Further Information
Literature
Directed ortho Metalation (DOM)
The reaction of an alkyllithium compound with an arene bearing a "Directed Metalation Group" (DMG) normally leads to an ortho-metalated intermediate. Good DMG's are strong complexing or chelating groups that have the effect of increasing the kinetic acidity of protons in the ortho-position.
The ortho-metalated intermediate can be reacted with a variety of electrophiles, after which the DMG can be retained if desired, converted to a different functional group, or in some cases removed.
Mechanism of Directed Ortho Metalation
The DMG does not necessarily have to be inert:
| strong DMGs: | -CON-R, -CONR2, | -N-COR, -N-CO2R |
 |
-OCONR2, -OMOM | |
| -SO3R | ||
| -CH=NR | -SO2NR2 | |
| -CN | -SO2tBu | |
| moderate | -CF3 | -NR2 |
| -NC | ||
| -OMe | ||
| -F | ||
| -Cl | ||
| weak | -CH2O- | -O- |
-C C- |
-S- | |
| Ph |
Recent Literature
Efficient Two-Step Synthesis of Salicylaldehydes via Directed ortho-Lithiation of in situ N-Silylated
O-Aryl N-Isopropylcarbamates
M. Kauch, D. Hoppe,
Synthesis, 2006, 1575-1577.
Directed Ortho-Metalation of Unprotected Benzoic Acids. Methodology and
Regioselective Synthesis of Useful Contiguously 3- and 6-Substituted
2-Methoxybenzoic Acid Building Blocks
T.-H. Nguyen, A.-S. Castanet, J. Mortier, Org. Lett., 2006, 8, 765-768.
Selective Ortho and Benzylic Functionalization of Secondary and
Tertiary p-Tolylsulfonamides. Ipso-Bromo Desilylation and Suzuki
Cross Coupling Reactions
S. L. MacNeil, O. B. Familoni, V. Snieckus, J. Org. Chem, 2001,
66, 3662-3670.
Palladium-Catalyzed Aryl-Aryl Cross-Coupling Reaction Using ortho-Substituted Arylindium Reagents
M. A. Pena, J. P. Sestelo, L. A. Sarandeses, J. Org. Chem., 2007,
72, 1271-1275.
