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Iron and Manganese Catalysts for the Selective Functionalization of Arene C(sp 2 )−H Bonds by Carbene Insertion
Author(s) -
Conde Ana,
Sabenya Gerard,
Rodríguez Mònica,
Postils Verònica,
Luis Josep M.,
DíazRequejo M. Mar,
Costas Miquel,
Pérez Pedro J.
Publication year - 2016
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201601750
Subject(s) - carbene , chemistry , surface modification , catalysis , cycloheptatriene , manganese , ethyl diazoacetate , medicinal chemistry , ligand (biochemistry) , alkylbenzenes , aryl , cyclopropanation , stereochemistry , organic chemistry , biochemistry , alkyl , receptor
The first examples of the direct functionalization of non‐activated aryl sp 2 C−H bonds with ethyl diazoacetate (N 2 CHCO 2 Et) catalyzed by Mn‐ or Fe‐based complexes in a completely selective manner are reported, with no formation of the frequently observed cycloheptatriene derivatives through competing Buchner reaction. The best catalysts are Fe II or Mn II complexes bearing the tetradentate pytacn ligand (pytacn= 1‐(2‐pyridylmethyl)‐4,7‐dimethyl‐1,4,7‐triazacyclononane). When using alkylbenzenes, the alkylic C(sp 3 )−H bonds of the substituents remained unmodified, thus the reaction being also selective toward functionalization of sp 2 C−H bonds.