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N‐Heterocyclic Carbene–Pd Polymers as Reusable Precatalysts for Cyanation and Ullmann Homocoupling of Aryl Halides: The Role of Solvent in Product Distribution
Author(s) -
Karimi Babak,
Vafaeezadeh Majid,
Akhavan Pari Fadavi
Publication year - 2015
Publication title -
chemcatchem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.497
H-Index - 106
eISSN - 1867-3899
pISSN - 1867-3880
DOI - 10.1002/cctc.201500383
Subject(s) - cyanation , chemistry , aryl , benzonitrile , carbene , aryl halide , solvent , catalysis , organic chemistry , halide , polyethylene glycol , coupling reaction , polymer chemistry , product distribution , combinatorial chemistry , ullmann reaction , palladium , alkyl
A main‐chain N‐heterocyclic carbene (NHC) polymer with N ‐dodecyl‐substituted groups was found to be a highly efficient precatalyst for cyanation of various aryl halides by using nontoxic cyanic source [K 4 Fe(CN) 6 ] under relatively mild reaction conditions. Several aryl iodides, bromides, and activated chlorides were successfully converted to their corresponding benzonitrile derivatives without using additives (such as reducing agents or exogenous organic ligands) in good to excellent yields. Our investigations showed that changing the solvent from DMF to polyethylene glycol (PEG‐200) resulted in dramatic decline of cyanation product formation to the benefit of the Ullmann homocoupling reaction. The catalyst could be reused four and five times with only slight loss of activity in cyanation and the Ullmann coupling, respectively.