Sustainable and Selective Aerobic Oxidative C–C Bond Cleavage of Vicinal Diols under Near-Room-Temperature Condition

Abstract

The selective oxidative C−C bond cleavage is essential for the production of functional molecules. Herein, a sustainable and efficient heterogeneous catalytic protocol is developed to facilitate the aerobic oxidative C−C bond cleavage, in which the selective conversion of vicinal diols to the corresponding aldehydes was achieved under a near-room-temperature condition with NH 3 -treated cobalt catalysts. Hydrobenzoin was selectively transformed to generate benzaldehyde with the solid Co m O n /C−N catalyst, where the conversion and product selectivity reached 96.7 and 99.0% under an oxygen atmosphere, respectively. Further investigations revealed that the high catalytic activity of the catalyst is contributed to numerous oxygen defects, which lead to efficient generation of active 1 O 2 species. Moreover, the Co m O n /C−N catalyst still exhibited a very high catalytic activity after it was continuously recycled five times. Finally, the oxidative cleavages of the C−C bond in the different 1,2-diols were also studied where more than 96.5% conversion of substrates and 99% selectivity of aldehydes were acquired under the optimal conditions.

Enhancing the photocatalytic upcycling of polystyrene to benzoic acid: a combined computational-experimental approach for acridinium catalyst design

“…2C(ii)). Compared with existing reported homogeneous photoredox catalysts reported to degrade PS into oxygenated aromatics (Section S6 †), [18][19][20][21]42,43 the catalytic turnover of FPh-Acr-Np was amongst the best, and is especially advantaged by the low catalyst loadings required using our reaction conditions.…”

Vanadium Catalyst in Micelles: Toward a Greener Aerobic Oxidative Cleavage of Vicinal Diols in Water

“…This important synthetic transformation has historically been performed in organic solvents with stoichiometric amounts of oxidants such as periodates 57 or lead tetra-acetate (Scheme 1a). 58 Transition metal-catalyzed aerobic oxidations (Scheme 1b) have also been reported using cobalt, 59,60 iron, 61,62 manganese, 63−65 nickel, 66 molybdenum, 67 silver, 68,69 cerium, 70 or vanadium complexes. 71−73 Very recently, the aerobic oxidative C−C bond cleavage of vicinal diols in CTABr micellar medium has been reported, using a heterogeneous graphitic carbon nitride photocatalyst.…”

Metal-Free Nitrogen-Doped Porous Carbons for Nitriles and Amides Synthesis from 1,2-Diols via Oxidative Cleavage of C–C Bonds

“…To this context, the development of environmentally benign oxidation methodologies has gained a growing attention, and continuing efforts have been dedicated to allow green and cheap molecular oxygen for the cleavage and functionalization of 1,2-diols. Up to now, although numerous catalytic systems allow for converting 1,2-diols into aldehydes, – ketones, – acids, – and esters , with oxygen as the oxidant (Scheme a), approaches aimed at installing the nitriles and amides directly from 1,2-diols still remain scarce. To the best of our knowledge, only two metal-catalyzed strategies, employing manganese-oxide and enzyme-mimic iron single-atom catalyst, have been disclosed to date for the ammoxidation of 1,2-diols to produce nitriles and amides (Scheme b). , Compared with metal-based catalysts, metal-free catalysis is of increasing interest in organic synthesis because of its unique advantages, such as no metal residue, lower cost, higher reliability, biocompatibility, and sustainability.…”