Mapping out the key carbon–carbon bond-forming steps in Mn-catalysed C–H functionalization

Hammarback, L. Anders; Clark, Ian P.; Sazanovich, Igor V.; Towrie, Michael; Robinson, Alan J.; Clarke, Francis; Meyer, Stephanie; Fairlamb, Ian J. S.; Lynam, Jason M.

doi:10.1038/s41929-018-0145-y

Cited by 68 publications

(79 citation statements)

References 65 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…To develop efficient heterogeneous catalysts with higher selectivity and activity is highly desirable due to the aspiration for energy‐saving chemical processes. Specifically, it is highly required to develop selective hydrogenation of vinyl (C=C) group catalysts that are used for production of fine chemicals, including pharmaceuticals, perfumes, polymers, and herbicides . When more than one reducible groups (such as C=C and nitro (NO 2 ) group) are present in a substrate molecular, the conventional precious metals (including Pt, Pd, and Ru) catalysts can simultaneously reduce both the groups, leading to limited selectivity .…”

Section: Figurementioning

confidence: 99%

“…Specifically, it is highly required to develop selective hydrogenation of vinyl (C=C) group catalysts that are used for production of fine chemicals, including pharmaceuticals, perfumes, polymers, and herbicides. [1][2][3][4] When more than one reducible groups (such as C=C and nitro (NO 2 ) group) are present in a substrate molecular, the conventional precious metals (including Pt, Pd, and Ru) catalysts can simultaneously reduce both the groups, leading to limited selectivity. [5][6][7][8][9][10] To overcome this limitation, traditional strategies are modifying the active sites with ligands, zeolite, metal-organic frameworks, and poisoned-additives.…”

Section: Rh Doping In Pd Nanocubes Optimizes the Adsorption Of 3-nitrmentioning

confidence: 99%

See 1 more Smart Citation

Rh Doping in Pd Nanocubes Optimizes the Adsorption of 3‐Nitrostyrene towards Selective Hydrogenation of Vinyl Group

Zhao

Cui

et al. 2019

ChemCatChem

View full text Add to dashboard Cite

For selective hydrogenation, the improvement in selectivity is often accompanied with the sacrifice of activity. Herein, we achieved the optimization of both activity and selectivity towards selective hydrogenation reaction of 3‐nitrostyrene over Rh‐doped Pd nanocubes. Specially, the Rh‐doped Pd nanocubes with 6 atm % of Rh (denoted as Pd94Rh6) achieved a remarkable high selectivity (99.5 %) for product 3‐ethylnitrobenzene with almost 100 % conversion. Mechanistic studies revealed that the introduction of Rh dopant into Pd nanocubes strengthened the adsorption of 3‐nitrostyrene relative Pd nanocubes, accounting for the enhanced activity. Moreover, the ensemble composed of Rh dopant and nearby Pd atoms in Rh‐doped Pd nanocubes induced the unique adsorption configuration of 3‐nitroethylbenzene that inhibited the hydrogenation of NO2, responsible for the high C=C selectivity.

show abstract

Section: Figurementioning

confidence: 99%

Section: Rh Doping In Pd Nanocubes Optimizes the Adsorption Of 3-nitrmentioning

confidence: 99%

Rh Doping in Pd Nanocubes Optimizes the Adsorption of 3‐Nitrostyrene towards Selective Hydrogenation of Vinyl Group

Zhao

Cui

et al. 2019

ChemCatChem

View full text Add to dashboard Cite

show abstract

“…However, at the lower excitation energies (465 nm, 2.66 eV) that are preferred for medical applications, fewer CO molecules are released (1.4 equivalent). The CH 3 CN group of TryptoCORM is labile, so that the TryptoCORM‐CH 3 CN complex (i.e. the TryptoCORM molecule minus the acetonitrile ligand) is likely to exist in a dynamic equilibrium with TryptoCORM in solution, leading to questions around the relative photochemical and hence medicinal effectiveness of the two species.…”

