Aerobic oxidative cleavage of 1,2-diols catalyzed by atomic-scale cobalt-based heterogeneous catalyst

Abstract

The oxidative cleavage of the CC bonds in 1,2-diols is an important transformation in synthetic organic chemistry. The challenge for this reaction is to develop a recyclable catalyst and an efficient catalytic system that operates under mild conditions. Here we report an atomically dispersed cobalt (3.8 wt% Co) on N-doped carbon catalyst, which exhibits improved catalytic activity toward the oxidative cleavage of a variety of 1,2-diols into esters, ketones or aldehydes using molecular oxygen under mild conditions. For example, the oxidative cleavage of internal diols is achieved at ambient temperature and air pressure. The robust catalyst can be reused at least seven times without regeneration treatment. The formation of highly dispersed active CoN x sites is demonstrated by catalyst characterization and potassium thiocyanate poisoning experiment. Mechanistic insights into monosubstituted diols indicate a sequence reaction including stepwise oxidation/nucleophilic addition/C-C bond cleavage, and reveal two reaction pathways.

One-pot synthesis of new alkyl 1-naphthoates bearing quinoline, pyranone and cyclohexenone moieties via metal-free sequential addition/oxidation reactions

“…According to our results and the other reports, 31,41 we have proposed a plausible mechanism for this synthetic process as depicted in Scheme 3, in which the alkoxide ion acts as the base to activate the 1,3-diketone 2, which subsequently attacks acenaphthoquinone 1 to produce the vicinal diol intermediate 4.…”

Cobalt Nanoparticles‐Catalyzed Widely Applicable Successive C−C Bond Cleavage in Alcohols to Access Esters

“…Then, there are two possible reaction pathways. On one hand, the generated 7 c is oxidized to 7 d , and then the cleavage of C−C bond affords the ester 2 o with release of formic acid followed by the decomposing to CO 2 and H 2 (Supporting Information, Figure S17 and 18) . On the other hand, 7 c reacts with water to form the hydrated a,a‐bis(hydroxy)acetophenone ( 7 e ).…”

The occurrence of inositolphosphoceramides in spirulina microalgae

“…4). This product ion may be generated by virtue of a 1,2-diol in the fatty acyl moiety whereby the C-C bond cleavage may be expected [31].…”