A designed and potentially decadentate ligand for use in lanthanide(<scp>iii</scp>) catalysed biomass transformations: targeting diastereoselective<i>trans</i>-4,5-diaminocyclopentenone derivatives

Peewasan, Krisana; Merkel, Marcus; Fuhr, Olaf; Powell, Annie K.

doi:10.1039/d0dt00183j

Cited by 10 publications

(5 citation statements)

References 24 publications

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“…Four and five‐coordinate Er III SMMs are known in the literature, but none of these contains alkoxides or aryloxides [116, 117, 121] . Among higher‐coordinate (CN>5) mononuclear Er III alkoxide and aryloxide SMMs, none show improved SMM behaviour over the Er III COT family or Dy III derivatives of higher‐coordinate alkoxide and aryloxide SMMs [78, 79, 81, 85, 89, 122–125] …”

Section: Other Ln Alkoxide and Aryloxide Smmsmentioning

confidence: 99%

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Mononuclear Dysprosium Alkoxide and Aryloxide Single‐Molecule Magnets

Parmar

Mills

Winpenny

2021

Chemistry A European J

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Recent studies have shown that mononuclear lanthanide (Ln) complexes can be high‐performing single‐molecule magnets (SMMs). Recently, there has been an influx of mononuclear Ln alkoxide and aryloxide SMMs, which have provided the necessary geometrical control to improve SMM properties and to allow the intricate relaxation dynamics of Ln SMMs to be studied in detail. Here non‐aqueous Ln alkoxide and aryloxide chemistry applied to the synthesis of low‐coordinate mononuclear Ln SMMs are reviewed. The focus is on mononuclear DyIII alkoxide and aryloxide SMMs with coordination numbers up to eight, covering synthesis, solid‐state structures and magnetic attributes. Brief overviews are also provided of mononuclear TbIII, HoIII, ErIII and YbIII alkoxide and aryloxide SMMs.

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Section: Other Ln Alkoxide and Aryloxide Smmsmentioning

confidence: 99%

“…[116,117,121] Among higher-coordinate (CN > 5) mononuclear Er III alkoxide and aryloxide SMMs,n one show improved SMM behaviour over the Er III COT family or Dy III derivatives of highercoordinate alkoxide and aryloxide SMMs. [78,79,81,85,89,[122][123][124][125]…”

Section: Enhancing Molecularrigidity By Ligand Functionalisationmentioning

confidence: 99%

Mononuclear Dysprosium Alkoxide and Aryloxide Single‐Molecule Magnets

Parmar

Mills

Winpenny

2021

Chemistry A European J

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“…In previous works, secondary amines were successfully used for this transformation, with morpholine and pyrrolidine as the two common starting amines. − Under the same conditions, primary amines either found to be inactive or only aniline were reported to react and lead to the corresponding trans -DACPs, as summarized in Table S4. In comparison, herein, H 4 SiW 12 O 40 was found to promote successfully the synthesis of a series of trans -DACPs, using either secondary amines or substituted anilines, under mild conditions and in good to high isolated yields.…”

Section: Resultsmentioning

confidence: 99%

“…On the other hand, microwave irradiation, tosylamine, and the ChCl/urea system were also used as metal-free procedures. In parallel, a series of heteronuclear {Ni(II) 2 Dy(III) 2 L 4 (DMF) 6 ] 2(OTf)} coordination complexes (where Ln = Y, Dy; and H 2 L = ( E )-2-(((2-hydroxyphenyl)imino)methyl)-6-methoxyphenol), − as well as MIL series of MOF, with Fe-MIL-100 and -101 and a Dy(III) complex, were reported to facilitate this reaction under mild conditions and with low catalyst loadings (Scheme , lower). It is worth noting that, in most of the above protocols, the reaction scope was limited to secondary amines; however, only sporadic examples applied to primary amines, i.e., aniline or 2-fluoroaniline with 3-bromofurfural …”

Section: Introductionmentioning

confidence: 99%

Polyoxometalate-Driven Ease Conversion of Valuable Furfural to trans-N,N-4,5-Diaminocyclopenten-2-ones

2022

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We investigated the catalytic efficacy of silicotungstic acid (H4SiW12O40) polyoxometalate (POM) toward the reaction between furfural and amines that selectively yields trans-N,N-4,5-substituted-diaminocyclopenten-2-ones (trans-DACPs). H4SiW12O40 facilitates the synthesis of a library of trans-DACPs with loadings as low as 0.05 mol %, in open air, without additives, in short times and good to high isolated yields. The protocol was applied to secondary amines as well as to aromatic primary amines with pK b higher than ca. 9. The present catalytic synthetic protocol has an extended substrate scope with high yields and represents, to the best of our knowledge, the first polyoxometalate-driven paradigm as an efficient method to produce cyclopentanone frameworks under mild reaction conditions.

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“…Recently, the usage of rare-earth/lanthanide complexes as catalysts in both organic reactions , and polymerization processes , has attracted increasing attention. In previous work, lanthanide-based complexes containing Schiff-base ligands have been utilized for triggering CO 2 /epoxide copolymerization, in which all dinuclear dysprosium complexes are air-insensitive molecules and highly active in such a homogeneous catalytic system .…”

Section: Introductionmentioning

confidence: 99%

Heterocyclic-Additive-Activated Dinuclear Dysprosium Electrocatalysts for Heterogeneous Water Oxidation

et al. 2021

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Heterogeneous catalysis based on air-stable lanthanide complexes is relatively rare, especially for electrochemical water oxidation and reduction. Therefore, it is highly desired to investigate the synergy caused by cocatalysts on the lanthanide complex family for heterogeneous catalysis because of their structural diversity, air/moisture insensitivity, and easy preparation under an air atmosphere. Two mononuclear and three dinuclear dysprosium complexes containing a series of Schiff-base ligands have been demonstrated as robust electrocatalysts for triggering heterogeneous water oxidation in alkaline solution, in which the complex [Dy2(hmb)2(OAc)4]·MeCN(3) was revealed to have the best activity toward heterogeneous water oxidation among all five complexes in the present study. The molecular activation of dysprosium complexes has also been investigated with a series of N-containing heterocyclic additives [i.e., 4-(dimethylamino)pyridine (DMAP), bis(triphenylphosphine)iminium chloride ([PPN]Cl), indole, and quinoline]. In particular, the corresponding overpotential was effectively enhanced by 211 mV (at a current density of 10 mA cm–2) with the assistance of DMAP. On the basis of electrochemical and ex situ/in situ spectroscopic investigations, the best catalyst, DMAP–complex 3 on a carbon paper electrode, was confirmed with well-maintained molecular identity during heterogeneous water oxidation free of forming any dysprosium oxide and/or undesired products.

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A designed and potentially decadentate ligand for use in lanthanide(iii) catalysed biomass transformations: targeting diastereoselectivetrans-4,5-diaminocyclopentenone derivatives

Abstract: The catalysis of furfural to diastereoselective trans-4,5-diaminocyclopentenone building blocks for natural product synthesis for a wide range of amines was achieved under mild aerobic conditions.

Cited by 10 publications

References 24 publications

Mononuclear Dysprosium Alkoxide and Aryloxide Single‐Molecule Magnets

Mononuclear Dysprosium Alkoxide and Aryloxide Single‐Molecule Magnets

Polyoxometalate-Driven Ease Conversion of Valuable Furfural to trans-N,N-4,5-Diaminocyclopenten-2-ones

Heterocyclic-Additive-Activated Dinuclear Dysprosium Electrocatalysts for Heterogeneous Water Oxidation

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