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Ligand-controlled product selectivity in gold-catalyzed double cycloisomerization of 1,11-Dien-3,9-Diyne benzoates
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Rao, Weidong, Susanti, Dewi, Ayers, Benjamin James and Chan, Philip Wai Hong (2015) Ligand-controlled product selectivity in gold-catalyzed double cycloisomerization of 1,11-Dien-3,9-Diyne benzoates. Journal of the American Chemical Society, 137 (19). pp. 6350-6355. doi:10.1021/jacs.5b02377 ISSN 1520-5126.
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WRAP-Ligand-controlled-selectivity-gold-catalyzed-cycloisomerization-benzoates-Chan-2017.pdf - Accepted Version - Requires a PDF viewer. Download (837Kb) | Preview |
Official URL: http://doi.org/10.1021/jacs.5b02377
Abstract
A synthetic method to prepare tricyclic bridged heptenones and hexenones from gold(I)-catalyzed double cycloisomerization of 1,11-dien-3,9-diyne benzoates is described. A divergence in product selectivity was achieved by fine-tuning the steric nature of the ligand of the Au(I) catalyst. In the presence of [MeCNAu(JohnPhos)]+SbF6– (JohnPhos = (1,1′-biphenyl-2-yl)-di-tert-butylphosphine) as the catalyst, tandem 1,3-acyloxy migration/metallo-Nazarov cyclization/1,6-enyne addition/Cope rearrangement of the substrate was found to selectively occur to afford the bridged heptenone adduct. In contrast, changing the Au(I) catalyst to [MeCNAu(Me4tBuXPhos)]+SbF6– (Me4tBuXPhos = di-tert-butyl(2′,4′,6′-triisopropyl-3,4,5,6-tetramethyl-[1,1′-biphenyl]-2-yl)phosphine) was observed to result in the 1,11-dien-3,9-diyne benzoate undergoing a more rapid tandem 1,3-acyloxy migration/metallo-Nazarov cyclization/[4 + 2]-cyclization pathway to give the bridged hexenone derivative.
Item Type: | Journal Article | ||||||||||||
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Subjects: | Q Science > QD Chemistry | ||||||||||||
Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry | ||||||||||||
SWORD Depositor: | Library Publications Router | ||||||||||||
Library of Congress Subject Headings (LCSH): | Benzoates, Catalysis | ||||||||||||
Journal or Publication Title: | Journal of the American Chemical Society | ||||||||||||
Publisher: | American Chemical Society (ACS) | ||||||||||||
ISSN: | 1520-5126 | ||||||||||||
Official Date: | 7 May 2015 | ||||||||||||
Dates: |
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Volume: | 137 | ||||||||||||
Number: | 19 | ||||||||||||
Page Range: | pp. 6350-6355 | ||||||||||||
DOI: | 10.1021/jacs.5b02377 | ||||||||||||
Status: | Peer Reviewed | ||||||||||||
Publication Status: | Published | ||||||||||||
Reuse Statement (publisher, data, author rights): | ** From Crossref via Jisc Publications Router. | ||||||||||||
Access rights to Published version: | Restricted or Subscription Access | ||||||||||||
Date of first compliant deposit: | 20 December 2017 | ||||||||||||
Date of first compliant Open Access: | 20 December 2017 | ||||||||||||
RIOXX Funder/Project Grant: |
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