Oxidation of alkanes with m-chloroperbenzoic acid catalyzed by iron(III) chloride and a polydentate amine

Abstract

Tetradentate amine N,N-bis(2-pyridylmethylene)-1,4-diaminodiphenyl ether (compound 1) dramatically accelerates the oxidation of alkanes with MCPBA in acetonitrile catalyzed by FeCl 3 , whereas N,N-bis(2-pyrrolidinmethylene)-1,4-diaminodiphenyl ether (2) does not affect the reaction. The selectivity of the reaction in the presence of 1 is noticeably higher than that in its absence. On the basis of the kinetic study and selectivity parameters a mechanism has been proposed which includes the formation of a complex between a molecule of MCPBA and coordinated to ligand 1 iron ion. This complex decomposes to produce a Fe(II) derivative which is further oxidized by MCPBA to generate a (1•Fe=O) 4+ species reacting with both alkane and acetonitrile. Finally, alkyl hydroperoxide is formed which partially decomposes to produce more stable corresponding alcohol and ketone (aldehyde).

New Trends in Oxidative Functionalization of Carbon–Hydrogen Bonds: A Review

“…So-called Shilov chemistry [1,[286][287][288][289][290][291] m-Chloroperbenzoic acid in the presence of certain metal compounds efficiently oxidizes alkanes at low temperature with a very high degree of stereoselectivity (trans/cis << 1) [160,227,284,285]. Apparently, radicals are not produced intermediately in the course of such oxidation, which occurs via a "concerted" mechanism.…”

Half‐Sandwich Scorpionate Vanadium, Iron and Copper Complexes: Synthesis and Application in the Catalytic Peroxidative Oxidation of Cyclohexane under Mild Conditions

“…In fact, M n À OOH species, which have also been invoked in some peroxidative alkane oxidations systems, can undergo, in principle, any of the following further reactions: [10,26] (i) attack at the alkane (RH), thus acting as a metalbased oxidant, to yield The promoting effect of 3-chloroperoxybenzoic acid, 3-ClC 6 H 4 C(=O)OOH, can be associated to the metal-assisted formation of the reactive hydroxyl radical (upon homolytic scission of the O À O 712 asc.wiley-vch.de bond), [27,28] of an oxo-metal (M=O) active species (by heterolytic O À O bond cleavage) [27,29] or of the reactive acylperoxy radical 3-ClC 6 H 4 C(=O)OOC [29,30] (which can oxygenate the alkane RH to give the alcohol ROH and the corresponding acyloxy radical 3-ClC 6 H 4 COOC).…”

Oxidations catalyzed by osmium compounds. Part 1: Efficient alkane oxidation with peroxides catalyzed by an olefin carbonyl osmium(0) complex

“…It is interesting to note that although iron plays an extremely important role in oxidations occurring in living cells (e.g., cytochrome P450 [1,2,36] and methanemonooxygenase, MMO [1,2,[37][38][39]) iron complexes and especially simple salts of this metal do not usually exhibit high activity in oxidations in vitro. Turnover numbers (TONs) in alkane oxidations are typically attain values only of 20-100 [34,35,[40][41][42][43][44][45]. Thus, TONs in FeCl 3 -catalyzed ''Gif oxidations'' (i.e., in the presence of pyridine) have been reported to equal values not higher than 1-20 [46].…”