Issue 16, 2024

Reactivity of α-diazo sulfonium salts: rhodium-catalysed ring expansion of indenes to naphthalenes

Abstract

In the presence of catalytic amounts of the paddlewheel dirhodium complex Rh2(esp)2, α-diazo dibenzothiophenium salts generate highly electrophilic Rh-coordinated carbenes, which evolve differently depending on their substitution pattern. Keto-moieties directly attached to the azomethinic carbon promote carbene insertion into one of the adjacent C–S bonds, giving rise to highly electrophilic dibenzothiopyrilium salts. This intramolecular pathway is not operative when the carbene carbon bears ester or trifluoromethyl substituents; in fact, these species react with olefins delivering easy to handle cyclopropyl-substituted sulfonium salts. When indenes are the olefins of choice, the initially formed cyclopropyl rings smoothly open with concomitant departure of dibenzothiophene, enabling access to a series of 2-functionalized naphthalenes.

Graphical abstract: Reactivity of α-diazo sulfonium salts: rhodium-catalysed ring expansion of indenes to naphthalenes

Supplementary files

Article information

Article type
Edge Article
Submitted
17 Feb 2024
Accepted
11 Mar 2024
First published
25 Mar 2024
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., 2024,15, 5938-5943

Reactivity of α-diazo sulfonium salts: rhodium-catalysed ring expansion of indenes to naphthalenes

S. Timmann, T. Wu, C. Golz and M. Alcarazo, Chem. Sci., 2024, 15, 5938 DOI: 10.1039/D4SC01138D

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.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements