title: Novel and Efficient Insertions of Carbons Carrying O-, S-, and N-Linked Substituents: Synthesis of alpha-Alkoxyalkyl, alpha-(Alkylthio)alkyl, and alpha-(Carbazol-9-yl)alkyl Ketones.
abstract: A wide variety of benzotriazolyl-stabilized anions 2, obtained by the lithiation of 1-(alpha-alkoxyalkyl)-, 1-[alpha-(alkylthio)alkyl]-, and 1-[alpha-(carbazol-9-yl)alkyl]benzotriazoles 1, on reaction with aliphatic and aromatic aldehydes and ketones, followed by rearrangement induced by heating in the presence of zinc bromide, furnish one-carbon-homologated alpha-alkoxyalkyl, alpha-(alkylthio)alkyl, and alpha-(carbazol-9-yl)alkyl ketones 4 in simple one-pot operations in good yields with excellent regioselectivity. In several alkoxymethylene insertions, intermediate 2-alkoxyoxiranes were separated in good yields, demonstrating the epoxide mechanism for the rearrangements and providing a facile approach to polysubstituted 2-alkoxyoxiranes, another class of important compounds.
authors.affiliation: Center for Heterocyclic Compounds, Department of Chemistry, University of Florida, Gainesville, Florida 32611-7200.
authors.forename: Alan R.
authors.initials: AR
authors.lastname: Katritzky
authors.forename: Linghong
authors.initials: L
authors.lastname: Xie
authors.forename: Larisa
authors.initials: L
authors.lastname: Serdyuk