Premium
New In Situ Trapping Metalations of Functionalized Arenes and Heteroarenes with TMPLi in the Presence of ZnCl 2 and Other Metal Salts
Author(s) -
Frischmuth Annette,
Fernández Maitane,
Barl Nadja M.,
Achrainer Florian,
Zipse Hendrik,
Berionni Guillaume,
Mayr Herbert,
Karaghiosoff Konstantin,
Knochel Paul
Publication year - 2014
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201403688
Subject(s) - transmetalation , metalation , chemistry , salt (chemistry) , group 2 organometallic chemistry , metal , substrate (aquarium) , structural isomer , nitro , main group element , combinatorial chemistry , inorganic chemistry , organic chemistry , transition metal , catalysis , molecule , alkyl , geology , oceanography
The addition of TMPLi to a mixture of an aromatic or heteroaromatic substrate with a metal salt such as MgCl 2 , ZnCl 2 , 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.