Synthesis of Fulvene Vinyl Ethers by Gold Catalysis.

aryl cations fulvene ethers gold catalysis vinyl cations vinyl ethers

Journal

Chemistry (Weinheim an der Bergstrasse, Germany)
ISSN: 1521-3765
Titre abrégé: Chemistry
Pays: Germany
ID NLM: 9513783

Informations de publication

Date de publication:
21 Apr 2020
Historique:
received: 21 01 2020
revised: 23 02 2020
pubmed: 25 2 2020
medline: 25 2 2020
entrez: 25 2 2020
Statut: ppublish

Résumé

Gold-catalyzed cyclization of 1,5-diynes with ketones as reagents and solvent provides diversely substituted vinyl ethers under mild conditions. The regioselectivity of such gold-catalyzed cyclizations is usually controlled by the scaffold of the diyne. Herein, we report the first solvent-controlled switching of regioselectivity from a 6-endo-dig- to 5-endo-dig-cyclization in these transformations, providing fulvene derivatives. With respect to the functional-group tolerance, aryl fluorides, chlorides, bromides, and ethers are tolerated. Furthermore, the mechanism and selectivity are put to scrutiny by experimental studies and a thermodynamic analysis of the product. Additionally, 6-(vinyloxy)fulvenes are a hitherto unknown class of compounds. Their reactivity is briefly evaluated, to give insights into their potential applications.

Identifiants

pubmed: 32092204
doi: 10.1002/chem.202000338
pmc: PMC7216831
doi:

Types de publication

Journal Article

Langues

eng

Sous-ensembles de citation

IM

Pagination

5280-5287

Subventions

Organisme : Brazilian Council for Scientific and Technological Development (CNPQ)

Informations de copyright

© 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

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Auteurs

Alexander Ahrens (A)

Organisch-Chemisches Institut, Heidelberg University, Im Neuenheimer Feld 270, 69120, Heidelberg, Germany.

Julia Schwarz (J)

Organisch-Chemisches Institut, Heidelberg University, Im Neuenheimer Feld 270, 69120, Heidelberg, Germany.

Danilo M Lustosa (DM)

Organisch-Chemisches Institut, Heidelberg University, Im Neuenheimer Feld 270, 69120, Heidelberg, Germany.
Interdisciplinary Center for Scientific Computing (IWR), Heidelberg University, Im Neuenheimer Feld 205A, 69120, Heidelberg, Germany.

Raheleh Pourkaveh (R)

Organisch-Chemisches Institut, Heidelberg University, Im Neuenheimer Feld 270, 69120, Heidelberg, Germany.
Laboratory of Organic Synthesis and Natural Products, Department of Chemistry, Sharif University of Technology, Azadi Street, PO Box 111559516, Tehran, Iran.

Marvin Hoffmann (M)

Interdisciplinary Center for Scientific Computing (IWR), Heidelberg University, Im Neuenheimer Feld 205A, 69120, Heidelberg, Germany.

Frank Rominger (F)

Organisch-Chemisches Institut, Heidelberg University, Im Neuenheimer Feld 270, 69120, Heidelberg, Germany.

Matthias Rudolph (M)

Organisch-Chemisches Institut, Heidelberg University, Im Neuenheimer Feld 270, 69120, Heidelberg, Germany.

Andreas Dreuw (A)

Interdisciplinary Center for Scientific Computing (IWR), Heidelberg University, Im Neuenheimer Feld 205A, 69120, Heidelberg, Germany.

A Stephen K Hashmi (ASK)

Organisch-Chemisches Institut, Heidelberg University, Im Neuenheimer Feld 270, 69120, Heidelberg, Germany.

Classifications MeSH