7.26 Glycol Cleavage Reactions

Wong, A.W.H.; Shing, Tony K. M.

doi:10.1016/b978-0-08-097742-3.00731-x

Cited by 5 publications

(5 citation statements)

References 62 publications

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“…The photo reaction setup was purchased from Anhui Kemi machinery technology Co., Ltd. GC analysis was acquired on a Shimadzu GC-2014 Series GC System equipped with a flameionization detector. 1 H NMR and 13 C NMR spectra were recorded on a Bruker Avance 400 spectrometer at ambient temperature. The following abbreviations are used to explain the multiplicities: s = singlet, d = doublet, t = triplet, q = quartet, and m = multiplet.…”

Section: Materials and Instrumentationmentioning

confidence: 99%

“…The aerobic oxidative cleavage of CÀ C bonds in 1,2-diols to prepare corresponding carbonyl compounds (carboxylic acid, aldehyde, ketone) is a very significant fundamental reaction in synthetic organic chemistry. This reaction is widely employed in various scenarios, such as organic synthesis, [1] biomass valorization, [2][3][4] analytical studies in biochemistry [5] and so on. In the early 20th century, the Malaprade reaction [6] and the Criegee oxidation [7] were the classical methods to transform 1,2diols to aldehydes or ketones.…”

Section: Introductionmentioning

confidence: 99%

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Metal‐free Photocatalytic Aerobic Oxidative Cleavage of C−C Bonds in 1,2‐Diols

et al. 2020

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The preparation of carbonyl compounds by the aerobic oxidative cleavage of CÀ C bonds in 1,2-diols under mild reaction conditions is a very significant reaction and is widely employed in various scenarios. Avoiding the use of harmful stoichiometric oxidants and adopting a greener chemical process remain a challenge for this reaction to date. In this manuscript, a heterogeneous metal-free photocatalytic strategy without any additive was developed for aerobic oxidative cleavage of CÀ C bonds in 1,2-diols at ambient conditions with visible light. The reaction mechanism was further studied through a series of control experiments and density functional theory (DFT) calculations. In addition, the catalytic system showed a broad substrates scope, including aliphatic (linear or cyclic) 1,2-diols, benzylic, alkenyl 1,2-diols, and α-hydroxy acids (such as lactic acid). Thus, this strategy could serve as a method for the transformation of 1,2-diols to corresponding carbonyl compounds by the aerobic oxidative cleavage of CÀ C bonds.

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Section: Materials and Instrumentationmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Metal‐free Photocatalytic Aerobic Oxidative Cleavage of C−C Bonds in 1,2‐Diols

et al. 2020

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“…The famous ones are biomass-derived cellulose, hemicelluloses, and lignin. Thus, the selective C–C bond cleavage is considered a promising way for the efficient valorization of biomass feedstocks. − In particular, it can provide the effective synthesis approach to achieve the sustainable production of value-added chemicals and pharmaceutical intermediates in the chemical industry. , As a representative technology, the direct oxidative cleavage processes of vicinal diols have been widely investigated . The traditional method for the direct oxidative C–C bond cleavage of vicinal diols requires a large amount of stoichiometric oxidants, including periodates, , lead tetraacetate, manganese dioxide, , chromium trioxide, , and so forth.…”

Section: Introductionmentioning

confidence: 99%

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

Meng

Tong

Sun

et al. 2022

ACS Sustainable Chem. Eng.

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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.

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“…24,25 Although catalytic alternatives have been proposed recently, they suffer from several drawbacks, as these catalysts are either based on precious metals or are homogeneous and not reusable. 26,27 The heterogeneous nature of the EcoMnOx catalyst and its reuse are thus key advantages, combined to the use of O 2 or air as benign oxidant. This Mn catalyst prepared by valorization of waste biomass provides thus an efficient and sustainable alternative to previous methods of 1,2-diols oxidative cleavage.…”

Section: ■ Introductionmentioning

confidence: 99%

“…This reaction is usually performed with stoichiometric reagents, such as sodium periodate or lead tetraacetate, producing large amounts of toxic byproducts. Classical reaction conditions for oxidative cleavage of 1,2-diols are thus challenged by current standards of green chemistry. , Although catalytic alternatives have been proposed recently, they suffer from several drawbacks, as these catalysts are either based on precious metals or are homogeneous and not reusable. , The heterogeneous nature of the EcoMnOx catalyst and its reuse are thus key advantages, combined to the use of O 2 or air as benign oxidant. This Mn catalyst prepared by valorization of waste biomass provides thus an efficient and sustainable alternative to previous methods of 1,2-diols oxidative cleavage.…”

Section: Introductionmentioning

confidence: 99%

EcoMnOx, a Biosourced Catalyst for Selective Aerobic Oxidative Cleavage of Activated 1,2-Diols

Escande

Lam²,

Grison

et al. 2017

ACS Sustainable Chem. Eng.

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A novel catalyst, EcoMnOx, was prepared from waste biomass of Mn-hyperaccumulating plants. The valorization of this Mn-rich biomass is an alternative to its costly usual disposing and provides a new source of Mn. Extracted metal ions, including Mn 2+ , were oxidized in mild conditions by H 2 O 2 /NaOH to afford EcoMnOx, as a polymetallic oxide material containing from 8.9 to 14.1 wt % Mn. Spectroscopic studies of this material revealed the presence of Mn layered mixed oxides, rich in Mn IV along with Mn III and Mn II species. EcoMnOx catalytic properties were assessed in the aerobic oxidative cleavage of 1,2-diols, under atmospheric pressure of O 2 or air. With only 10 mol % Mn, up to complete conversions were obtained on activated benzylic and allylic diols, with excellent selectivity toward aldehydes or ketones (98− 99%). Moreover, because of its heterogeneous nature, the catalyst can be removed easily by filtration, and reapplied for a minimum of six successive runs without any loss of activity. Finally, E-factor analysis showed the EcoMnOx generates 4 to 17 times less waste compared to classical reagents such as NaIO 4 and Pb(OAc) 4 , respectively, highlighting the sustainable assets of this new heterogeneous catalyst.

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7.26 Glycol Cleavage Reactions

Cited by 5 publications

References 62 publications

Metal‐free Photocatalytic Aerobic Oxidative Cleavage of C−C Bonds in 1,2‐Diols

Metal‐free Photocatalytic Aerobic Oxidative Cleavage of C−C Bonds in 1,2‐Diols

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

EcoMnOx, a Biosourced Catalyst for Selective Aerobic Oxidative Cleavage of Activated 1,2-Diols

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