Browsing by Subject "Photoredox catalysis"

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    Generation of Alkyl Radicals Via C-H Functionalization and Halogen Atom Transfer Processes
    (2022-12) Niu, Ben; Laulhé, Sébastien; Long, Eric; Minto, Robert E.; Pu, Jingzhi
    Alkyl radicals are powerful intermediates for the generation of carbon-carbon bonds, which play an indispensable role in the synthesis of natural products, pharmaceuticals, and pesticides. Traditionally, there are two main methods for the generation of alkyl radicals. The first is C-H bond functionalization via hydrogen-atom-transfer (HAT). HAT processes have been used as an effective approach for selectively activating C-H bonds via radical pathways. The other strategy to explore the generation of alkyl radicals is C-X bond functionalization via halogen-atom-transfer (XAT). Alkyl halides are one of the largest classes of building blocks in synthesis and they can be obtained from the corresponding alcohols. The most straightforward and effective way to form such alkyl radicals is the direct homolytic cleavage of C-X bonds. In past decades, photoredox catalysis has emerged as a powerful and greener tool for the synthesis of radicals under mild reaction conditions, which has brought tremendous attention. Although remarkable success has been made in this field, some methods still require costly transition metal catalysts or toxic reagents. Herein, we display a series of visible light-induced approaches under transition-metal free conditions or using earth-abundant metals. These novel photo-induced transformations and corresponding mechanistic work will be discussed in the following order: We will first present our work on metal-free visible-light-promoted C(sp3)-H functionalization of aliphatic cyclic ethers using trace O2. This reaction uses a trace amount of aerobic oxygen as the sole green oxidant under blue light at room temperature to achieve the synthesis of sulfone and phosphate derivatives in good to excellent yields using cyclic ethers and vinyl sulfones. Then, we report on a photo-induced C(sp3)-H chalcogenation of amide derivatives and ethers via a ligand-to-metal charge-transfer. This reaction converts secondary and tertiary amides, sulfonamides, and carbamates into the corresponding amido-N,S-acetal derivatives in good yields, using an earth abundant metal catalyst under mild conditions. Finally, we present a photoredox polyfluoroarylation of alkyl halides via halogen atom transfer. This method converts primary, secondary, and tertiary unactivated abundant alkyl halides into the corresponding polyfluoroaryl compounds in good yields and has good functional group compatibility.
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    Greener Photoredox-Catalyzed Phosphonations of Aryl Halides
    (2024-05) Kelley, Alexandra S.; Laulhe, Sébastien; Minto, Robert; Deng, Yongming
    Aromatic phosphonates and phosphine oxides are highly desirable synthetic targets used in pharmaceuticals, natural products, agrichemicals, catalysis, and materials science. While a variety of aromatic precursors have been used to access these motifs, aryl halides remain one of the most desirable coupling partners owing to their low cost, commercial availability, and regioselective reactivity. Traditional phosphonation often requires the use of harsh reductants in the presence of liquid ammonia, which are caustic and pose incredible environmental concerns. Milder, transition metal-catalyzed approaches have been developed, but can be limited by air sensitivity, cost, low reaction selectivity, and low functional group compatibility. Photoredox catalysis has been significantly advanced in the past decade in the pursuit of greener, more sustainable avenues to facilitate desirable reaction transformations under mild conditions. These methods most commonly use a dual catalytic strategy in which a metal is paired with an organocatalyst. While these approaches enable facile phosphonation of a variety of aromatic precursors, the metals and organocatalysts used are often expensive and toxic. Indeed, there remains unexplored chemical space for transition metal-free photoredox-catalyzed aryl C-P bond formations. Herein, we present a series of transition metal-free, photoredox-catalyzed approaches to the phosphonation of aryl halides. The approaches and mechanistic works will be discussed in the following order: First, the discovery that 10H-phenothiazine (PTZ) enables the transition metal-free phosphonation of aryl halides using trialkyl phosphites will be presented. PTZ serves as a photocatalyst capable of reducing the aryl halide to access aryl radicals, which readily couple with phosphite esters. This transformation exhibits broad functional group tolerance in good to excellent yields. Then, photoredox catalysis by PTZ enables the formation of unsymmetrical aromatic phosphine oxides using triphenylphosphine (PPh3) and aryl halides. This is the first work in which PPh3 has been used as the starting material, and the reaction proceeds via the alkaline hydrolysis of quaternary phosphonium salts. The final work exhibits novel photocatalytic activity of N-heterocyclic carbenes (NHC) to activate aryl halides, form aryl radicals, and enable phosphonation. This method displays broad functional group tolerance under mild conditions and highlights its untapped synthetic utility as a photocatalyst.
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    Recent Advances in Synthetic Methods by Photocatalytic Single-Electron Transfer Chemistry of Pyridine N-Oxides
    (American Chemical Society, 2024) Satheesh, Vanaparthi; Deng, Yongming; Chemistry and Chemical Biology, School of Science
    By adoption of the enabling technology of modern photoredox catalysis and photochemistry, the generation of reactive and versatile pyridine N-oxy radicals can be facilely achieved from single-electron oxidation of pyridine N-oxides. This Synopsis highlights recent methodologies mediated by pyridine N-oxy radicals in developing (1) pyridine N-oxide-based hydrogen atom transfer catalysts for C(sp3)-H functionalizations and (2) β-oxyvinyl radical-mediated cascade reactions. In addition, recent research revealed that direct photoexcitation of pyridine N-oxides allowed for the generation of alkyl carbon radicals from alkylboronic acids.