Development of a Flow Photochemical Aerobic Oxidation of Benzylic C–H Bonds

Lesieur, Mathieu; Génicot, Christophe; Pasau, Patrick

doi:10.1021/acs.orglett.8b00540

Cited by 48 publications

(30 citation statements)

References 58 publications

(18 reference statements)

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“…This clearly highlights the importance of counterions in the catalytic performance of charged MOFs and provides a relatively simple method of enhancing reactivity through tunability. Improved performance of perchlorate salts used as additives or cocatalysts in aerobic oxidation reactions has already been observed, although there are no reports toward C–C bond cleavage for lignin model compounds. The weak coordination ability of perchlorate anions presumably facilitates the formation of metal–substrate bonds, which accounts for the superior performance of Cu(ClO 4 ) 2 as a homogeneous catalyst when compared to other copper(II) salts …”

Section: Results and Discussionmentioning

confidence: 99%

Anion-Dependent Catalytic C–C Bond Cleavage of a Lignin Model within a Cationic Metal–Organic Framework

Pim

Mendonça

Brunet

et al. 2020

ACS Appl. Mater. Interfaces

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The development of heterogeneous catalysts capable of selectively converting lignin model compounds into products of added value offers an exciting avenue to explore in the production of renewable chemical feedstocks. The use of metal–organic frameworks (MOFs) in such chemical transformations relies largely on the presence of accessible open metal sites found within highly porous networks that simultaneously allow for fast transport and strong interactions with desired substrates. Here, we present the first systematic study on the modulation of catalytic performance of a cationic framework, [Cu2(L)(H2O)2](NO3)2·5.5H2O (L = 1,1′-bis(3,5-dicarboxylatophenyl)-4,4′-bipyridinium), achieved through the exchange of anionic guests. Remarkably, the catalytic activity proves to be highly anion-dependent, with a nearly 10-fold increase toward the aerobic C–C bond cleavage of a lignin model compound when different anionic species are incorporated within the MOF. Moreover, we demonstrate that the cationic nature of the MOF, imparted by the incorporation of viologen moieties within the linker, tunes the electrophilicity of the active copper(II) sites, resulting in stronger interactions with the substrate. As such, the copper-based framework exhibits enhanced catalytic performance when compared to its neutral counterpart, emphasizing the appeal of charged frameworks for use as green heterogeneous catalysts.

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Section: Results and Discussionmentioning

confidence: 99%

Anion-Dependent Catalytic C–C Bond Cleavage of a Lignin Model within a Cationic Metal–Organic Framework

Pim

Mendonça

Brunet

et al. 2020

ACS Appl. Mater. Interfaces

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“…Pasau and co-workers developed a new mesofluidic flow photo-oxygenation process for benzylic C–H oxidation by using riboflavin tetraacetate (RFT) as the photosensitizer and Fe(ClO 4 ) 2 as an additive with a UV lamp. 237 The desired carbonyl or hydroxyl derivatives were obtained efficiently and selectively without over-oxidation via incorporation of 1 O 2 to the radical intermediate (Fig. 74).…”

Section: Oxidation Reactions In Flow Photochemistrymentioning

confidence: 99%

Continuous flow technology-a tool for safer oxidation chemistry

et al. 2022

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“…In addition, a series of elegant methods were successfully applied to construct C=O, C=C, and C=N double bonds (Scheme B). The direct oxidation of benzylic C(sp 3 )—H bond to aryl ketone was the most common . In 2012, Zhang and Patel accomplished a Pd‐catalyzed benzylic C(sp 3 )—H arylation/oxidation reaction.…”

Section: Background and Originality Contentmentioning

confidence: 99%

Copper‐Catalyzed Benzylic C—H Functionalization, Oxidation and Cyclization of Methylarenes: Direct Access to 2‐Arylbenzothiazoles

Jiang

2019

Chin. J. Chem.

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Summary of main observation conclusion The direct C—H functionalization of methylarenes is of great significance. Herein, a copper‐catalyzed oxidative C—N/C—S bond formation through benzylic C(sp3)—H functionalization, oxidation and cyclization of methylarenes is reported. Various 2‐arylbenzothiazoles have been synthesized in moderate to excellent yields with readily available o‐iodoaniline, potassium sulfide, and methylarenes as raw materials.

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Development of a Flow Photochemical Aerobic Oxidation of Benzylic C–H Bonds

Cited by 48 publications

References 58 publications

Anion-Dependent Catalytic C–C Bond Cleavage of a Lignin Model within a Cationic Metal–Organic Framework

Anion-Dependent Catalytic C–C Bond Cleavage of a Lignin Model within a Cationic Metal–Organic Framework

Continuous flow technology-a tool for safer oxidation chemistry

Copper‐Catalyzed Benzylic C—H Functionalization, Oxidation and Cyclization of Methylarenes: Direct Access to 2‐Arylbenzothiazoles

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