Selective Catalytic Oxidation of Alcohols, Aldehydes, Alkanes and Alkenes Employing Manganese Catalysts and Hydrogen Peroxide

Abstract

The manganese-containing catalytic system [Mn IV,IV 2 O 3 A C H T U N G T R E N N U N G (tmtacn) 2 ] 2+ (1)/carboxylic acid (where tmtacn = N,N',N''-trimethyl-1,4,7-triazacyclononane), initially identified for the cis-dihydroxylation and epoxidation of alkenes, is applied for a wide range of oxidative transformations, including oxidation of alkanes, alcohols and aldehydes employing H 2 O 2 as oxidant. The substrate classes examined include primary and secondary aliphatic and aromatic alcohols, aldehydes, and alkenes. The emphasis is not primarily on identifying optimum conditions for each individual substrate, but understanding the various factors that affect the reactivity of the Mn-tmtacn cata-lytic system and to explore which functional groups are oxidised preferentially. This catalytic system, of which the reactivity can be tuned by variation of the carboxylato ligands of the in situ formed [Mn III,III 2

Bioinspired oxidations of aliphatic C–H groups with H2O2 in the presence of manganese complexes

“…A set of Me 3 tacn derivatives, including optically pure frameworks of the type 3, were prepared and tested as ligands for Mn-catalyzed oxidation of isopropyl alcohol and several alkanes with H 2 O 2 , either with oxalate or with ascorbic acid as co-catalysts [33]. High ketone selectivities were reported for benzylic oxidations catalyzed by 1 in the presence of trichloroacetic acid [37].…”

Ionic liquids as reaction media in catalytic oxidations with manganese and iron pyridyl triazacyclononane complexes

“…1) belong to this type of compounds and their catalytic activity in oxidation reactions with H 2 O 2 was reported. These complexes have also coincident structural elements with the well-studied Mn(TMTACN) (TMTACN = N,N 0 ,N 00 -trimethyl-1,4,7-triazacyclonona ne) system, which shows excellent performance in a number of oxidative processes, including olefin epoxidation and cis-dihydroxylation reactions [14][15][16][17][18].…”

Direct Selective Oxidative Functionalization of C–H Bonds with H2O2: Mn-Aminopyridine Complexes Challenge the Dominance of Non-Heme Fe Catalysts

“…Ethylbenzene oxidations with H 2 O 2 proceeded with good acetophenone selectivities, while the addition of carboxylate buffers increased the yield of 1-phenylethanol ( Table 2, entry 4). High ketone selectivities were reported for benzylic oxidations, catalyzed by 6, in the presence of trichloroacetic acid [73].…”