Aerobic Oxidation of Benzylic Hydrocarbons by Iron‐Based Metal Organic Framework as Solid Heterogeneous Catalyst

Abstract

In the present work, the aerobic oxidation of indan is reported using Fe(BTC) (BTC: 1,3,5‐benzenetricarboxylate) as solid heterogeneous catalyst and tetrabutylammonium bromide (TBAB) as an additive under mild reaction conditions. Although aerobic oxidation of indane has been reported earlier using MOFs as heterogeneous catalysts, these methods require higher reaction temperature and catalytic amounts of radical initiator. Therefore, this study aims to report the aerobic oxidation of indan employing Fe(BTC) as catalyst without the need of initiators under mild reaction temperature. The catalytic data reveal that the indan conversion reaches to 18% with 97% selectivity of indanol at 80 °C in acetonitrile as solvent. Furthermore, the catalyst stability is surveyed by performing reusability experiments and observing no decay in its activity. On other hand, comparison of fresh with three times reused Fe(BTC) samples by powder X‐ray diffraction (XRD) and scanning electron microscope (SEM) indicates that the crystallinity and morphology of the reused sample, respectively is retained during the course of the reaction. Finally, two times reused Fe(BTC) exhibits similar electron spin resonance (ESR) pattern with that of fresh Fe(BTC), suggesting no changes in the oxidation state of iron.

A superhydrophobic MOF facilitating efficient solvent-free catalytic chemical fixation of CO2 and oxidation of hydrocarbons and MOF@cotton@starch composite-based selective sensing of a herbicide

“…16 Besides these conventional MOF catalysts, porphyrin-based MOFs have also been reported as oxidation catalysts. 17 Due to these features of MOFs compared to other heterogeneous catalysts, wide ranges of MOFs have been reported for the aerobic oxidation of hydrocarbons, including Au-Pd/MIL-101, 18 MIL-101, 19 NHPI/Fe(BTC), 20 Fe(BTC)/TBAB, 21 {[Cu 0.5 La 2 (HPDC)(PDC) 2 (SO 4 )(H 2 O) 2 ]H 2 O} n , 22 NHPI/Fe(BTC), 23 Cu-doped ZIF-8 24 and Ce-based MOF. 25 However, the catalytic performance of a MOF solid in the oxidation of hydrocarbon depends on many factors, such as the nature of active sites, the nature of the oxidant, reaction temperature, and solvent.…”

Organo-photocatalytic C–H bond oxidation: an operationally simple and scalable method to prepare ketones with ambient air

“… 6 However, due to the inertness of O 2 towards closed-shell organic molecules and limited solubility of O 2 in organic solvents under ambient pressure, 7 a unified approach, capable of delivering scalable aerobic C–H bond oxidation in an operationally simple fashion such as batch setting with ambient air, is highly valuable but challenging to develop. Many thermal methods for C–H bond oxidation of alcohols and alkylbenzenes require pure O 2 atmosphere or high pressure of inert-gas-diluted O 2 , 8 elevated temperature, 9 toxic/corrosive solvents, 10 expensive transition metal catalysts, 11 and prolonged reaction time 12 which are undesirable from cost and safety considerations especially when large-scale applications are concerned ( Fig. 1A ).…”

Cu2O−CD nanosuperstructures as a Biomimetic Catalyst for Oxidation of Benzylic sp3 C−H bonds and Secondary Amines using Molecular Oxygen: First Total Synthesis of proposed Swerilactone O

“…Many such strategies integrating transition-metal catalysts along with oxygen or peroxides as the terminal oxidants have seen limelight. [4,5] A plethora of metal catalysts are showcased for the benzylic sp 3 CÀ H bond oxidation reactions, such as those involving chromium, [6][7][8][9][10][11][12][13] manganese, [14][15][16][17] iron, [18][19][20][21][22][23][24] cobalt, [25][26][27][28][29] bismuth, [30,31] ruthenium, [32][33][34] and rhodium. [35,36] Yet, many of these metal catalysts are toxic, expensive, functional only in organic solvents, involve the use of peroxides, and are also nonrecoverable which are the limitations of these protocols.…”