Photochemical Activation of Sulfur Hexafluoride: A Tool for Fluorination and Pentafluorosulfanylation Reactions

Rombach, David; Wagenknecht, Hans‐Achim

doi:10.1055/a-1877-5231

Cited by 14 publications

(1 citation statement)

References 153 publications

(151 reference statements)

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“…While photocatalytic SET reduction of SF 6 had been achieved previously with Ir(ppy) 2 (dtb-ppy)PF 6 by Jamison’s group [ 129 ], the fragmentation pattern of SF 6 •− was proposed to be highly dependent on the excess energy provided by SET. The less potent reducing iridium species in Jamison’s work favors the lower energy fragmentation pathway to F • and SF 5 − whereas highly potent reductant * N -Ph PTZ provides enough energy for access to SF 5 • and thus, pentafluorosulfanylation [ 16 , 130 ]. Addition of catalytic amounts of Cu(acac) 2 was found to favor product formation by suppressing undesired side reactions.…”

Section: Reviewmentioning

confidence: 99%

Photoredox catalysis harvesting multiple photon or electrochemical energies

Lepori,

Schmid,

Barham

2023

Beilstein J. Org. Chem.

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Photoredox catalysis (PRC) is a cutting-edge frontier for single electron-transfer (SET) reactions, enabling the generation of reactive intermediates for both oxidative and reductive processes via photon activation of a catalyst. Although this represents a significant step towards chemoselective and, more generally, sustainable chemistry, its efficacy is limited by the energy of visible light photons. Nowadays, excellent alternative conditions are available to overcome these limitations, harvesting two different but correlated concepts: the use of multi-photon processes such as consecutive photoinduced electron transfer (conPET) and the combination of photo- and electrochemistry in synthetic photoelectrochemistry (PEC). Herein, we review the most recent contributions to these fields in both oxidative and reductive activations of organic functional groups. New opportunities for organic chemists are captured, such as selective reactions employing super-oxidants and super-reductants to engage unactivated chemical feedstocks, and scalability up to gram scales in continuous flow. This review provides comparisons between the two techniques (multi-photon photoredox catalysis and PEC) to help the reader to fully understand their similarities, differences and potential applications and to therefore choose which method is the most appropriate for a given reaction, scale and purpose of a project.

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Section: Reviewmentioning

confidence: 99%

Photoredox catalysis harvesting multiple photon or electrochemical energies

Lepori,

Schmid,

Barham

2023

Beilstein J. Org. Chem.

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Ambiphilic Reactivity of SF₅‐Alkynes Applied to Regioselective and Stereodivergent Halogenation Reactions: An Experimental and Theoretical Case Study

Matchavariani,

Popek,

Cabrera‐Trujillo

et al. 2024

Adv Synth Catal

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We explored the ambiphilic reactivity of SF5‐alkynes, and we proved they can act as both nucleophiles and electrophiles. We selected halogenation reactions as benchmark reactions and developed highly selective stereodivergent hydrohalogenation (I, Br, Cl, F) reactions of SF5‐alkynes. The stereochemistry is finely controlled thanks to the nature of the acids used (strong or soft) in the presence of halide source, while the high regioselectivity is governed by the strong polarization of SF5‐alkynes. Mechanistic studies supported by DFT calculations shed light on two different reaction mechanisms responsible of the excellent stereocontrol. This stereoselectivity was quantitatively rationalized with the ASM and EDA methods. A few dihalogenation reactions are reported and DFT calculations rationalize this cis‐stereoselectivity. Relative configuration of all the SF5‐haloalkenes was unambiguously determined by X‐ray diffraction. Noteworthy, several post‐functionalization reactions such as cross‐couplings, cyanation and reductions are described to strengthen the synthetic potential.

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Expanding the Frontier of Linear Drug Design: Cu‐Catalyzed C_sp–C_sp³‐Coupling of Electron‐Deficient SF₄‐Alkynes with Alkyl Iodides

Narra,

Bacho,

Hattori

et al. 2023

Advanced Science

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Despite the attractive properties of tetrafluorosulfanyl (SF4) compounds in drug discovery, medicinal research on SF4 molecules is hindered by the scarcity of suitable synthetic methodologies. Drawing inspiration from the well‐established Sonogashira cross‐coupling of terminal alkynes under Pd‐catalysis, it is envisioned that SF4‐alkynes can serve as effective coupling partners. To overcome the challenges associated with the electron‐deficient nature of SF4‐alkynes and the lability of the SF4 unit under transition‐metal catalysis, an aryl radical mediated Csp–Csp3 cross‐coupling reaction is successfully developed under Cu catalysis. This methodology facilitates the coupling of SF4‐alkynes with alkyl iodides, leading to the immediate synthesis of SF4‐attached drug‐like molecules. These findings highlight the potential impact of SF4‐containing molecules in the drug industry, paving the way for further research in this emerging field.

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Photochemical Activation of Sulfur Hexafluoride: A Tool for Fluorination and Pentafluorosulfanylation Reactions

Cited by 14 publications

References 153 publications

Photoredox catalysis harvesting multiple photon or electrochemical energies

Photoredox catalysis harvesting multiple photon or electrochemical energies

Ambiphilic Reactivity of SF₅‐Alkynes Applied to Regioselective and Stereodivergent Halogenation Reactions: An Experimental and Theoretical Case Study

Expanding the Frontier of Linear Drug Design: Cu‐Catalyzed C_sp–C_sp³‐Coupling of Electron‐Deficient SF₄‐Alkynes with Alkyl Iodides

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Photochemical Activation of Sulfur Hexafluoride: A Tool for Fluorination and Pentafluorosulfanylation Reactions

Cited by 14 publications

References 153 publications

Photoredox catalysis harvesting multiple photon or electrochemical energies

Photoredox catalysis harvesting multiple photon or electrochemical energies

Ambiphilic Reactivity of SF5‐Alkynes Applied to Regioselective and Stereodivergent Halogenation Reactions: An Experimental and Theoretical Case Study

Expanding the Frontier of Linear Drug Design: Cu‐Catalyzed Csp–Csp3‐Coupling of Electron‐Deficient SF4‐Alkynes with Alkyl Iodides

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Product

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About

Ambiphilic Reactivity of SF₅‐Alkynes Applied to Regioselective and Stereodivergent Halogenation Reactions: An Experimental and Theoretical Case Study

Expanding the Frontier of Linear Drug Design: Cu‐Catalyzed C_sp–C_sp³‐Coupling of Electron‐Deficient SF₄‐Alkynes with Alkyl Iodides