title: A Vinyl-Cation-Induced 1,3-Aryl Shift.
abstract: A net insertion of an unactivated, internal alkyne into a sp2-sp3C-C bond of simple benzylic alcohols was achieved using the rearrangement of a highly reactive vinyl cation intermediate to a stabilized allyl cation as the driving force for an unusual 1,3-carbon shift reaction. In the presence of 10 mol % of Al(OTf)3as a simple, inexpensive, and abundant catalyst, high selectivity for the rearrangement was achieved. The reaction scope proved general with regard to both the alkyne and the benzylic alcohol and a range of 1,2-dihydroquinolines as well as 2H-chromenes were obtained.
authors.affiliation: Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, 52074, Aachen, Germany.
authors.forename: Liang
authors.initials: L
authors.lastname: Fu
authors.affiliation: Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, 52074, Aachen, Germany.
authors.forename: Helena
authors.initials: H
authors.lastname: Damsen
authors.affiliation: Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, 52074, Aachen, Germany.
authors.forename: Meike
authors.initials: M
authors.lastname: Niggemann
keywords: aluminum catalysis; carbon shift; cation rearrangement; transition-metal free; vinyl cation