Organic amine mediated cleavage of C<sub>aromatic</sub>–C<sub>α</sub> bonds in lignin and its platform molecules

Yu, Xin; Shen, Xiaojun; Dong, Min; Cheng, Xuewu; Liu, Shulin; Yang, Jun; Wang, Zhenpeng; Liu, Huizhen

doi:10.1039/d1sc05231d

“…The versatility of this approach is demonstrated by its successful application to other lignin monomers containing CC bonds or native grasslike lignin as substrates, resulting in high yields of phenols and N , N -dimethylethylamine. The activation mode of amine-assisted prefunctionalization offers a novel approach to break C–C bonds, promoting the full utilization of both the aromatic nuclei and side chains in lignin and its derivatives . We have further extended this strategy of side chain utilization to chitin, which allows for the selective utilization of acetyl groups in chitin, enabling the production of acetamides by reacting chitin with amines …”

Section: Full Utilization Of Aromatic Nuclei and Side Chainsmentioning

confidence: 99%

“…The activation mode of amine-assisted prefunctionalization offers a novel approach to break C−C bonds, promoting the full utilization of both the aromatic nuclei and side chains in lignin and its derivatives. 4 We have further extended this strategy of side chain utilization to chitin, which allows for the selective utilization of acetyl groups in chitin, enabling the production of acetamides by reacting chitin with amines. 57 Above all, our findings demonstrate promising opportunities for creatively utilizing methyl or alkyl groups from lignin in various chemical reactions.…”

Section: Full Utilization Of Aromatic Nuclei and Side Chainsmentioning

confidence: 99%

Catalytic Conversion of Lignin into Valuable Chemicals: Full Utilization of Aromatic Nuclei and Side Chains

Zhang,

Meng,

Liu

et al. 2023

Acc. Chem. Res.

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Transition‐Metal‐Free Synthesis of Functionalized Quinolines by Direct Conversion of β‐O‐4 Model Compounds

Ding

¹

,

Guo

²

,

Li

³

et al. 2022

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Direct production of heterocyclic aromatic compounds from lignin β‐O‐4 models remains a huge challenge due to the incompatible catalysis for aryl ether bonds cleavage and heterocyclic ring formation. Herein, the first example of quinoline synthesis from β‐O‐4 model compounds by a one‐pot cascade reaction is reported in yields up to 89 %. The reaction pathway involves selective cleavage of C−O bonds, dehydrogenation, aldol condensation, C−N bond formation along with heterocyclic aromatic ring construction. The control experiments suggest that both imine and chalcone were identified as the key intermediates, and the rate determining step as well as the preferred pathway were experimentally clarified and supported by density functional theory (DFT) calculations. Based on this protocol, the conversion of β‐O‐4 polymer delivered 56 wt % yield of quinoline derivative in three steps. This transformation provides a potential petroleum‐independent choice for heterocyclic aromatic chemicals.

show abstract

Transition‐Metal‐Free Synthesis of Functionalized Quinolines by Direct Conversion of β‐O‐4 Model Compounds

Ding

¹

,

Guo

²

,

Li

³

et al. 2022

View full text Add to dashboard Cite

Direct production of heterocyclic aromatic compounds from lignin β‐O‐4 models remains a huge challenge due to the incompatible catalysis for aryl ether bonds cleavage and heterocyclic ring formation. Herein, the first example of quinoline synthesis from β‐O‐4 model compounds by a one‐pot cascade reaction is reported in yields up to 89 %. The reaction pathway involves selective cleavage of C−O bonds, dehydrogenation, aldol condensation, C−N bond formation along with heterocyclic aromatic ring construction. The control experiments suggest that both imine and chalcone were identified as the key intermediates, and the rate determining step as well as the preferred pathway were experimentally clarified and supported by density functional theory (DFT) calculations. Based on this protocol, the conversion of β‐O‐4 polymer delivered 56 wt % yield of quinoline derivative in three steps. This transformation provides a potential petroleum‐independent choice for heterocyclic aromatic chemicals.

show abstract

Organic amine mediated cleavage of C_aromatic–C_α bonds in lignin and its platform molecules

Abstract: Pre-functionalization with amine sources mediated the cleavage of Caromatic–Cα bonds to produce two valuable chemicals with high yields, for the full utilization of the aromatic rings and side-chains in lignin and its platform molecules.

Cited by 10 publications

References 46 publications

Catalytic Conversion of Lignin into Valuable Chemicals: Full Utilization of Aromatic Nuclei and Side Chains

Catalytic Conversion of Lignin into Valuable Chemicals: Full Utilization of Aromatic Nuclei and Side Chains

Transition‐Metal‐Free Synthesis of Functionalized Quinolines by Direct Conversion of β‐O‐4 Model Compounds

Transition‐Metal‐Free Synthesis of Functionalized Quinolines by Direct Conversion of β‐O‐4 Model Compounds

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Organic amine mediated cleavage of Caromatic–Cα bonds in lignin and its platform molecules

Abstract: Pre-functionalization with amine sources mediated the cleavage of Caromatic–Cα bonds to produce two valuable chemicals with high yields, for the full utilization of the aromatic rings and side-chains in lignin and its platform molecules.

Cited by 10 publications

References 46 publications

Catalytic Conversion of Lignin into Valuable Chemicals: Full Utilization of Aromatic Nuclei and Side Chains

Catalytic Conversion of Lignin into Valuable Chemicals: Full Utilization of Aromatic Nuclei and Side Chains

Transition‐Metal‐Free Synthesis of Functionalized Quinolines by Direct Conversion of β‐O‐4 Model Compounds

Transition‐Metal‐Free Synthesis of Functionalized Quinolines by Direct Conversion of β‐O‐4 Model Compounds

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Organic amine mediated cleavage of C_aromatic–C_α bonds in lignin and its platform molecules