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1,10‐Phenanthroline Carboxylic Acids for Preparation of Functionalized Metal‐Organic Frameworks
Author(s) -
Abel Anton S.,
Yu Mitrofanov Alexander,
Yakushev Aleksei A.,
Zenkov Ilya S.,
Morozkov Gleb V.,
Averin Alexei D.,
Beletskaya Irina P.,
Michalak Julien,
Brandès Stéphane,
BessmertnykhLemeune Alla
Publication year - 2019
Publication title -
asian journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.846
H-Index - 44
eISSN - 2193-5815
pISSN - 2193-5807
DOI - 10.1002/ajoc.201900569
Subject(s) - chemistry , phenanthroline , nucleophile , carbonylation , carboxylate , catalysis , medicinal chemistry , organic chemistry , sonogashira coupling , palladium , bromine , carboxylic acid , hydrolysis , polymer chemistry , carbon monoxide
Synthetic approaches to 1,10‐phenanthroline‐3‐carboxylic acid ( 2 ), 1,10‐phenanthroline‐3,8‐dicarboxylic acid ( 3 ) and their functionalized derivatives were investigated. Acids 2 and 3 were prepared in good yields from bromophenanthrolines via palladium‐catalyzed alkoxycarbonylation. Moreover, butyl 8‐bromo‐1,10‐phenanthroline‐3‐carboxylate was obtained in acceptable yield (25–35%) by ceasing the carbonylation of the dibromide 5 after 30–70% consumption of the starting compound. To prepare functionalized derivatives of acids 2 and 3 , the reactions of butyl 8‐bromo‐1,10‐phenanthroline‐3‐carboxylate and diethyl 4,7‐dichloro‐1,10‐phenanthroline‐3,8‐dicarboxylate with various nucleophiles were investigated. S N Ar reactions are suitable for the synthesis of 4,7‐diazido‐, dimethoxy‐ and diamino‐substituted 3,8‐bis(ethoxycarbonyl)phenanthrolines, including the macrocyclic derivatives. The bromine atom at position 8 of the phenanthroline ring reacts with nucleophiles only in the presence of the palladium catalysts. The scope of these reactions was briefly investigated conducting Sonogashira, Suzuki‐Miyaura and Hirao reactions. Hydrolysis of the functionalized esters of phenanthroline leads to corresponding acids in good yields.