title: New in situ trapping metalations of functionalized arenes and heteroarenes with TMPLi in the presence of ZnCl2 and other metal salts.
abstract: The addition of TMPLi to a mixture of an aromatic or heteroaromatic substrate with a metal salt such as MgCl2, ZnCl2, or CuCN at -78 °C first leads to lithiation of the arene followed by transmetalation with the metal salt to afford functionalized organometallic compounds of Mg, Zn, or Cu. This in situ trapping method allows an expedited metalation (-78 °C, 5 min) of a range of sensitive pyridines (bearing a nitro, ester, or cyano group) and allows the preparation of kinetic regioisomers of functionalized aromatic compounds or heterocycles not otherwise available by standard metalating agents, such as TMPMgCl⋅LiCl or TMPZnCl⋅LiCl.
authors.affiliation: Ludwig Maximilians-Universität München, Department Chemie, Butenandtstrasse 5-13, Haus F, 81377 München (Germany).
authors.forename: Annette
authors.initials: A
authors.lastname: Frischmuth
authors.forename: Maitane
authors.initials: M
authors.lastname: Fernández
authors.forename: Nadja M
authors.initials: NM
authors.lastname: Barl
authors.forename: Florian
authors.initials: F
authors.lastname: Achrainer
authors.forename: Hendrik
authors.initials: H
authors.lastname: Zipse
authors.forename: Guillaume
authors.initials: G
authors.lastname: Berionni
authors.forename: Herbert
authors.initials: H
authors.lastname: Mayr
authors.forename: Konstantin
authors.initials: K
authors.lastname: Karaghiosoff
authors.forename: Paul
authors.initials: P
authors.lastname: Knochel
keywords: amide bases; cross-coupling; metalation; nitrogen heterocycles; organometallic compounds