Biomimetic Oxidation of Hydrocarbons with Air over Metalloporphyrins

摘要: The oxidation of C-H, C-C and C=C hydrocarbons, from the syntheses many fine chemicals to manufacture various commodities in large scale, plays great important role transformation basic materials useful synthetic building organic chemistry conversion hydrocarbon oxygen-containing industrial production especially hydroxylation, epoxidation, degradation derivatives[1-6]. Conventional methodologies often suffer low chemoand/or regio-selectivity with turnover number (TON) an unfriendly way both economical environmental aspects which catalyst is very expensive generates amounts hazardous waste. Oxidation reactions catalyzed by non-metal[7-8] metal[9-14] catalysts have been receiving increasing attention, particularly for highly selective aerobic oxidations metal complexes[15-17]. In nature, processes are carried out a manner monoor dioxygenases under mild conditions[18-19]. A well-known type monooxygenase cytochrome P-450(CP-450)[2023], features iron porphyrin core, can catalyze wide variety including dealkylation, degradation, dehydrogenation, amines, sulfides, alcohols aldehydes, even unreactive substrates such as unactivated hydrocarbons. This stimulates numerous efforts developing biomimetic systems[24-26]. Metalloporphyrins, core structure closely resembling that CP-450, extensively studied oxidate series kind mimic natural style[24,27]. 1979, Groves co-workers[28] reported first system metalloporphyrin catalyst. They developed terminal oxidant iodosylbenzene(PhIO) ironporphyrin [FeIII(por)Cl], effect epoxidation styrene cyclohexene, hydroxylation cyclohexane adamantane. Subsequently, reports focusing on metalloporphyrin-catalyzed systems appeared literature, described previous reviews[29-34]. As documented alkanes alkenes iron, manganese ruthenium porphyrins traditional oxidants PhIO, NaOCl 2,6-dichloropyridine-N-oxide, enantioselective most systems.