Palladium-Catalyzed Decarboxylative Couplings of 2-(2-Azaaryl)acetates with Aryl Halides and Triflates

Abstract

Pd-catalyzed decarboxylative cross-couplings of 2-(2-azaaryl)acetates with aryl halides and triflates have been discovered. This reaction is potentially useful for the synthesis of some functionalized pyridines, quinolines, pyrazines, benzoxazoles, and benzothiazoles. Theoretical analysis shows that the nitrogen atom at the 2-position of the heteroaromatics directly coordinates to Pd(II) in the decarboxylation transition state.

Palladium‐Catalyzed Carbonylative Coupling of (2‐Azaaryl)methyl Anion Equivalents with (Hetero)Aryl Bromides

“…[16] However, when our carbonylative process was conducted under similar conditions no desired product could be identified (entry 6). Gratifyingly, when we switched to the (2-pyridyl)acetone (3), the reaction proceeded cleanly using the previously developed conditions.…”

Mechanistic study on the regioselectivity of Co-catalyzed hydroacylation of 1,3-dienes

“…Computational studies were performed with Gaussian 09 program [9][10][11][12][13][14][15][16][17][18][19][20][21][22][23]. Geometry optimization was conducted in gas phase with M06 method [24].…”

Transition metal-catalyzed decarboxylative cross-coupling reactions

“…Therefore, it is interesting and important to study the decarboxylative cross-coupling reactions that break the C sp3 COOH bonds. In 2010 our group reported the Pd-catalyzed decarboxylative cross-coupling of 2-(2-azaaryl)acetates with aryl halides and triflates (Scheme 27) [38]. This reaction is potentially useful for the synthesis of functionalized pyridines, quinolines, pyrazines, benzoxazoles, and benzothiazoles.…”