A Vinyl‐Cation‐Induced 1, 3‐Aryl Shift. Issue 50 (10th May 2017)

• Record Type: Journal Article
• Authors: Fu, Liang; Damsen, Helena; Niggemann, Meike
• Is Part Of: Chemistry. Volume 23:Issue 50(2017)
• Page Start: 12158
• Page End: 12161
• Publication Date: 2017-05-10
• Subjects: aluminum catalysis -- carbon shift -- cation rearrangement -- transition-metal free -- vinyl cation; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201701255
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: A net insertion of an unactivated, internal alkyne into a sp 2 –sp 3 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 2 H ‐chromenes were obtained. Abstract : 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 sp 2 –sp 3 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 2 H ‐chromenes were obtained.