AlCl3-catalyzed ring expansion cascades of bicyclic cyclobutenamides involving highly strained cis,trans-cycloheptadienone intermediates

Wang, Xiao-Na, Krenske, Elizabeth H., Johnston, Ryne C., Houk, K. N. and Hsung, Richard P. (2015) AlCl3-catalyzed ring expansion cascades of bicyclic cyclobutenamides involving highly strained cis,trans-cycloheptadienone intermediates. Journal of the American Chemical Society, 137 16: 5596-5601. doi:10.1021/jacs.5b02561


Author Wang, Xiao-Na
Krenske, Elizabeth H.
Johnston, Ryne C.
Houk, K. N.
Hsung, Richard P.
Title AlCl3-catalyzed ring expansion cascades of bicyclic cyclobutenamides involving highly strained cis,trans-cycloheptadienone intermediates
Formatted title
AlCl3-catalyzed ring expansion cascades of bicyclic cyclobutenamides involving highly strained cis,trans-cycloheptadienone intermediates
Journal name Journal of the American Chemical Society   Check publisher's open access policy
ISSN 1520-5126
0002-7863
1943-2984
Publication date 2015-04-29
Year available 2015
Sub-type Article (original research)
DOI 10.1021/jacs.5b02561
Volume 137
Issue 16
Start page 5596
End page 5601
Total pages 6
Place of publication Washington, DC, United States
Publisher American Chemical Society
Collection year 2016
Language eng
Formatted abstract
We report the first experimental evidence for the generation of highly strained cis,trans-cycloheptadienones by electrocyclic ring opening of 4,5-fused cyclobutenamides. In the presence of AlCl3, the cyclobutenamides rearrange to [2.2.1]-bicyclic ketones; DFT calculations provide evidence for a mechanism involving torquoselective 4π-electrocyclic ring opening to a cis,trans-cycloheptadienone followed by a Nazarov-like recyclization and a 1,2-alkyl shift. Similarly, 4,6-fused cyclobutenamides undergo AlCl3-catalyzed rearrangements to [3.2.1]-bicyclic ketones through cis,trans-cyclooctadienone intermediates. The products can be further elaborated via facile cascade reactions to give complex tri- and tetracyclic molecules.
Keyword Catalysis
Ketones
Cascade reactions
Q-Index Code C1
Q-Index Status Confirmed Code
Institutional Status UQ

Document type: Journal Article
Sub-type: Article (original research)
Collections: Official 2016 Collection
School of Chemistry and Molecular Biosciences
 
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