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Selective Catalytic Oxidation of Alcohols, Aldehydes, Alkanes and Alkenes Employing Manganese Catalysts and Hydrogen Peroxide
Author(s) -
Saisaha Pattama,
Buettner Lea,
van der Meer Margarethe,
Hage Ronald,
Feringa Ben L.,
Browne Wesley R.,
de Boer Johannes W.
Publication year - 2013
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.201300275
Subject(s) - chemistry , catalysis , reactivity (psychology) , manganese , hydrogen peroxide , alcohol oxidation , substrate (aquarium) , dihydroxylation , peroxide , organic chemistry , medicinal chemistry , selectivity , catalytic oxidation , primary (astronomy) , alkane , aldehyde , enantioselective synthesis , medicine , geology , oceanography , alternative medicine , physics , pathology , astronomy
Abstract The manganese‐containing catalytic system [Mn IV,IV 2 O 3 (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 catalytic 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 (O)(RCO 2 ) 2 (tmtacn) 2 ] 2+ dimers, employs H 2 O 2 in a highly atom efficient manner. In addition, several substrates containing more than one oxidation sensitive group could be oxidised selectively, in certain cases even in the absence of protecting groups.