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

John T.R. Liddon; James A. Rossi-Ashton; Aimee K. Clarke; Jason M. Lynam; Richard J.K. Taylor; William P. Unsworth

doi:10.1055/s-0037-1610181

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

John T.R. Liddon, James A. Rossi-Ashton, Aimee K. Clarke, Jason M. Lynam, Richard J.K. Taylor, William P. Unsworth

Research output: Contribution to journal › Article › peer-review

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.

Original language	English
Journal	SYNTHESIS-STUTTGART
DOIs	https://doi.org/10.1055/s-0037-1610181
Publication status	Accepted/In press - 4 Jul 2018

Bibliographical note

© 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

Access to Document

10.1055/s-0037-1610181

Silver_vs_Gold_Synthesis_Special_issue_version_7_revision
© 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
Accepted author manuscript, 294 KBLicence: Unspecified

Cite this

@article{d38c356f74984f9888b46137cbb8f1c1,

title = "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.",

keywords = "carbazoles, catalysis, gold, indoles, silver, spirocycles, ynones",

author = "Liddon, {John T.R.} and Rossi-Ashton, {James A.} and Clarke, {Aimee K.} and Lynam, {Jason M.} and Taylor, {Richard J.K.} and Unsworth, {William P.}",

note = "{\textcopyright} Georg Thieme Verlag Stuttgart. This is an author-produced version of the published paper. Uploaded in accordance with the publisher{\textquoteright}s self-archiving policy. Further copying may not be permitted; contact the publisher for details",

year = "2018",

month = jul,

day = "4",

doi = "10.1055/s-0037-1610181",

language = "English",

journal = "SYNTHESIS-STUTTGART",

issn = "0039-7881",

publisher = "Georg Thieme Verlag",

}

TY - JOUR

T1 - Divergent Reactivity of Indole-Tethered Ynones with Silver(I) and Gold(I) Catalysts

T2 - A Combined Synthetic and Computational Study

AU - Liddon, John T.R.

AU - Rossi-Ashton, James A.

AU - Clarke, Aimee K.

AU - Lynam, Jason M.

AU - Taylor, Richard J.K.

AU - Unsworth, William P.

N1 - © 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

PY - 2018/7/4

Y1 - 2018/7/4

N2 - 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.

AB - 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.

KW - carbazoles

KW - catalysis

KW - gold

KW - indoles

KW - silver

KW - spirocycles

KW - ynones

UR - http://www.scopus.com/inward/record.url?scp=85049599162&partnerID=8YFLogxK

U2 - 10.1055/s-0037-1610181

DO - 10.1055/s-0037-1610181

M3 - Article

AN - SCOPUS:85049599162

SN - 0039-7881

JO - SYNTHESIS-STUTTGART

JF - SYNTHESIS-STUTTGART

ER -

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

Abstract

Bibliographical note

Keywords

Access to Document

Other files and links

Spiroclip Technology: from Catalogue to Spirocycle in One Step

Spirocycles, Carbocycles and Heterocycles: Unified Routes via Catalyst Selection