Efficiency and Selectivity Aspects in the C–H Functionalization of Aliphatic Oxygen Heterocycles by Photocatalytic Hydrogen Atom Transfer

Raviola, Carlotta; Ravelli, Davide

doi:10.1055/s-0037-1612079

Cited by 22 publications

(15 citation statements)

References 17 publications

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“…In rare instances, the activation of the C–H bond was applied to cyclic carbonates ( 16.1a,b , Scheme ), where the presence of the carbonyl group did not hamper the C–H cleavage in these substrates. The importance of using TBADT is evident in this case, since the same process promoted by aromatic ketones gave no products 16.3a,b . Introducing a methyl group in carbonate 16.1b drove the cleavage to the most labile C–H bond present.…”

Section: Formation Of C–c Bondsmentioning

confidence: 92%

Direct Photocatalyzed Hydrogen Atom Transfer (HAT) for Aliphatic C–H Bonds Elaboration

2021

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Direct photocatalyzed hydrogen atom transfer (d-HAT) can be considered a method of choice for the elaboration of aliphatic C–H bonds. In this manifold, a photocatalyst (PCHAT) exploits the energy of a photon to trigger the homolytic cleavage of such bonds in organic compounds. Selective C–H bond elaboration may be achieved by a judicious choice of the hydrogen abstractor (key parameters are the electronic character and the molecular structure), as well as reaction additives. Different are the classes of PCsHAT available, including aromatic ketones, xanthene dyes (Eosin Y), polyoxometalates, uranyl salts, a metal-oxo porphyrin and a tris(amino)cyclopropenium radical dication. The processes (mainly C–C bond formation) are in most cases carried out under mild conditions with the help of visible light. The aim of this review is to offer a comprehensive survey of the synthetic applications of photocatalyzed d-HAT.

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Section: Formation Of C–c Bondsmentioning

confidence: 92%

Direct Photocatalyzed Hydrogen Atom Transfer (HAT) for Aliphatic C–H Bonds Elaboration

2021

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“…Furthermore, the TBADT catalyst tends to close the cycle and promoted further reusable behavior in the catalyst when performing this kind of addition reaction. These reactions are carried out by UV irradiation but even a solar simulator is a good choice [12][13][14][15][16]. Bearing this in mind, we are concentrating on the process of dehydrogenation to produce hydrogen gas (H 2 ) by using the versatility of TBADT.…”

Section: Introductionmentioning

confidence: 99%

Tungsten Catalysts for Visible Light Driven Ofloxacin Photocatalytic Degradation and Hydrogen Production

et al. 2022

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Some tungsten catalysts of interest that are synthesized are bismuth tungstate (BT) and Tetrabutylammonium decatungstate (TBADT), using two consolidated procedures. BT is used as a photo-catalyst for the simulated solar light degradation of ofloxacin (OFL) antibiotic under relevant real conditions (µg L−1, fresh water) with the limit of 0.05 g L−1 of catalyst. A quantitative drug decomposition occurred following a bi-exponential first-order law, with an efficiency comparable with the most used P25 TiO2 catalyst. The photocatalytic profiles of OFL at µg L−1 and mg L−1 were monitored by high-pressure liquid chromatography (HPLC) coupled with fluorescence (FD) and ultraviolet (UV) detectors. Additionally, the main photoproducts were identified by high-pressure liquid chromatography coupled to electrospray ionization in tandem with mass spectrometry (HPLC-ESI-MS/MS). The catalyst Tetrabutylammonium decatungstate (TBADT) was used as a catalyst to produce hydrogen from glucose and 2-propanol in aqueous solution, providing hydrogen gas evolution up to 10 µmol g−1 h−1.

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“…This selectivity pattern has been previously reported and can be rationalized based on the stability of the involved radical intermediates. 16b , 18 When trioxane ( 1g ) was used in the role of H-Donor, in addition to the expected alkyne 9 (45% yield), the hydroalkylation adduct 9′ was isolated as well in 26% yield.…”

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confidence: 99%

“…Differently, the selectivity diverted to the methine C(sp 3 )–H in the case of 2-methyl-1,3-dioxolane ( 1e ), affording products 7 A and 7 B in 75% overall yield with a 3.3:1 ratio. This selectivity pattern has been previously reported and can be rationalized based on the stability of the involved radical intermediates. , When trioxane ( 1g ) was used in the role of H-Donor, in addition to the expected alkyne 9 (45% yield), the hydroalkylation adduct 9′ was isolated as well in 26% yield.…”

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confidence: 99%

Decatungstate as Direct Hydrogen Atom Transfer Photocatalyst for SOMOphilic Alkynylation

Capaldo

Ravelli

2021

Org. Lett.

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A versatile approach for the alkynylation of a variety of aliphatic hydrogen donors, including alkanes, is reported. We used tetrabutylammonium decatungstate as photocatalyst to generate organoradicals from C–H/Si–H bonds via hydrogen atom transfer. The latter intermediates underwent SOMOphilic alkynylation by methanesulfonyl alkynes to afford internal alkynes upon loss of a sulfonyl radical. The effect of different radicofugal groups on the reaction outcome was evaluated and rationalized via a combined experimental and computational approach.

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Efficiency and Selectivity Aspects in the C–H Functionalization of Aliphatic Oxygen Heterocycles by Photocatalytic Hydrogen Atom Transfer

Cited by 22 publications

References 17 publications

Direct Photocatalyzed Hydrogen Atom Transfer (HAT) for Aliphatic C–H Bonds Elaboration

Direct Photocatalyzed Hydrogen Atom Transfer (HAT) for Aliphatic C–H Bonds Elaboration

Tungsten Catalysts for Visible Light Driven Ofloxacin Photocatalytic Degradation and Hydrogen Production

Decatungstate as Direct Hydrogen Atom Transfer Photocatalyst for SOMOphilic Alkynylation

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