Aromatic Aza-Claisen Rearrangement of Arylpropargylammonium Salts Generated in situ from Arynes and Tertiary Propargylamines.

Chemistry : a European Journal
Lu HanShi-Kai Tian

Abstract

The charge-accelerated aza-Claisen rearrangement of ammonium salts serves as a key step in the construction of complex nitrogen-containing molecules. However, much less attention has been paid to the aromatic aza-Claisen rearrangement than to the aliphatic one. Herein, we report an unprecedented aromatic aza-Claisen rearrangement of arylpropargylammonium salts, generated in situ from arynes and tertiary propargylamines, delivering structurally diverse 2-propargylanilines in moderate to good yields with high regioselectivity. This rearrangement proceeds in the absence of strong bases or transition metals, is compatible with moisture and air, tolerates a wide variety of functional groups, and is amenable to forming 11- to 13-membered heterocycles with a triple bond. The 2-propargylaniline products were treated with aluminum chloride in ethanol to afford multisubstituted indoles in moderate to excellent yields. Finally, a series of deuterium-labeling experiments was performed to elucidate the reaction mechanism.

References

Jun 14, 1996·The Journal of Organic Chemistry·John D. SpenceMichael H. Nantz
Jun 10, 2004·Chemical Reviews·Ana M Martín Castro
Jul 14, 2006·Chemical Reviews·Guy R Humphrey, Jeffrey T Kuethe
Aug 24, 2006·Journal of the American Chemical Society·Hiroto YoshidaAtsutaka Kunai
Jan 23, 2009·The Journal of Organic Chemistry·Akio SaitoYuji Hanzawa
Jun 16, 2009·Angewandte Chemie·Alastair A CantMichael F Greaney
Nov 8, 2012·Organic & Biomolecular Chemistry·Anton V DubrovskiyRichard C Larock
Feb 13, 2013·Journal of the American Chemical Society·Yuwen ZengJinbo Hu
Oct 16, 2013·Organic Letters·Sachin Suresh BhojgudeAkkattu T Biju
Mar 8, 2014·The Journal of Organic Chemistry·Rajender NallagondaPrasanta Ghorai
May 2, 2014·Chemistry : a European Journal·Yuwen Zeng, Jinbo Hu
Sep 18, 2014·Chemical Communications : Chem Comm·Adam E GoetzNeil K Garg
Oct 11, 2014·Journal of the American Chemical Society·Jose M MedinaK N Houk
Aug 26, 2016·Accounts of Chemical Research·Sachin Suresh BhojgudeAkkattu T Biju
Oct 19, 2016·Chemical Society Reviews·José-Antonio García-López, Michael F Greaney
Nov 23, 2016·Chemistry : a European Journal·Sam G MossJoseph B Sweeney
Feb 22, 2017·Chemical Society Reviews·Jiarong ShiYang Li
Feb 15, 2018·Chemical Communications : Chem Comm·Tony Roy, Akkattu T Biju
May 26, 2018·Chemical Communications : Chem Comm·Meng-Guang ZhouShi-Kai Tian
Jul 4, 2018·The Journal of Organic Chemistry·Gyoungwook MinHaye Min Ko
Oct 20, 2019·Chemistry : a European Journal·Sherif J KaldasArmido Studer
Jan 28, 2020·Accounts of Chemical Research·Jia HeYang Li

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