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Title

Factors Controlling the Alkyne Prins Cyclization: The Stability of Dihydropyranyl Cations

AuthorsMiranda, Pedro O. ; Ramírez, Miguel A.; Martín, Víctor S.; Padrón, Juan I.
KeywordsAlcohols
Cations
Cyclization
Rearrangement
Silanes
Issue Date4-Jul-2008
PublisherWiley-VCH
CitationChemistry - a European Journal 14(20): 6260-6268 (2008)
AbstractThe relative stability of the intermediates involved in the alkyne Prins cyclization and the competitive 2‐oxonia‐[3,3]‐sigmatropic rearrangement was studied. This rearrangement was shown to occur slowly under typical alkyne Prins cyclization conditions when the allenyl oxocarbenium ion that results from the rearrangement is similar to or higher in energy than the starting alkynyl oxocarbenium ion. The formal 2‐oxonia‐[3,3]‐sigmatropic rearrangement may be disfavored by destabilizing the resultant allenyl oxocarbenium ion or by stabilizing an intermediate dihydropyranyl cation. The trimethylsilyl group as a substituent at the alkyne and electron‐withdrawing groups (CH2Cl and CH2CN) located at the α‐position to the carbinol center are shown to be effective. DFT calculations suggest that these substituents stabilize the dihydropyranyl cations, thus leading to a more uniform reorganization of the electronic density in the ring, and do not have a direct effect on the formally positively charged carbon atom.
Publisher version (URL)https://doi.org/10.1002/chem.200800281
URIhttp://hdl.handle.net/10261/212231
DOI10.1002/chem.200800281
ISSN0947-6539
E-ISSN1521-3765
Appears in Collections:(IPNA) Artículos
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