Issue 19, 2021

Divergent reactivity of sulfinates with pyridinium salts based on one- versus two-electron pathways

Abstract

One of the main goals of modern synthesis is to develop distinct reaction pathways from identical starting materials for the efficient synthesis of diverse compounds. Herein, we disclose the unique divergent reactivity of the combination sets of pyridinium salts and sulfinates to achieve sulfonative pyridylation of alkenes and direct C4-sulfonylation of pyridines by controlling the one- versus two-electron reaction manifolds for the selective formation of each product. Base-catalyzed cross-coupling between sulfinates and N-amidopyridinium salts led to the direct introduction of a sulfonyl group into the C4 position of pyridines. Remarkably, the reactivity of this set of compounds is completely altered upon exposure to visible light: electron donor–acceptor complexes of N-amidopyridinium salts and sulfinates are formed to enable access to sulfonyl radicals. In this catalyst-free radical pathway, both sulfonyl and pyridyl groups could be incorporated into alkenes via a three-component reaction, which provides facile access to a variety of β-pyridyl alkyl sulfones. These two reactions are orthogonal and complementary, achieving a broad substrate scope in a late-stage fashion under mild reaction conditions.

Graphical abstract: Divergent reactivity of sulfinates with pyridinium salts based on one- versus two-electron pathways

Supplementary files

Article information

Article type
Edge Article
Submitted
08 feb 2021
Accepted
30 mar 2021
First published
31 mar 2021
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., 2021,12, 6629-6637

Divergent reactivity of sulfinates with pyridinium salts based on one- versus two-electron pathways

M. Kim, E. You, S. Park and S. Hong, Chem. Sci., 2021, 12, 6629 DOI: 10.1039/D1SC00776A

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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