Synthesis and Applications of (ONO Pincer)Ruthenium-Complex-Bound Norvalines

Abstract

Two (ONO pincer)ruthenium-complex-bound norvalines, Boc-[Ru(pydc)(terpy)]Nva-OMe (1; Boc=tert-butyloxycarbonyl, terpy=terpyridyl, Nva=norvaline) and Boc-[Ru(pydc)(tBu-terpy)]Nva-OMe (5), were successfully synthesized and their molecular structures and absolute configurations were unequivocally determined by single-crystal X-ray diffraction. The robustness of the pincer Ru complexes and norvaline scaffolds against acidic/basic, oxidizing, and high-temperature conditions enabled us to perform selective transformations of the N-Boc and C-OMe termini into various functional groups, such as alkyl amide, alkyl urea, and polyether groups, without the loss of the Ru center or enantiomeric purity. The resulting dialkylated Ru-bound norvaline, n-C11H23CO-l-[Ru(pydc)(terpy)]Nva-NH-n-C11H23 (l-4) was found to have excellent self-assembly properties in organic solvents, thereby affording the corresponding supramolecular gels. Ru-bound norvaline l-1 exhibited a higher catalytic activity for the oxidation of alcohols by H2O2 than parent complex [Ru(pydc)(terpy)] (11 a).