Directed Ring-Opening of 1,5-Dioxaspiro[3.2]hexanes: Selective Formation of 2,2-Disubstituted Oxetanes
Date
2003Author
Taboada, Rosa
Ordonio, Grace G
Ndakala, Albert J
Howell, Amy R
Type
ArticleLanguage
enMetadata
Show full item recordAbstract
1,5-Dioxaspiro[3.2]hexanes undergo ring-opening reactions with many heteroatom nucleophiles to provide α-substituted-β‘-hydroxy ketones. However, certain Lewis acidic nucleophiles provide 2,2-disubstituted oxetanes. Herein, the results of reactions of 3-phenyl-1,5-dioxaspiro[3.2]hexane with a variety of nitrogen-containing heteroaromatic bases are reported. There appears to be a correlation between the pKa of the nucleophile and the reaction outcome with more acidic nucleophiles providing 2,2-disubstituted oxetanes. Moreover, the mode of ring opening can be directed toward the substituted oxetane by the addition of a Lewis acid. These results are rationalized by calculation of stationary points on the potential energy surfaces for the various possible reaction pathways using ab initio molecular orbital methods.
URI
http://pubs.acs.org/doi/abs/10.1021/jo0206465http://erepository.uonbi.ac.ke:8080/xmlui/handle/123456789/35052
Citation
J. Org. Chem., 2003, 68 (4), pp 1480–1488Publisher
Department of Chemistry, University of Nairobi