Heterogeneous Diels–Alder catalysis for biomass-derived aromatic compounds

Settle, Amy E.; Berstis, Laura; Rorrer, Nicholas A.; Román‐Leshkov, Yuriy; Beckham, Gregg T.; Richards, Ryan M.; Vardon, Derek R.

doi:10.1039/c7gc00992e

Cited by 218 publications

(184 citation statements)

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“…A more recent example of the confinement‐induced reactivity in zeolite catalysis is a series of computational works by Rohling et al on Diels‐Alder Cycloaddition‐dehydration (DACD) reaction between furanic compounds and alkenes by FAU‐type zeolites . DACD is considered as an important step in a perspective chemocatalytic technology for the production of aromatic products from renewable cellulosic biomass feedstock . The conversion of dimethylfuran with ethylene over different alkali‐exchanged Y zeolites has been studied in detail by periodic DFT calculations complemented with electronic structure analysis, microkinetic modelling and catalytic tests using a range of alkali‐exchanged FAU‐type zeolites .…”

Section: Confinement‐induced Reactivity and Molecular Recognition Phementioning

confidence: 99%

The Nature and Catalytic Function of Cation Sites in Zeolites: a Computational Perspective

Pidko

2018

ChemCatChem

104

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Zeolites have a broad spectrum of applications as robust microporous catalysts for various chemical transformations. The reactivity of zeolite catalysts can be tailored by introducing heteroatoms either into the framework or at the extraframework positions that gives rise to the formation of versatile Brønsted acid, Lewis acid and redox‐active catalytic sites. Understanding the nature and catalytic role of such sites is crucial for guiding the design of new and improved zeolite‐based catalysts. This work presents an overview of recent computational studies devoted to unravelling the molecular level details of catalytic transformations inside the zeolite pores. The role of modern computational chemistry in addressing the structural problem in zeolite catalysis, understanding reaction mechanisms and establishing structure‐activity relations is discussed. Special attention is devoted to such mechanistic phenomena as active site cooperativity, multifunctional catalysis as well as confinement‐induced and multisite reactivity commonly encountered in zeolite catalysis.

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Section: Confinement‐induced Reactivity and Molecular Recognition Phementioning

confidence: 99%

The Nature and Catalytic Function of Cation Sites in Zeolites: a Computational Perspective

Pidko

2018

ChemCatChem

104

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“…The Diels–Alder cycloaddition of alkenes to furanic compounds yields substituted benzenes. The reaction involves substituted 7‐oxanorbornene cycloadducts, which high ring strain renders reactive towards isomerization into an alcohol intermediate that can dehydrate to aromatic products . Such a consecutive cycloaddition, isomerization and dehydration process is usually carried out as a one‐pot tandem reaction and will here be denoted as the Diels–Alder cycloaddition–dehydration (DAC D) reaction.…”

Section: Introductionmentioning

confidence: 99%

Multi‐site Cooperativity in Alkali‐Metal‐Exchanged Faujasites for the Production of Biomass‐Derived Aromatics

2017

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The catalytic Diels–Alder cycloaddition–dehydration (DACD) reaction of furanics with ethylene is a promising route to bio‐derived aromatics. The reaction can be catalyzed by alkali‐metal‐exchanged faujasites. Herein, the results of periodic DFT calculations based on accurate structural models of alkali‐metal‐exchanged zeolites are presented, revealing the fundamental roles that confinement and the nature of the exchangeable cations in zeolite micropores have in the performance of faujasite‐based catalysts in the DACd reaction. Special attention is devoted to analyzing the effect of functional substituents on furanic substrates (furan, 2,5‐dimethylfuran, 2,5‐furandicarboxylic acid) on the catalyst behavior. It is demonstrated that the conventional reactivity theories of the Diels–Alder chemistry based on simplistic single‐site Lewis acidity and substituent effects do not apply if catalytic processes in the multiple‐site confined environment of zeolite nanopores are considered. The nature and cooperativity of the interactions between the multiple exchangeable cations and the substrates determine the reaction energetics of the elementary steps involved in the DACD process.

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“…Many preeminent reviews regarding the transformation of bio‐sugars have already emerged, but they are mainly focused on the conversion pathways toward various biomass‐derived platform chemicals, or catalysts on the basis of acid type . Nevertheless, increasing attention has been recently paid to control of the carbon chain length during upgrading of biomass‐derived molecules to either biofuels (e.g., C 7 –C 20 ) with desired fuel properties or small fine chemicals (e.g., C 1 –C 6 ) . Clarifying changes to the carbon atom number during sugar conversions has scientific importance and practical guidance to subsequent upgrading of biomass‐derived molecules to biofuels.…”

Section: Introductionmentioning

confidence: 55%

Catalytic Upgrading of Biomass‐Derived Sugars with Acidic Nanoporous Materials: Structural Role in Carbon‐Chain Length Variation

Saravanamurugan

et al. 2018

ChemSusChem

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Shifting from petroleum‐based resources to inedible biomass for the production of valuable chemicals and fuels is one of the significant aspects in sustainable chemistry for realizing the sustainable development of our society. Various renowned biobased platform molecules, such as 5‐hydroxymethylfurfural, furfural, levulinic acid, and lactic acid, are successfully accessible from the transformation of biobased sugars. To achieve the specific reaction routes, heterogeneous nanoporous acidic materials have served as promising catalysts for the conversion of bio‐sugars in the past decade. This Review summarizes advances in various nanoporous acidic materials for bio‐sugar conversion, in which the number of carbon atoms is variable and controllable with the assistance of the switchable structure of nanoporous materials. The major focus of this Review is on possible reaction pathways/mechanisms and the relationships between catalyst structure and catalytic performance. Moreover, representative examples of catalytic upgrading of biobased platform molecules to biochemicals and fuels through selective C−C cleavage and coupling strategies over nanoporous acidic materials are also discussed.

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Heterogeneous Diels–Alder catalysis for biomass-derived aromatic compounds

Abstract: This review highlights Diels–Alder heterogeneous catalysis for the production of biomass-derived aromatic compounds.

Cited by 218 publications

References 186 publications

The Nature and Catalytic Function of Cation Sites in Zeolites: a Computational Perspective

The Nature and Catalytic Function of Cation Sites in Zeolites: a Computational Perspective

Multi‐site Cooperativity in Alkali‐Metal‐Exchanged Faujasites for the Production of Biomass‐Derived Aromatics

Catalytic Upgrading of Biomass‐Derived Sugars with Acidic Nanoporous Materials: Structural Role in Carbon‐Chain Length Variation

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