Uncommon reactivity of the propargylamine and propargylamide substituents in the functionalized clathrochelate iron(II) complexes.
Автор(и)
R. A. Selin
PBMR Labs Ukraine
Vernadsky Institute of General and Inorganic Chemistry NAS
V. Y. Chernii
Vernadsky Institute of General and Inorganic Chemistry NAS
S. V. Vakarov
Vernadsky Institute of General and Inorganic Chemistry NAS
Y. Z. Voloshin
Nesmeyanov Institute of Organoelement Compounds RAS
Kurnakov Institute of General and Inorganic Chemistry RAS
Анотація
Nowadays, the compounds with ethynyl group(s) are frequently used for their further modifications using the methods of modern so-called “click”-chemistry, based on the metalpromoted 1,3-dipolar cycloaddition reactions. We performed an attempt to obtain new monoribbed-difunctionalized clathrochelate iron(II) complexes with propargylamine- or propargylamide-terminated ribbed substituents as the prospective macrobicyclic precursors of their Sonogashira reactions. However, we observed an uncommon low chemical stability of these propargylamine and propargylamide cage complexes under basic conditions. In particular, the propargylamide substituent of the iron(II) complex 1 (Scheme) underwent a slow hydrolysis in the presence of triethylamine in its dichloromethane solution, thus giving the terminal carboxyl group, while, in the case, of the clathrochelate 2, its reductive elimination reaction occurred. The same result was observed after a stirring of the dichloromethane solution of this monopropargylamine iron(II) cage complex with NaHCO3 aqueous solution.
