Substituted anilides from chitin-based 3-acetamido-furfural

van der Loo, Cornelis H. M.; Kaniraj, J. P.; Wang, Ting; Broekman, J. O. P.; Borst, Mark L. G.; Pouwer, Kees; Heeres, André; Deuss, Peter J.; Minnaard, Adriaan J.

doi:10.1039/d3ob01461d

Cited by 6 publications

(2 citation statements)

References 44 publications

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“…10−12 The diene moiety in chitin-based furans makes these substrates suitable for chemical structure diversification via Diels−Alder (DA) chemistry and, for example, coupled to an aromatization reaction to yield aniline derivatives. 13 With 100% atom economy, the DA cycloaddition is a powerful tool for sustainable upgrading of biobased furan derivatives. 14 Recent studies have explored the synthesis of sixmembered carbocyclic and polycyclic compounds from biomass via DA cycloadditions.…”

Section: ■ Introductionmentioning

confidence: 99%

“…The main approach for the utilization of chitin typically involves the initial chemical or biological hydrolysis of chitin to its monomeric unit: N -acetylglucosamine (NAG), from which one can readily envision several valuable intermediates such as 3-acetamido-5-acetylfuran (3A5AF) and dihydroxyethyl acetamidofuran (Di-HAF) (Figure b). These amido-furans show great application potential in the polymer and pharmaceutical industry. − The diene moiety in chitin-based furans makes these substrates suitable for chemical structure diversification via Diels–Alder (DA) chemistry and, for example, coupled to an aromatization reaction to yield aniline derivatives …”

Section: Introductionmentioning

confidence: 99%

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Insights into Endo/Exo Stereopreference in Diels–Alder Cycloadditions of Chitin-Derived Furans

Wang,

van der Loo,

Zhang

et al. 2024

ACS Sustainable Chem. Eng.

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Chitin represents an abundant source of nitrogenous polysaccharides, making it a suitable feedstock for organonitrogen platform chemicals. In particular, furanic compounds, such as 3-acetamido-5-acetylfuran (3A5AF), can be readily obtained. Furans can be further functionalized using a Diels−Alder (DA) cycloaddition with a variety of dienophiles. Herein, we report on the DA of 3A5AF, dihydroxyethyl acetamidofuran (Di-HAF), and several derivatives, with maleimide dienophiles. The formation of exo and endo isomers was monitored in detail, and reactivity trends were established experimentally. Kinetic modeling allowed us to establish a reaction network that included a hydration side reaction involving specifically the exo isomer which affects the overall endo/exo ratio of the reaction. Carbonyl and alkyl hydroxyl substituents on the furans changed the DA rate significantly and shifted the selectivity from the exo to the endo product. Density functional theory (DFT) calculations revealed that the presence of a hydroxyl group leads to a thermodynamically favored endo isomer, evidenced by a decreased ΔG endo . Stronger hydrogen bonding interactions and van der Waals interaction in HMFA-involved TS are responsible for its lower ΔG ⧧ values as evidenced by noncovalent interaction analysis, probably promoting the cycloaddition rate in the HMFA case. The activation strain model revealed that a faster cycloaddition rate can be attributed to lower interaction and distortion energies in the HMFA case. Additionally, it is the orbital interactions and electrostatic attractions that favor the endo addition in the HMFA case, while easier structural distortion possibly causes the exo selectivity for 3A5AF. These findings aid the development of synthetic strategies for complex chiral skeletons containing compounds based on chitin-derived building blocks.

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Section: ■ Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Insights into Endo/Exo Stereopreference in Diels–Alder Cycloadditions of Chitin-Derived Furans

Wang,

van der Loo,

Zhang

et al. 2024

ACS Sustainable Chem. Eng.

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Synthesis of Difuropyridines from Chitin‐Derived 3‐Acetamidofuran and their Application to Photocatalytic Reactions

Gan,

Ma,

Yang

et al. 2024

Adv Synth Catal

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On the Valorisation of Chitin‐Derived Furans by Milling

Mattioli,

Santos,

de Souza

et al. 2024

ChemSusChem

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Chitin‐derived furans offer a sustainable alternative feedstock for nitrogen appended aromatic compounds. Herein, we address the challenge of using chitin‐derived furans, 3‐acetamido‐5‐acetylfuran (3A5AF) and 3‐acetamido‐5‐furfural aldehyde (3A5F), to favour the formation of exo Diels–Alder adducts and 4‑acetylaminophthalimides respectively, using a mechanochemical ball‐milling technique. Mechanochemical activation is explored through the synthesis of 7‐oxa‐norbornene backbones with novel substitution pattern from 3A5AF in yields up to 77% and improved exo:endo selectivity compared to solution‐phase reactions. The synthesis of 4‑acetylaminophthalimides from 3A5F in yields up to 79% is also showcased from hydrazone derivatives.

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Substituted anilides from chitin-based 3-acetamido-furfural

Abstract: A Diels–Alder/aromatization cascade reaction with chitin-based furans is a powerful tool for the synthesis of nitrogen-containing aromatics.

Cited by 6 publications

References 44 publications

Insights into Endo/Exo Stereopreference in Diels–Alder Cycloadditions of Chitin-Derived Furans

Insights into Endo/Exo Stereopreference in Diels–Alder Cycloadditions of Chitin-Derived Furans

Synthesis of Difuropyridines from Chitin‐Derived 3‐Acetamidofuran and their Application to Photocatalytic Reactions

On the Valorisation of Chitin‐Derived Furans by Milling

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