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Copper‐Catalyzed Formal CH Carboxylation of Aromatic Compounds with Carbon Dioxide through Arylaluminum Intermediates
Author(s) -
Ueno Atsushi,
Takimoto Masanori,
O Wylie W. N.,
Nishiura Masayoshi,
Ikariya Takao,
Hou Zhaomin
Publication year - 2015
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.201403247
Subject(s) - carboxylation , chemistry , benzofuran , aryl , catalysis , amide , organic chemistry , medicinal chemistry , alkyl
The CH bond carboxylation of various aromatic compounds with CO 2 was achieved by the deprotonative alumination with a mixed alkyl amido lithium aluminate compound i Bu 3 Al(TMP)Li followed by the NHC‐copper‐catalyzed carboxylation of the resulting arylaluminum species, which afforded the corresponding carboxylation products in high yield and high selectivity. In addition to benzene derivatives, heteroarenes such as benzofuran, benzothiophene, and indole derivatives are also suitable substrates. Functional groups such as Cl, Br, I, vinyl, amide, and CN could survive the reaction conditions. Some key reaction intermediates such as the copper aryl and isobutyl complexes and their carboxylation products were isolated and structurally characterized by X‐ray crystallographic analyses, thus offering important information on the reaction mechanism.