan 2022
08 Apr 2022
First published
09 Apr 2022
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., 2022,13, 5164-5170

Sulfur(IV)-mediated umpolung α-heterofunctionalization of 2-oxazolines

Q. Zhang, Y. Liang, R. Li, Z. Huang, L. Kong, P. Du and B. Peng, Chem. Sci., 2022, 13, 5164 DOI: 10.1039/D2SC00476C

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