Selective functionalization of C(sp³)–H bonds: catalytic chlorination and bromination by Iron^III-acacen-halide under ambient condition

Abstract

The oxidative catalytic halogenation of the C(sp3)–H bond of alkanes promoted by FeIII(acacen)Cl (1III-Cl) and FeIII(acacen)Br (1III-Br) in the presence of trifluoroacetic acid (TFA) was investigated. Four major steps were...

Natural Abiotic Iron-Oxido-Mediated Formation of C1 and C2 Compounds from Environmentally Important Methyl-Substituted Substrates

“…Based on all data discussed so far, it appears that all products characterized, also in terms of their origin on the basis of isotope labeling experiments, and to a large extent quantified, primarily originate from a reaction cascade that in the first step produces CH 3 radicals, initiated by oxygen atom transfer from LFe IV O to the sulfur atom of DMSO. This is further supported by experiments, where either CH 2 Br 2 or CCl 3 Br was added to the standard experiment (see the Supporting Information for experimental conditions and detailed results, Figure S11): both CH 2 Br 2 and CCl 3 Br are known to trap alkyl radicals and lead to the corresponding brominated products, i.e., CD 3 Br in our experiments with d 6 -DMSO, and the resulting products of the quencher; i.e., CH 2 Br and CCl 3 radicals abstract H (or D) atoms from the molecules present in solution to produce CH 3 Br (or CH 2 DBr) and CHCl 3 (or CDCl 3 ), respectively. ,, As for the CD 3 radicals produced from d 6 -DMSO, a range of C 1 and C 2 products are expected from CH 2 Br and CCl 3 radicals with CH 3 Br and CHCl 3 as the main products. Unfortunately, the solubility of the two quenchers in aqueous solution is limited.…”