title: Diastereoselectivity control in formal nucleophilic substitution of bromocyclopropanes with oxygen- and sulfur-based nucleophiles.
abstract: A diastereoconvergent formal nucleophilic substitution of bromocyclopropanes with oxygen- and sulfur-based nucleophiles is described. The reaction proceeds via in situ formation of a highly reactive cyclopropene intermediate and subsequent diastereoselective addition of a nucleophile across the strained C═C bond. Three alternative means of controlling the diastereoselectivity of addition have been demonstrated: (1) thermodynamically driven epimerization of enolizable carboxamides, (2) steric control by bulky substituents, and (3) directing effect of carboxamide or carboxylate functions.
authors.affiliation: Department of Chemistry, The University of Kansas, 1251 Wesoce Hall Drive, Lawrence, Kansas 66045-75832, United States.
authors.forename: Joseph E
authors.initials: JE
authors.lastname: Banning
authors.forename: Anthony R
authors.initials: AR
authors.lastname: Prosser
authors.forename: Bassam K
authors.initials: BK
authors.lastname: Alnasleh
authors.forename: Jason
authors.initials: J
authors.lastname: Smarker
authors.forename: Marina
authors.initials: M
authors.lastname: Rubina
authors.forename: Michael
authors.initials: M
authors.lastname: Rubin
mesh_terms: D003521:Cyclopropanes / Q000737:chemistry*; D010100:Oxygen / Q000737:chemistry*; D013237:Stereoisomerism; D013379:Substrate Specificity; D013455:Sulfur / Q000737:chemistry*
chemical_list: D003521:Cyclopropanes; D013455:Sulfur; C030797:cyclopropane; D010100:Oxygen