Section: Introductionmentioning

confidence: 99%

Direct Measurement of the Visible to UV Photodissociation Processes for the PhotoCORM TryptoCORM

Cercola

Fischer

Sherman

et al. 2020

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

PhotoCORMs are light‐triggered compounds that release CO for medical applications. Here, we apply laser spectroscopy in the gas phase to TryptoCORM, a known photoCORM that has been shown to destroy Escherichia coli upon visible‐light activation. Our experiments allow us to map TryptoCORM's photochemistry across a wide wavelength range by using novel laser‐interfaced mass spectrometry (LIMS). LIMS provides the intrinsic absorption spectrum of the photoCORM along with the production spectra of all of its ionic photoproducts for the first time. Importantly, the photoproduct spectra directly reveal the optimum wavelengths for maximizing CO ejection, and the extent to which CO ejection is compromised at redder wavelengths. A series of comparative studies were performed on TryptoCORM‐CH 3 CN which exists in dynamic equilibrium with TryptoCORM in solution. Our measurements allow us to conclude that the presence of the labile CH 3 CN facilitates CO release over a wider wavelength range. This work demonstrates the potential of LIMS as a new methodology for assessing active agent release (e.g. CO, NO, H 2 S) from light‐activated prodrugs.

show abstract

“…[7] Thus,n oble-metal palladium and ruthenium catalysts have set the stage for versatile peptide diversification, as reported by the groups of Lavilla/Albericio, [8] Corey, [9] Chen, [10] Daugulis, [11] Shi, [12] Yu, [13] and Ackermann, [14] among others. [15] In sharp contrast, peptide modification with the aid of less expensive base metals,a nd specifically less-toxic manganese catalysis, [16][17][18][19] continues to be limited to ar ecent single example of alkynylation. [20] As part of our program on sustainable CÀHactivation, [21] we now report on the first manganese-catalyzed CÀHa llylation of structurally complex peptides with easily accessible Morita-Baylis-Hillman adducts.N otable features of our strategy include 1) an unprecedented manganese(I)-catalyzed peptide C À Ha lkylation, 2) the first metal-catalyzed peptide modifications that install synthetically useful a,b-unsaturated esters, 3) orthogonal late-stage diversification, and 4) au niquely versatile manganese catalyst that proved applicable to CÀH fusion with peptides,n atural products,s teroids,d rug molecules,a nd nucleobases,among others ( Figure 1).…”

mentioning

confidence: 99%

Late‐Stage Diversification through Manganese‐Catalyzed C−H Activation: Access to Acyclic, Hybrid, and Stapled Peptides

et al. 2019

View full text Add to dashboard Cite

Bioorthogonal C À Hallylation with ample scope was accomplished through av ersatile manganese(I)-catalyzed CÀHactivation for the late-stage diversification of structurally complex peptides.The unique robustness of the manganese(I) catalysis manifold was reflected by full tolerance of sensitive functional groups,such as iodides,esters,amides,and OH-free hydroxy groups,therebysetting the stage for the racemizationfree synthesis of CÀHfused peptide hybrids featuring steroids, drug molecules,n atural products,n ucleobases,a nd saccharides.

show abstract

Mapping out the key carbon–carbon bond-forming steps in Mn-catalysed C–H functionalization

Cited by 68 publications

References 65 publications

Rh Doping in Pd Nanocubes Optimizes the Adsorption of 3‐Nitrostyrene towards Selective Hydrogenation of Vinyl Group

Rh Doping in Pd Nanocubes Optimizes the Adsorption of 3‐Nitrostyrene towards Selective Hydrogenation of Vinyl Group

Direct Measurement of the Visible to UV Photodissociation Processes for the PhotoCORM TryptoCORM

Late‐Stage Diversification through Manganese‐Catalyzed C−H Activation: Access to Acyclic, Hybrid, and Stapled Peptides

Contact Info

Product

Resources

About