Organic Transformations Promoted by Lewis Acid Iron Catalysts

Vrancken, Emmanuel; Campagne, Jean‐Marc

doi:10.1002/9780470682531.pat0656

Cited by 7 publications

(6 citation statements)

References 295 publications

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“…This further supports the hypothesis that wear processes which generate Lewis acids such as iron oxides can accelerate wear processes in the absence of a pH buffer. 43 The pH buffer PBS is known to positively influence the tribology of Si-DLCs in a variety of applications. 44 In the absence of a buffer solution the formation of silicon rich wear debris that are known to give low coefficients of friction in these types of system are highly likely.…”

Section: Discussionmentioning

confidence: 99%

Understanding friction mechanisms of Si-DLC/steel interfaces under aqueous lubrication

Lanigan

Lewis

2023

RSC Adv.

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Section: Discussionmentioning

confidence: 99%

Understanding friction mechanisms of Si-DLC/steel interfaces under aqueous lubrication

Lanigan

Lewis

2023

RSC Adv.

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“…Iron(III) salts are hard Lewis acids and have been used in hydrofunctionalisation reactions to increase the susceptibility of alkenes and alkynes to nucleophilic attack. [60] Methodologies have been developed for the addition of amines, alcohols, carboxylic acids, thiols and 1,3dicarbonyls to alkenes, alkynes and allenes, most commonly using either FeCl 3 114 or Fe(OTf) 3 115 (Tf = CF 3 SO 2 ) as a (pre-)catalyst. The hydrofunctionalisation of unactivated alkenes 113 has been mostly confined to intramolecular reactions (Scheme 1.19 A), with intermolecular reactions generally limited to those using either strained alkenes, such as norbornene 46, or those capable of stabilising a cationic intermediate, such as styrene derivatives, 1,3-dienes and enol ethers (Scheme 1.19 B).…”

Section: High Oxidation-state Iron-catalysed Hydrofunctionalisationmentioning

confidence: 99%

Iron-Catalysed Hydrofunctionalisation of Alkenes and Alkynes

Greenhalgh

2016

Springer Theses

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The iron-catalysed hydrofunctionalisation of alkenes and alkynes has been developed to give a range of functionalised products with control of regio-, chemo-and stereochemistry. Using a bench-stable iron(II) pre-catalyst, the hydrosilylation, hydroboration, hydrogermylation and hydromagnesiation of alkenes and alkynes has been achieved.Iron-catalysed hydrosilylation, hydroboration and hydrogermylation of terminal, 1,1-and 1,2-disubstituted alkyl and aryl alkenes and alkynes was developed, in which the active iron catalyst was generated in situ (Scheme A1). Alkyl and vinyl silanes and pinacol boronic esters were synthesised in good to excellent yield in the presence of a range of functional groups. Catalyst loadings as low as 0.07 mol% were demonstrated, along with catalyst turn-over frequencies of up to 60 000 mol h −1 . Scheme A1. Iron-catalysed hydrosilylation and hydroboration of alkenes and alkynesThe iron-catalysed formal hydrocarboxylation of a range of styrene derivatives has been developed for the synthesis of -aryl carboxylic acids using carbon dioxide and ethylmagnesium bromide as the stoichiometric hydride source (Scheme A2). Detailed mechanistic studies have shown this reaction proceeds by iron-catalysed hydromagnesiation to give an intermediate benzylic organomagnesium reagent. The nature of the active catalyst and reaction mechanism have been proposed. Scheme A2. Iron-catalysed hydromagnesiation of styrene derivatives I would firstly and foremostly like to thank Steve for the past 4 years for making my PhD a thoroughly enjoyable experience. The amount of time he has invested in helping, advising and inspiring me has been truly remarkable and I genuinely could not be more thankful. I will certainly miss our 'discussions' about chemistry, and would finally like to admit that Steve is often right. I am very thankful for having had the chance to meet and work with various people over the years, both here in Edinburgh and in Bristol. I would like to thank the members of the Aggarwal and Pringle groups in Bristol, and all current and past members of the Thomas group. In particular I would like to thank Nick Barron for those days when we were the Thomas group, and Dominik Frank who always knew when it was time for a beer. I am also grateful for all those who have specifically worked with me on projects during my PhD: Dominik Frank, Fern Sinclair, Adam Kolodiej and Jonathan Kwan. I wish everybody the best for the future. I would like to thank the University of Bristol for financial support and those who worked on the Chemical Synthesis DTC (CDT now), in particular Eoghan McGarrigle, Mar and Kevin Booker-Milburn. I would also like to thank Paul Pringle for the time I spent working in his group. I am thankful to the University of Edinburgh for providing the financial support to allow me to move north of the border with Steve. I would also like to thank the RSC for financing my trip to speak at the J-NOST conference in India, despite the food poisoning. The technical and analytical staff at both Bristol and E...

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“…Comprehensive literature reviews about iron catalysis in organic synthesis have been published over the years, displaying their wide applications in the production of various chemicals [66,67]. However, the other iron-based compounds tested in the present work were not able to effectively convert galactaric acid, as FDME was detected only in traces in those trials (#9-11; Table 1).…”

Section: Discussionmentioning

confidence: 73%

“…Fe 2 (SO 4 ) 3 and iron salts in general have been reported as efficient catalysts able to promote several reactions, also playing different roles in the same one-pot procedure [66].…”

Section: Discussionmentioning

confidence: 99%

Iron(III) Sulfate-Mediated Synthesis of 2,5-Furandicarboxylic Acid Dimethyl Ester from Galactaric Acid

Trapasso,

Chícharo,

Gherardi

et al. 2023

Catalysts

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2,5-furandicarboxylic acid (FDCA) is one of the most studied bio-based monomers, being considered the best substitute for fossil-derived terephthalic acid in plastic production. FDCA is employed in the preparation of polyethylene furanoate (PEF), demonstrating superior mechanical and thermal proprieties compared to the widely used polyethylene terephthalate (PET). Nevertheless, FDCA synthesis mostly relies on the oxidation of the bio-based platform chemical hydroxymethyl furfural (HMF), whose notoriously instable nature renders FDCA yield and industrial scale-up production complicated. On the contrary, FDCA esters are less studied, even though they have greater solubility in organic media, which would favor their isolation and potential application as monomers for PEF. On these premises, we report herein an alternative green synthetic approach to FDCA methyl ester (FDME) using galactaric acid as the substrate, dimethyl carbonate (DMC) as the green media, and Fe2(SO4)3 as the heterogeneous Lewis acid. Optimization of the reaction conditions allowed the selective production of FDME in a 70% isolated yield; product purification was achieved via flash column chromatography over silica. Furthermore, it was possible to employ up to 5.0 g of galactaric acid in a single reaction, leading to a good isolated yield of FDME.

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Organic Transformations Promoted by Lewis Acid Iron Catalysts

Cited by 7 publications

References 295 publications

Understanding friction mechanisms of Si-DLC/steel interfaces under aqueous lubrication

Understanding friction mechanisms of Si-DLC/steel interfaces under aqueous lubrication

Iron-Catalysed Hydrofunctionalisation of Alkenes and Alkynes

Iron(III) Sulfate-Mediated Synthesis of 2,5-Furandicarboxylic Acid Dimethyl Ester from Galactaric Acid

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