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
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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