Divergent Reactivity of Indole-Tethered Ynones with Silver(I) and Gold(I) Catalysts : A Combined Synthetic and Computational Study

Abstract

A combined synthetic and computational (DFT) study has been performed to account for the divergent reactivity of indole-tethered ynones when treated with Ag(I) and Au(I) catalysts. The two catalyst systems deliver spirocyclic indolenines and carbazoles, respectively, from the same precursors, with the reaction outcomes believed to be a result of differences in the rates of a key protodemetalation step. A ring-opening/ring-closing isomerisation process is proposed to enable the interconversion of spirocyclic and C-2 annulated indole intermediates, in contrast to the 1,2-migration mechanism tentatively proposed in previous studies.

Metadata

Authors/Creators:

Liddon, John T.R. https://orcid.org/0000-0002-5287-9817
Rossi-Ashton, James A. (jra520@york.ac.uk)
Clarke, Aimee K. (akc504@york.ac.uk)
Lynam, Jason M. https://orcid.org/0000-0003-0103-9479
Taylor, Richard J.K. https://orcid.org/0000-0002-5880-2490
Unsworth, William P. https://orcid.org/0000-0002-9169-5156

© Georg Thieme Verlag Stuttgart. This is an author-produced version of the published paper. Uploaded in accordance with the publisher’s self-archiving policy. Further copying may not be permitted; contact the publisher for details

Keywords:

carbazoles, catalysis, gold, indoles, silver, spirocycles, ynones

Dates: