Divergent Mechanistic Scenarios for the C−sp2 and C−sp3 C−H Insertion of Aurated Aryl Cations

Janina Bucher; Thomas Wurm; Kaveh Farshadfar; Michael Schukin; Georgios Uzunidis; Matthias Rudolph; Frank Rominger; Alireza Ariafard; A. Stephen K. Hashmi

doi:10.1002/adsc.202300548

Divergent Mechanistic Scenarios for the C−sp² and C−sp³ C−H Insertion of Aurated Aryl Cations

Janina Bucher, Thomas Wurm, Kaveh Farshadfar, Michael Schukin, Georgios Uzunidis, Matthias Rudolph, Frank Rominger, Alireza Ariafard, A. Stephen K. Hashmi^*

^*Corresponding author for this work

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

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Abstract

By employing the sterically highly demanding steering ligand IPr* at a gold(I) center, it is possible to induce a 6-endo-dig cyclization pathway in 1,5-diynes bearing terminal alkyne moieties. The resulting aurated naphthyl cations are utilized for the intermolecular formation of C−C bonds via C−H insertion of aromatic and aliphatic C−H bonds. The mechanisms of these transformations were studied by quantum chemical calculations.

Original language	English
Pages (from-to)	3320-3327
Number of pages	8
Journal	Advanced Synthesis and Catalysis
Volume	365
Issue number	19
Early online date	23 Aug 2023
DOIs	https://doi.org/10.1002/adsc.202300548
Publication status	Published - 13 Oct 2023
MoE publication type	A1 Journal article-refereed

Keywords

aryl cations
C−H insertion
diynes
gold catalysis
high energy intermediates

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CHEM_Bucher_et_al_Divergent Mechanistic_2023_Adv_Synth_CatalFinal published version, 5.03 MBLicence: CC BY-NC-ND

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title = "Divergent Mechanistic Scenarios for the C−sp2 and C−sp3 C−H Insertion of Aurated Aryl Cations",

abstract = "By employing the sterically highly demanding steering ligand IPr* at a gold(I) center, it is possible to induce a 6-endo-dig cyclization pathway in 1,5-diynes bearing terminal alkyne moieties. The resulting aurated naphthyl cations are utilized for the intermolecular formation of C−C bonds via C−H insertion of aromatic and aliphatic C−H bonds. The mechanisms of these transformations were studied by quantum chemical calculations.",

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note = "Funding Information: J. Bucher is grateful for a Chemiefonds scholarship of the Fonds der Chemischen Industrie. The authors thank Umicore AG & Co. KG for the generous donation of gold salts. Publisher Copyright: {\textcopyright} 2023 The Authors. Advanced Synthesis & Catalysis published by Wiley-VCH GmbH.",

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T1 - Divergent Mechanistic Scenarios for the C−sp2 and C−sp3 C−H Insertion of Aurated Aryl Cations

AU - Bucher, Janina

AU - Wurm, Thomas

AU - Farshadfar, Kaveh

AU - Schukin, Michael

AU - Uzunidis, Georgios

AU - Rudolph, Matthias

AU - Rominger, Frank

AU - Ariafard, Alireza

AU - Hashmi, A. Stephen K.

N1 - Funding Information: J. Bucher is grateful for a Chemiefonds scholarship of the Fonds der Chemischen Industrie. The authors thank Umicore AG & Co. KG for the generous donation of gold salts. Publisher Copyright: © 2023 The Authors. Advanced Synthesis & Catalysis published by Wiley-VCH GmbH.

PY - 2023/10/13

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N2 - By employing the sterically highly demanding steering ligand IPr* at a gold(I) center, it is possible to induce a 6-endo-dig cyclization pathway in 1,5-diynes bearing terminal alkyne moieties. The resulting aurated naphthyl cations are utilized for the intermolecular formation of C−C bonds via C−H insertion of aromatic and aliphatic C−H bonds. The mechanisms of these transformations were studied by quantum chemical calculations.

AB - By employing the sterically highly demanding steering ligand IPr* at a gold(I) center, it is possible to induce a 6-endo-dig cyclization pathway in 1,5-diynes bearing terminal alkyne moieties. The resulting aurated naphthyl cations are utilized for the intermolecular formation of C−C bonds via C−H insertion of aromatic and aliphatic C−H bonds. The mechanisms of these transformations were studied by quantum chemical calculations.

KW - aryl cations

KW - C−H insertion

KW - diynes

KW - gold catalysis

KW - high energy intermediates

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Divergent Mechanistic Scenarios for the C−sp² and C−sp³ C−H Insertion of Aurated Aryl Cations

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Keywords

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