University of Sussex
Browse

File(s) not publicly available

Palladium-Catalyzed Cascade Oligocyclizations Involving Competing Elementary Steps Such as Thermal [1,5]-Acyl Shifts

journal contribution
posted on 2023-06-08, 07:42 authored by Wajdi M Tokan, Stefan Schweizer, Claudia Thies, Frank E Meyer, Philip J Parsons, Armin de Meijere
Palladium(Pd)-catalyzed oligocyclizations of 2-bromotetradec-1-ene-7,13-diynes with an unsubstituted terminal acetylene moiety like 3 and 5 and 15-bromohexadec-15-ene-3,9-diyn-2-ones like 4 and 6 afforded fulvene derivatives 20 and 21 (Scheme 7) and bis(cyclohexane)-annulated methylenecyclopentene systems 16 and 18 (Schemes 5 and 6), respectively. These transformations constitute cascades of cyclizing carbopalladation steps with ensuing [1,5]-sigmatropic H-atom and acyl shifts, respectively (Scheme 8). In contrast, analogous substrates with one three-atom and one four-atom tether between the unsaturated C,C-bonds, such as 1 and 2, behave differently in that the Pd-substituted hexa-1,3,5-triene intermediates 12 undergo a 6p-electrocyclization instead of a 5-exo-trig carbopalladation followed by ß-hydride elimination to furnish tricyclic bis-annulated benzene derivatives 13 and 14 (Scheme 4).

History

Publication status

  • Published

Journal

Helvetica Chimica Acta

ISSN

0018-019X

Issue

9

Volume

92

Page range

1729-1740

Pages

12.0

Department affiliated with

  • Chemistry Publications

Full text available

  • No

Peer reviewed?

  • Yes

Legacy Posted Date

2012-02-06

Usage metrics

    University of Sussex (Publications)

    Categories

    No categories selected

    Exports

    RefWorks
    BibTeX
    Ref. manager
    Endnote
    DataCite
    NLM
    DC