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AlCl₃-Catalyzed Ring Expansion Cascades of Bicyclic Cyclobutenamides Involving Highly Strained Cis,Trans-Cycloheptadienone Intermediates.
- Source :
-
Journal of the American Chemical Society [J Am Chem Soc] 2015 Apr 29; Vol. 137 (16), pp. 5596-601. Date of Electronic Publication: 2015 Apr 20. - Publication Year :
- 2015
-
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.
- Subjects :
- Aluminum Chloride
Amides chemical synthesis
Bridged Bicyclo Compounds chemical synthesis
Catalysis
Cyclization
Cyclobutanes chemical synthesis
Ketones chemical synthesis
Ketones chemistry
Models, Molecular
Stereoisomerism
Aluminum Compounds chemistry
Amides chemistry
Bridged Bicyclo Compounds chemistry
Chlorides chemistry
Cyclobutanes chemistry
Subjects
Details
- Language :
- English
- ISSN :
- 1520-5126
- Volume :
- 137
- Issue :
- 16
- Database :
- MEDLINE
- Journal :
- Journal of the American Chemical Society
- Publication Type :
- Academic Journal
- Accession number :
- 25895058
- Full Text :
- https://doi.org/10.1021/jacs.5b02561