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Synfacts 2023; 19(02): 0171
DOI: 10.1055/s-0042-1753206
Polymer-Supported Synthesis

Metal-Free Oxidative C–C Bond Cleavage of Ketones Promoted by Biomass-Derived Carbons

Contributor(s):
Yasuhiro Uozumi
,
Shintaro Okumura
Liu X, Qin J, Dai W, *, Zhu Z, Zhou P, Wang Y, Nie J, Yang Y, Zhang Z. * Dalian Institute of Chemical Physics and South-Central University for Nationalities, Wuhan, P. R. of China
Metal-Free and Additive-Free Synthesis of Imides and Nitriles from Ketones via Oxidative Cleavage of C(O)–C Bonds.

ACS Catal. 2022;
12: 13300-13311
DOI: 10.1021/acscatal.2c02847.
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Key words

C–C bond cleavage - carbon materials - ketones - nitriles - phthalimides

Significance

A carbon material (C-800), prepared by the pyrolysis of biomass (bamboo) with K2CO3 at 800 °C, promoted the C(carbonyl)–C bond cleavage of aromatic cyclic ketones with amines and O2 to give the corresponding phthalimides in up to 99% yield (eq. 1). C-800 also cleaved the C(carbonyl)–C bonds and C (benzylic)–C bonds of acyclic ketones with NH3 and O2 at 160 °C to give the corresponding aryl nitriles in up to 97% yield (eq. 2).


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Comment

In the reaction of acetophenone with NH3, the catalyst was recovered by centrifugation and reused five times without significant loss of its catalytic activity. Experimental and computational studies suggested that functional oxygen groups on the surface of the catalyst adsorbed ketones and that the defective sites of the catalyst activated O2 to generate a superoxide radical.


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Publication History

Article published online:
17 January 2023

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