title: Nucleophilic addition to silyl-protected five-membered ring oxocarbenium ions governed by stereoelectronic effects.
abstract: A series of fused-bicyclic acetals containing a disiloxane ring was investigated to evaluate the source of selectivity in silyl-protected 2-deoxyribose systems. The disiloxane ring unexpectedly enables the diaxial conformer of the cation to be stabilized by an electronegative atom at C-3. This low energy conformer subsequently undergoes stereoelectronically controlled nucleophilic addition to give substituted tetrahydrofurans with high diastereoselectivity.
authors.affiliation: Department of Chemistry, New York University, 100 Washington Square East, New York, New York 10003, USA.
authors.forename: Vi Tuong
authors.initials: VT
authors.lastname: Tran
authors.forename: K A
authors.initials: KA
authors.lastname: Woerpel
mesh_terms: D000080:Acetals / Q000737:chemistry*; D001643:Bridged Bicyclo Compounds / Q000737:chemistry*; D003855:Deoxyribose / Q000737:chemistry*; D008968:Molecular Conformation; D012833:Siloxanes / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D000080:Acetals; D001643:Bridged Bicyclo Compounds; D012833:Siloxanes; D003855:Deoxyribose