Pyrrolylsulfonium salts: stable, accessible and versatile pseudohalides for Stille couplings

Jodie Hann; Catherine Lyall; Gabriele Kociok-Kohn; Simon E. Lewis

doi:10.1039/D4QO01793E

Pyrrolylsulfonium salts: stable, accessible and versatile pseudohalides for Stille couplings

Jodie Hann, Catherine Lyall, Gabriele Kociok-Kohn, Simon E. Lewis

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Abstract

Pyrrolyl halides can be difficult to synthesise in a regioselective manner and are often unstable, which has hampered their application in cross-coupling. Here we introduce pyrrolylsulfonium salts as advantageous pseudohalide coupling partners and showcase their applicability in Stille couplings. Benefits of these salts include their straightforward synthesis via an “interrupted Pummerer” process, their high stability, and the ability to selectively introduce the sulfonium group at either the pyrrole α- or β- position as required. The Stille coupling has been demonstrated for aryl, heteroaryl and alkynylstannanes, and the effect of the pyrrole substituents on the regioselectivity of S–C bond activation has been investigated. Conditions to effect N-desulfonylation of N-trisyl coupling products have been identified.

Original language	English
Pages (from-to)	7011-7026
Number of pages	16
Journal	Organic Chemistry Frontiers
Volume	11
Issue number	24
Early online date	24 Oct 2024
DOIs	https://doi.org/10.1039/D4QO01793E
Publication status	Published - 21 Dec 2024

Data Availability Statement

The data supporting this article have been included as part of the ESI.† Crystallographic data for 2·PF6 and 5f have been deposited at the CCDC under 2382855 and 2382856.†

Acknowledgements

We acknowledge the research facilities at the University of Bath (https://doi.org/10.15125/mx6j-3r54). We thank Dr Alex Cresswell for helpful discussions.

Funding

We thank EPSRC for a DTP PhD studentship to J. L. H. (EP/T518013/1).

Funders	Funder number
Engineering and Physical Sciences Research Council	EP/T518013/1

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10.1039/D4QO01793ELicence: CC BY

___OCF_2024_11_7011___Final published version, 1.7 MBLicence: CC BY

Cite this

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AB - Pyrrolyl halides can be difficult to synthesise in a regioselective manner and are often unstable, which has hampered their application in cross-coupling. Here we introduce pyrrolylsulfonium salts as advantageous pseudohalide coupling partners and showcase their applicability in Stille couplings. Benefits of these salts include their straightforward synthesis via an “interrupted Pummerer” process, their high stability, and the ability to selectively introduce the sulfonium group at either the pyrrole α- or β- position as required. The Stille coupling has been demonstrated for aryl, heteroaryl and alkynylstannanes, and the effect of the pyrrole substituents on the regioselectivity of S–C bond activation has been investigated. Conditions to effect N-desulfonylation of N-trisyl coupling products have been identified.

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Pyrrolylsulfonium salts: stable, accessible and versatile pseudohalides for Stille couplings

Abstract

Data Availability Statement

Acknowledgements

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