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Synthesis of Heterodinuclear Hemisalen Complexes on a Hexaarylbenzene Scaffold and their Application for the Cross‐Pinacol Coupling Reaction
Author(s) -
Miyasaka Akihiro,
Amaya Toru,
Hirao Toshikazu
Publication year - 2014
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201303946
Subject(s) - pinacol , chemistry , vanadium , coupling reaction , catalysis , ligand (biochemistry) , titanium , diol , selectivity , hydroxymethyl , medicinal chemistry , combinatorial chemistry , organic chemistry , polymer chemistry , biochemistry , receptor
Abstract Intermolecular cross‐pinacol coupling reaction between aliphatic and aromatic aldehydes by using heterodinuclear hemisalen complexes 1 cis with vanadium(V) and titanium(IV) on a hexaarylbenzene scaffold is reported. Our ligand design is based on the individual activation of two aldehydes by vanadium and titanium, which are positioned with a suitable space on the rigid scaffold. Ligands such as 1 cis were synthesized by Diels–Alder addition and decarbonylation reaction, followed by condensation of dialdehyde 3 cis with various aminophenols. The influence of the substituents on the ligands on the pinacol coupling reaction was investigated. As a result, the reductive coupling reaction between aliphatic and aromatic aldehydes by using a catalytic amount of 1 cis in the presence of Me 3 SiCl and Zn provided the corresponding cross‐coupled 1,2‐diol in good yields with high cross‐selectivity.