Combined Furan C–H Activation and Furyl Ring-Opening by an Iron(II) Complex

Taylor, Kathleen H.; Kalman, Steven E.; Gunnoe, T. Brent; Sabat, Michal

doi:10.1021/acs.organomet.6b00276

Cited by 10 publications

(5 citation statements)

References 40 publications

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“…Of these, several data were considered to be unreliable and should be treated with caution due to their low quality. Similar short Fe–P bond lengths as in our complex are found in the compounds [FeH 2 (CO) 2 {P(OPh) 3 } 2 ] [210.04(7) pm], and [FeCp*(2-furyl){P(OCH 2 ) 3 CEt} 2 ] [209.6(1)/207.5(1) pm], as well as [{Fe(CO) 3 (μ-PR)} 2 ] (R = OC 6 H 2 -2,6- t -Bu 2 -4-Me), which exhibits a structure similar to cyclobutadiene with two different Fe–P bond lengths of 220.2(1) and 211.2(1) pm, for example.…”

Section: Resultssupporting

confidence: 83%

Free Difluorobis(pentafluoroethyl)phosphoranide Ion and Its Ligand Properties

et al. 2022

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In this contribution, we report on the “free” [P(C2F5)2F2]− ion and its ligand properties in transition metal complex chemistry. For this purpose, Ag[P(C2F5)2F2] was treated with [{(Et2N)3PN}3PNHC(CH3)3]Cl ([EtP4H]Cl) to yield [EtP4H][P(C2F5)2F2], featuring a weakly coordinating phosphazenium cation. Due to the weak interaction between the cation and anion, the [P(C2F5)2F2]− ion meets the so-called pseudo-gas-phase conditions. To determine the Tolman electronic parameter, [EtP4H][Ni(CO)3{P(C2F5)2F2}] was prepared from [EtP4H][P(C2F5)2F2] and [Ni(CO)4], facilitating the classification of the P(C2F5)2F2 moiety as a moderately π-acidic ligand. By treatment of [EtP4H][P(C2F5)2F2] with [AuCl(tht)], the neutral tetrahydrothiophene ligand was substituted by the phosphoranide ion, yielding [EtP4H][AuCl{P(C2F5)2F2}]. When Ag[P(C2F5)2F2] was treated with [AuCl(tht)], on the other hand, the chloride was substituted. Transmetalation reactions of this type proved to be an efficient transfer method of the P(C2F5)2F2 moiety, as further demonstrated by the reactions of Ag[P(C2F5)2F2] with [FeCl(CO)2Cp], [FeCl(CO)2Cp*], and [PdCl2(NCMe)2]. Surprisingly, P(C2F5)2F demonstrated fluorinating abilities toward [FeCl(CO)2Cp], [FeCl(CO)2Cp*], [AuCl(tht)], and [PdCl2(NCMe)2]. Apparently, fluorido transition metal complexes were generated in situ under the formation of P(C2F5)2Cl. The fluorido iron and palladium complexes transfer their fluoride ions onto P(C2F5)2F, yielding the respective phosphoranido complexes, featuring the P(C2F5)2F2 moiety.

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Section: Resultssupporting

confidence: 83%

Free Difluorobis(pentafluoroethyl)phosphoranide Ion and Its Ligand Properties

et al. 2022

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“…Biomass‐derived furans such as 2‐furfuraldehyde (furfural) and 5‐hydroxymethyl‐2‐furfural (HMF) can be efficiently produced by the acid‐catalysed dehydration of pentose and hexose, respectively . As furans have highly reactive side chains, ‐CHO and/or ‐CH 2 OH with furan ring, these can be explored for the production of different C5, C6 or higher carbon containing valuable chemicals such as 2,5‐furandicarboxylic acid (FDCA), 2‐furoic acid, levulinic acid (LA), ketones/diketones, 1,6‐hexanediol (1,6‐HDO), 1‐hydroxyhexane‐2,5‐dione (1‐HHD), cyclopentanone (CPO), adipic acid, maleic anhydride (MA), caprolactam, caprolactone, γ‐valerolactone, 2,5‐dimethylfuran (DMF), alkanes and so on, having wide applications in various pharmaceutical and polymer industries as well as in the production of fuel components …”

