Shang R, Ilies L, * Nakamura E. * The University of Tokyo, Japan
Iron-Catalyzed Directed C(sp
2)–H and C(sp
3)–H Functionalization with Trimethylaluminum.
J. Am. Chem. Soc. 2015;
137: 7760-7663
Key words
C–H functionalization - trimethylaluminum - iron
Significance
The iron(III)-catalyzed directed functionalization of C(sp2)−H and C(sp3)−H bonds was achieved by Nakamura and co-workers. The methylation of anilides and
carboxamides bearing a picolinoyl or 8-aminoquinolyl group with trimethylaluminum
is tolerant of electron-withdrawing (CF3, F, Cl, Br, CO2R) and electron-donating (OMe, NMe2) groups, as well as heterocyclic amines.
Comment
The authors present an alternative to the use of AlMe3 by isolating the air-stable diamine intermediate formed by complexation of AlMe3 with the iron(III) salt and 1,2-bis(diphenylphosphino)ethane (dppen). This robust
catalyst could be recovered and a turnover number of more than 6500 was reached.
