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Synfacts 2015; 11(9): 0969
DOI: 10.1055/s-0035-1560075
Metal-Mediated Synthesis
© Georg Thieme Verlag Stuttgart · New York

Directed Iron-Catalyzed C–H Methylation

Contributor(s):
Paul Knochel
,
Sarah Fernandez
Shang R, Ilies L, * Nakamura E. * The University of Tokyo, Japan
Iron-Catalyzed Directed C(sp2)–H and C(sp3)–H Functionalization with Trimethylaluminum.

J. Am. Chem. Soc. 2015;
137: 7760-7663
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Publication History

Publication Date:
18 August 2015 (online)

 
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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.


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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.


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