3 years ago

A Vinyl-Cation-Induced 1,3-Aryl Shift

A Vinyl-Cation-Induced 1,3-Aryl Shift
Helena Damsen, Meike Niggemann, Liang Fu
A net insertion of an unactivated, internal alkyne into a sp2–sp3 C−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)3 as 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. Hop scotch: The rearrangement of a vinyl cation to a stabilized allyl cation was used as the driving force for a highly unusual 1,3-aryl shift reaction. Thereby a net insertion of an unactivated, internal alkyne into a sp2–sp3 C−C bond of benzylic alcohols was achieved in the presence of 10 mol % of Al(OTf)3 as a simple, inexpensive, and abundant catalyst. The reaction scope proved general and a range of 1,2-dihydroquinolines as well as 2H-chromenes were obtained.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/chem.201701255

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