Divergent Reaction Pathways of a Cationic Intermediate: Rearrangement and Cyclization of 2-Substituted Furyl and Benzofuryl Enones Catalyzed by Iridium(III)

Autor:	Gerald F. Manbeck, Richard Eisenberg, Sylvia Chen, Alison J. Frontier, Tulaza Vaidya
Rok vydání:	2011
Předmět:	Stereochemistry Cationic polymerization chemistry.chemical_element General Chemistry Alkylation Biochemistry Catalysis chemistry.chemical_compound Colloid and Surface Chemistry Malonate chemistry Intramolecular force Electrophile Iridium Pyrrole
Zdroj:	Journal of the American Chemical Society. 133:3300-3303
ISSN:	1520-5126 0002-7863
DOI:	10.1021/ja111317q
Popis:	In contrast to 2-substituted pyrrole enones, furyl and benzofuryl enones do not undergo the Nazarov electrocyclization. Instead, these furyl and benzofuryl enones exhibit unusual rearrangement sequences in the presence of catalytic amounts of [IrBr(CO)(DIM)((R)-(+)-BINAP)](SbF(6))(2) (1; DIM = diethylisopropylidene malonate) and AgSbF(6) (1:1). A 1,2-H shift followed by intramolecular Friedel-Crafts alkylation leads to synthetically valuable cyclohexanones with furanylic quaternary centers. The electrophilicity of 1 is essential for this rearrangement.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_dedup___::5c81724a151456e45853ee4ef543438a https://doi.org/10.1021/ja111317q Zobrazit plný text záznamu