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

Item Type:	Article
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
Copyright, Publisher and Additional Information:	© 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:	Accepted: 4 July 2018
Institution:	The University of York
Academic Units:	The University of York The University of York > Faculty of Sciences (York) > Chemistry (York)
Funding Information:	Funder Grant number EPSRC EP/R013748/1 EPSRC EP/N035119/1
Depositing User:	Pure (York)
Date Deposited:	17 Jul 2018 13:50
Last Modified:	20 Sep 2025 00:37
Published Version:	https://doi.org/10.1055/s-0037-1610181
Status:	In Press
Refereed:	Yes
Identification Number:	10.1055/s-0037-1610181
Related URLs:	http://www.scopus.com/inward/record.url?...
Open Archives Initiative ID (OAI ID):	oai:eprints.whiterose.ac.uk:133441

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

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