Photocatalytic ATRA reaction promoted by iodo-Bodipy and sodium ascorbate

Magagnano, Giandomenico; Gualandi, Andrea; Marchini, Marianna; Ceroni, Paola; Cozzi, Pier Giorgio

doi:10.1039/c6cc09387f

Cited by 87 publications

(56 citation statements)

References 33 publications

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“…In this case, only one example using bromoacetonitrile was reported . A very recent photoorganocatalytic example, demonstrating a single example with bromoacetonitrile was also reported by Cozzi and co‐workers . Also, two methods were developed for the addition of bromoacetonitrile to styrene derivatives under photoredox catalysis (Scheme C) .…”

Section: Introductionsupporting

confidence: 87%

Expanding the Scope of Photocatalysis: Atom Transfer Radical Addition of Bromoacetonitrile to Aliphatic Olefins

2018

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An efficient photocatalyzed bromocyanomethylation of alkenes is reported. Among a range of organocatalysts and metal complexes, Ir(ppy)3 proved to be the best photocatalyst in promoting the addition of BrCH2CN to olefins. This photocatalytic atom transfer protocol can be expanded into a wide substrate scope of aliphatic olefins bearing various functional groups, leading to the corresponding products in good to excellent yields. In addition, linchpin catalysis was developed, since the bromo group can undergo further transformation into useful functional groups, such as the synthesis of amino acids.

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Section: Introductionsupporting

confidence: 87%

Expanding the Scope of Photocatalysis: Atom Transfer Radical Addition of Bromoacetonitrile to Aliphatic Olefins

2018

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“…Based on thorough investigation of the polymerization process, we greatly enhanced the polymerization efficiency and successfully outlined the full mechanism of O‐START polymerization. During our research process, Gualandi and co‐workers reported photomediated atom transfer radical addition (ATRA) catalyzed by iodo‐Bodipy/ l (+)‐ascorbic acid sodium salt, which further validated the mechanism we proposed. As our polymerization was a free radical mechanism and high tolerant to functional groups, various polar or ionic groups could be easily inserted into the polymerization chain through monomer structure design, not restricted to those presented here ( Scheme b).…”

Section: Methodssupporting

confidence: 73%

Organocatalytic Approach to Functional Semifluorinated Polymers Driven by Visible Light

Cheng

et al. 2018

Macromol. Rapid Commun.

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Through the construction of an organic photocatalysis system, photoredox catalyst (PC)/additive, where PC stands for photoredox catalyst, an organocatalyzed step transfer-addition and radical-termination (O-START) polymerization irradiated by blue LED light at room temperature is realized. Different types of α,ω-diiodoperfluoroalkane A and α,ω-unconjugated diene B are copolymerized through O-START efficiently, and generate various kinds of functional semifluorinated polymers, including polyolefins and polyesters. The process is affected by several factors; solvents, additives, and feed ratio of A to B. After optimization of all these components, the polymerization efficiency is greatly improved, generating polymers with both relatively high yield and molecular weight. Considering the mild reaction condition, easy operation process, and free-of-metal-catalyst residues in the polymer product, the organocatalytic polymerization strategy provides a simple and efficient approach to functional semifluorinated polymer materials and hopefully opens up their application in high-tech fields.

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“…and the corresponding iminium, thereby self‐propagating the reaction in a radical chain fashion (Scheme ) . Control experiments in aerated solutions did not show any significant conversion to acetophenone or other dehalogenated species, suggesting that the presence of O 2 (both at the triplet ground state and at its singlet excited state) is detrimental to the evolution of the radical mechanism as depicted in Scheme . Furthermore, we expect that, given their slow deactivation in deaerated solvents (around 50 μs in C 6 H 6 for PXXMI and PXXDI ), the triplet excited states of imide‐derivatives could also contribute to some extent to trigger the same transformation via an ET process.…”

Section: Resultsmentioning

confidence: 95%

Customizing Photoredox Properties of PXX‐based Dyes through Energy Level Rigid Shifts of Frontier Molecular Orbitals

Sciutto

Fermi

Folli

et al. 2018

Chemistry A European J

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Here we describe the synthesis of electron-rich PXX derivatives in which the energy levels of the excited states have been rigidly shifted through the insertion of imide groups. This has allowed the development of a new series of oxygen-doped photoredox-active chromophores with improved oxidizing and reducing properties. Capitalizing on the dehalogenation of organic halides as a model reaction, we could investigate the photooxidative and photoreductive potential of these molecules in model chemical transformations. Depending on the substrate, solvent and dye the reaction mechanism can follow different paths. This prompted us to consider the first chemoselective transformation protocol, in which two different C-Br bonds could be chemoselectively reacted through the sequential photoactivation of two different colorants.

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Photocatalytic ATRA reaction promoted by iodo-Bodipy and sodium ascorbate

Abstract: Using ascorbate as a sacrificial reductant, iodo-Bodipy dye 1b is able to promote the ATRA reaction between bromoderivatives and alkenes. This finding expands the possibility of using Bodipy dyes to promote photocatalytic reactions in efficient ways.

Cited by 87 publications

References 33 publications

Expanding the Scope of Photocatalysis: Atom Transfer Radical Addition of Bromoacetonitrile to Aliphatic Olefins

Expanding the Scope of Photocatalysis: Atom Transfer Radical Addition of Bromoacetonitrile to Aliphatic Olefins

Organocatalytic Approach to Functional Semifluorinated Polymers Driven by Visible Light

Customizing Photoredox Properties of PXX‐based Dyes through Energy Level Rigid Shifts of Frontier Molecular Orbitals

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