Sequential meta-/ortho-C–H Functionalizations by One-Pot Ruthenium(II/III) Catalysis
Citations Over TimeTop 10% of 2017 papers
Abstract
Sequential twofold meta-C–H/ortho-C–H functionalization was achieved by means of versatile ruthenium(II) biscarboxylate catalysis. The double C–H activation proved viable in a one-pot fashion with the assistance of synthetically useful imidates. The operationally simple twofold C–H functionalization occurred with high levels of positional selectivity control and was conducted in a nonsequential manner by the judicious choice of the reaction temperature. Detailed experimental mechanistic studies, including unprecedented electron paramagnetic resonance (EPR) experiments, provided strong support for homolytic C–X bond cleavage and facile C–H ruthenation, while a computational density functional theory (DFT) analysis was supportive of a novel mechanistic scenario involving synergistic catalysis via cyclometalated ruthenium(III) complexes as key intermediates.
Related Papers
- → Hydroperoxysterols as a probe for the mechanism of cytochrome P-450scc-mediated hydroxylation. Homolytic versus heterolytic oxygen-oxygen bond scission.(1986)29 cited
- → Pressure effects as mechanistic probes for homolytic thermal cobaltcarbon bond cleavage of cobalamins(1992)9 cited
- → Ab initio calculations on P?C bond cleavage in phosphoranyl radicals: implications for the biodegradation of organophosphonate derivatives(1998)8 cited
- → Formation and homolytic cleavage of the Ni(II)–styryl σ‐bond(1973)2 cited
- → ChemInform Abstract: THERMAL DECOMPOSITION OF TERTIARY ALKYL PEROXIDES, SUBSTITUENT EFFECTS IN PEROXIDE BOND HOMOLYSIS AND BETA SCISSION OF ALKOXY RADICALS(1974)