Regioselective Synthesis of Alkylarenes by Two-Step ipso-Substitution of Aromatic Dicarboxylic Acids

被引:8
作者
Bramborg, Andrea [1 ]
Linker, Torsten [1 ]
机构
[1] Univ Potsdam, Dept Chem, D-14476 Potsdam, Germany
关键词
Synthetic methods; Alkylation; Birch reduction; Arenes; Regioselectivity; CROSS-COUPLING REACTIONS; CARBOXYLIC-ACIDS; HECK REACTION; ALKYL; TRANSFORMATIONS; OLEFINATION; REDUCTIONS; OXYGEN; ARYL; IRON;
D O I
10.1002/ejoc.201200823
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
A strategy for the regioselective alkylation of arenes was developed, starting from commercially available and inexpensive terephthalic acid or naphthalene-1,4-dicarboxylic acid. The method entails a formal ipso-substitution of the carboxylate groups by a sequence of reductive alkylation under Birch conditions and subsequent acid-mediated rearomatization with loss of carbon monoxide and carbon dioxide. More than 20 different arenes with various side-chains were synthesized. With naphthalene-1,4-dicarboxylic acid as starting material, we were able to control the degree of alkylation by choosing the appropriate electrophile in the Birch reduction. Thus, bisalkylated naphthalenes and naphthoic acids became available chemoselectively. All reactions afforded a single regioisomer exclusively in high yields. Overall, aromatic dicarboxylic acids are suitable substrates for a two-step ipso-substitution that allows the selective synthesis of alkylated benzenes and naphthalenes.
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页码:5552 / 5563
页数:12
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