Experimental and computational studies on interrupted Nazarov reactions: Exploration of umpolung reactivity at the α-carbon of cyclopentanones

Yen-Ku Wu, Christine R. Dunbar, Robert McDonald, Michael J. Ferguson, F. G. West*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

42 Scopus citations

Abstract

A set of densely substituted, α-functionalized cyclopentanones can be generated by a two-component, domino reaction sequence entailing the Nazarov electrocyclization of divinyl ketones and nucleophilic addition of the resulting 2-oxidocyclopentenyl cations by selected trapping modalities. Bypassing the typical eliminative termination, Nazarov oxyallyl species can react with carbon π-nucleophiles through cycloadditions (or formal cycloadditions), in which bridged bicyclic systems are established, or nucleophilic trappings whereby one terminal carbon of the oxyallyl intermediate is subjected to carbon-carbon bond formation. A detailed investigation of reaction parameters to explicitly control the course of the "interrupted" Nazarov reactions is described. This methodology allows for facile installation of α-quaternary centers bearing allyl, alkynyl, and heteroaryl groups in an umpolung fashion. In addition, the trapping event of a Nazarov intermediate with furan was studied by DFT computations, in conjunction with experimental data, offering a rationale for the observed reaction pattern and diastereoselectivity. (Chemical Equation Presented)

Original languageEnglish
Pages (from-to)14903-14911
Number of pages9
JournalJournal of the American Chemical Society
Volume136
Issue number42
DOIs
StatePublished - 22 Oct 2014

Fingerprint Dive into the research topics of 'Experimental and computational studies on interrupted Nazarov reactions: Exploration of umpolung reactivity at the α-carbon of cyclopentanones'. Together they form a unique fingerprint.

Cite this