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Molecular mechanism of the transformation of oxidized lignin to N-substituted aromatics.
Mu, Xueli; Sun, Shijie; Li, Zhihao; Han, Lingli; Lv, Kang; Liu, Tao.
Afiliação
  • Mu X; School of Chemistry, Chemical Engineering and Materials, Jining University, Qufu 273155, Shandong, China. hll_2002@sina.com.
  • Sun S; School of Chemistry, Chemical Engineering and Materials, Jining University, Qufu 273155, Shandong, China. hll_2002@sina.com.
  • Li Z; School of Chemistry, Chemical Engineering and Materials, Jining University, Qufu 273155, Shandong, China. hll_2002@sina.com.
  • Han L; School of Chemistry, Chemical Engineering and Materials, Jining University, Qufu 273155, Shandong, China. hll_2002@sina.com.
  • Lv K; School of Chemistry, Chemical Engineering and Materials, Jining University, Qufu 273155, Shandong, China. hll_2002@sina.com.
  • Liu T; School of Chemistry, Chemical Engineering and Materials, Jining University, Qufu 273155, Shandong, China. hll_2002@sina.com.
Org Biomol Chem ; 21(47): 9356-9361, 2023 Dec 06.
Article em En | MEDLINE | ID: mdl-37927135
The cleavage of C-C bonds in oxidized lignin model compounds is a highly effective methodology for achieving lignin depolymerization, as well the generation of N-substituted aromatics. Here, density functional theory calculations were performed to understand the mechanism of the transformation of an oxidized lignin model compound (ligninox) and hydroxylamine hydrochloride to N-substituted aromatics. The reaction was proposed to proceed via an energetically viable mechanism featuring the initial production of HOAc acting as proton bridge. According to our calculations, Z-type oxime is the major intermediate of the reaction, with an energy barrier of 22.9 kcal mol-1, owing to the weak interactions between methoxy and oximino groups being stronger than that of E-type oxime. Additionally, the hydroxy addition is the rate-determining step, with an energy barrier of 27.0 kcal mol-1. Moreover, the huge net energy change of Beckmann and abnormal Beckmann rearrangements is the main overall thermodynamic driving force for producing N-substituted aromatics from oximes. The theoretical results have provided a clear picture of how ligninox transforms into N-substituted aromatics and are expected to provide valuable theoretical guidance for lignin depolymerization.

Texto completo: 1 Coleções: 01-internacional Base de dados: MEDLINE Idioma: En Revista: Org Biomol Chem Assunto da revista: BIOQUIMICA / QUIMICA Ano de publicação: 2023 Tipo de documento: Article País de afiliação: China País de publicação: Reino Unido

Texto completo: 1 Coleções: 01-internacional Base de dados: MEDLINE Idioma: En Revista: Org Biomol Chem Assunto da revista: BIOQUIMICA / QUIMICA Ano de publicação: 2023 Tipo de documento: Article País de afiliação: China País de publicação: Reino Unido