Section: Introductionmentioning

confidence: 99%

Metal Catalysts for the Efficient Transformation of Biomass‐derived HMF and Furfural to Value Added Chemicals

2018

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Catalytic transformation of biomass‐derived compounds to different platform chemicals and liquid fuel is a prominent way to reduce the global dependence on fossil resources. In past few decades, biomass‐derived furans such as 2‐furfuraldehyde (furfural) and 5‐hydroxymethyl‐2‐furfural (HMF) have received outstanding attention because of their wide applications in the production of various industrially important value‐added chemicals and fuel components. Various catalytic systems and methodologies have been extensively explored for the transformation of these furans to a wide range of products including open ring diketones, ketoacids, alcohols and long chain alkanes. This Review is aimed to provide an extensive overview of the recent developments of several high‐performing heterogeneous catalysts for the catalytic upgradation of the key biomass‐derived furans (furfural and HMF) to value‐added chemicals. Moreover, the role of these catalysts in the catalytic transformations including hydrogenation, decarbonylation, oxidation, hydrogenolysis and ring opening reactions, and the mechanistic pathways are also highlighted in this Review.

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“…87,88 This observation was similar to the early report by Hata et al 80 The half-sandwich-type iron(II) complex Cp*Fe(II)PhL 2 [where L = P(OR) 3 ] can activate the C−H bond of furans at the 2-position. 89 This reaction proceeds through σ-bond metathesis, in which the phenyl group bound to the iron center acts as a base to deprotonate the C-2 hydrogen (Scheme 9). The half-sandwich iron(II) carbonyl complex Cp*Fe(II) (CO)Ph-(MeCN) was also reported to cleave regioselectively the C−H bond of five-membered ring heteroaromatics, including furan, thiophene, and thiazole.…”

Section: Activation Of C(sp 2 )−H Bonds By Iron Complexesmentioning

confidence: 99%

“…The half-sandwich-type iron(II) complex Cp*Fe(II)PhL 2 [where L = P(OR) 3 ] can activate the C–H bond of furans at the 2-position . This reaction proceeds through σ-bond metathesis, in which the phenyl group bound to the iron center acts as a base to deprotonate the C-2 hydrogen (Scheme ).…”

Section: Stoichiometric C–h Activation By Iron Complexes and Examples...mentioning

confidence: 99%

Iron-Catalyzed C–H Bond Activation

2017

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Catalytic C-H bond activation, which was an elusive subject of chemical research until the 1990s, has now become a standard synthetic method for the formation of new C-C and C-heteroatom bonds. The synthetic potential of C-H activation was first described for ruthenium catalysis and is now widely exploited by the use of various precious metals. Driven by the increasing interest in chemical utilization of ubiquitous metals that are abundant and nontoxic, iron catalysis has become a rapidly growing area of research, and iron-catalyzed C-H activation has been most actively explored in recent years. In this review, we summarize the development of stoichiometric C-H activation, which has a long history, and catalytic C-H functionalization, which emerged about 10 years ago. We focus in this review on reactions that take place via reactive organoiron intermediates, and we excluded those that use iron as a Lewis acid or radical initiator. The contents of this review are categorized by the type of C-H bond cleaved and the type of bond formed thereafter, and it covers the reactions of simple substrates and substrates possessing a directing group that anchors the catalyst to the substrate, providing an overview of iron-mediated and iron-catalyzed C-H activation reported in the literature by October 2016.

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Combined Furan C–H Activation and Furyl Ring-Opening by an Iron(II) Complex

Cited by 10 publications

References 40 publications

Free Difluorobis(pentafluoroethyl)phosphoranide Ion and Its Ligand Properties

Free Difluorobis(pentafluoroethyl)phosphoranide Ion and Its Ligand Properties

Metal Catalysts for the Efficient Transformation of Biomass‐derived HMF and Furfural to Value Added Chemicals

Iron-Catalyzed C–H Bond Activation

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