Photoredox Allylation Reactions Mediated by Bismuth in Aqueous Conditions

Potenti, Simone; Gualandi, Andrea; Puggioli, Alessio; Fermi, Andrea; Bergamini, Giacomo; Cozzi, Pier Giorgio

doi:10.1002/ejoc.202001640

Cited by 15 publications

(19 citation statements)

References 42 publications

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“…These dyes display Thermally Activated Delayed Fluorescence (TADF) [29] and, on the basis of our experience, give successful results in other metal mediated photoredox processes [25d] . Additionally, in the mentioned photoredox processes, the presence of Hantzsch's ester (HE) was also crucial for the allylation reaction performed with titanium, [10] cobalt, [11b] and bismuth [12] …”

Section: Resultsmentioning

confidence: 99%

Nickel‐Mediated Enantioselective Photoredox Allylation of Aldehydes with Visible Light

et al. 2022

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Here we report a practical, highly enantioselective photoredox allylation of aldehydes mediated by chiral nickel complexes with commercially available allyl acetate as the allylating agent. The methodology allows the clean stereoselective allylation of aldehydes in good to excellent yields and up to 93 % e.e. using a catalytic amount of NiCl2(glyme) in the presence of the chiral aminoindanol‐derived bis(oxazoline) as the chiral ligand. The photoredox system is constituted by the organic dye 3DPAFIPN and a Hantzsch's ester as the sacrificial reductant. The reaction proceeds under visible‐light irradiation (blue LEDs, 456 nm) at 8–12 °C. Compared to other published procedures, no metal reductants (such as Zn or Mn), additives (e.g. CuI) or air‐sensitive Ni(COD)2 are necessary for this reaction. Accurate DFT calculations and photophysical experiments have clarified the mechanistic picture of this stereoselective allylation reaction.

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Section: Resultsmentioning

confidence: 99%

Nickel‐Mediated Enantioselective Photoredox Allylation of Aldehydes with Visible Light

et al. 2022

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“…The environmentally benign nature of bismuth compounds offers access to novel sustainable materials and led to developments, e.g., in catalysis, medicine, radiopaque additives, and electronics [ 1 , 2 , 3 , 4 , 5 , 6 , 7 , 8 , 9 , 10 , 11 , 12 ]. Among the starting materials used for the synthesis of solid-state materials, bismuth(III) nitrate pentahydrate is one of the most common and readily available compounds.…”

Section: Introductionmentioning

confidence: 99%

Deposition of Nanosized Amino Acid Functionalized Bismuth Oxido Clusters on Gold Surfaces

et al. 2022

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Bismuth compounds are of growing interest with regard to potential applications in catalysis, medicine, and electronics, for which their environmentally benign nature is one of the key factors. One thing that currently hampers the further development of bismuth oxido-based materials, however, is the often low solubility of the precursors, which makes targeted immobilisation on substrates challenging. We present an approach towards the solubilisation of bismuth oxido clusters by introducing an amino carboxylate as a functional group. For this purpose, the bismuth oxido cluster [Bi38O45(NO3)20(dmso)28](NO3)4·4dmso (dmso = dimethyl sulfoxide) was reacted with the sodium salt of tert-butyloxycabonyl (Boc)-protected phenylalanine (L-Phe) to obtain the soluble and chiral nanocluster [Bi38O45(Boc–Phe–O)24(dmso)9]. The exchange of the nitrates by the amino carboxylates was proven by nuclear magnetic resonance, Fourier-transform infrared spectroscopy, as well as elemental analysis and X-ray photoemission spectroscopy. The solubility of the bismuth oxido cluster in a protic as well as an aprotic polar organic solvent and the growth mode of the clusters upon spin, dip, and drop coating on gold surfaces were studied by a variety of microscopy, as well as spectroscopic techniques. In all cases, the bismuth oxido clusters form crystalline agglomerations with size, height, and distribution on the substrate that can be controlled by the choice of the solvent and of the deposition method.

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“…164 Bismuth has also been used in allylation reactions under various conditions. 165−171 Potenti and colleagues 172 have recently found the photocatalyzed allylation reaction of aldehydes mediated by Bi(OTf) 3 (10 mol %), employing 2,4,6-tri(9H-carbazol-9-yl)-5-chloroisophthalonitrile (3CzClIPN, 5 mol %) as the photocatalyst in EtOH:H 2 O (1:1) as the mixture of solvents, and Hantzsch ester (HE, 2 equiv) as the electron source under blue LED irradiation. The authors 172 avoided the use of Ir or Ru photocatalysts.…”

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“…Aliphatic aldehydes such as valeraldehyde, 2-phenylacetaldehyde, 3phenylpropanal, cyclohexanecarbaldehyde, and cinnamaldehyde also provide good product yields. 172 The authors investigated the mechanism of the reaction performing luminescence quenching experiments of the photocatalyst (i.e., 3CzClIPN). In the presence of increasing amounts of Bi(OTf) 3 or allyl bromide, no decrease in the emission intensity of 3CzClIPN* was observed.…”

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Advances in Photocatalytic Organic Synthetic Transformations in Water and Aqueous Media

Barata‐Vallejo

Yerien

Postigo

2021

ACS Sustainable Chem. Eng.

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Advances in visible light-photocatalyzed preparative synthetic organic transformations in water or aqueous media are studied. Both the convenience of visible light photocatalytic strategies to achieve synthetic organic transformations and the employment of water or aqueous mixtures make this approach a very resourceful methodology. Mechanistic aspects for such photocatalyzed processes are discussed. The effects of water in the stereoselectivity of some reactions and considerations regarding the improved enantioselectivity in chiral catalytic photoredox reactions are manifested with the use of water. The use of water as a result of a protocol improvement or environmentally friendlier methodology as compared to the same reaction performed in organic solvents are also considered. All these combined effects of water as a reaction medium or its very presence in photocatalytic reactions have an ultimate goal which is to diminish the environmental impact of synthetic and photocatalytic processes. This perspective highlights the progress and state of the art organic transformations realized by photocatalytic techniques in water or aqueous systems as well as water as a reactant. In this regard, aromatic substitution reactions, radical additions to carbon–carbon double bonds, photooxidation reactions, decarboxylation processes, and miscellaneous reactions are presented.

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Photoredox Allylation Reactions Mediated by Bismuth in Aqueous Conditions

Cited by 15 publications

References 42 publications

Nickel‐Mediated Enantioselective Photoredox Allylation of Aldehydes with Visible Light

Nickel‐Mediated Enantioselective Photoredox Allylation of Aldehydes with Visible Light

Deposition of Nanosized Amino Acid Functionalized Bismuth Oxido Clusters on Gold Surfaces

Advances in Photocatalytic Organic Synthetic Transformations in Water and Aqueous Media

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