Iridium Photoredox-Catalyzed Stereoselective C-Glycosylation with Tetrafluoropyridin-4-yl Thioglycosides: A Facile Synthesis of C-α/β-Glucogallins and Their Antioxidant Activity DOI
Shenghao Li, Han Ding, Ruge Cao

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: unknown, P. 17727 - 17738

Published: Nov. 18, 2024

We demonstrate an efficient, scalable, and stereoselective C-glycosylation with thioglycosides possessing a unique photoactive tetrafluoropyridin-4-yl (TFPy) thio radical leaving group, affording editable medicinally biologically essential C-α-glucogallin derivatives. In the presence of silyl enol ether acceptors, desulfurative coupling reaction performs smoothly under mild conditions upon exposure to blue light irradiation. This versatile protocol permits synthesis sugar-drug chimeras by C1 ketonylation complex drug-derived ethers. The scale-up synthesis, anomeric epimerization, post-C-glycosylation modification ketone sugars showcase reaction's potential utilities. Furthermore, could be applied direct carbohydrate skeleton editing equipping group on nonanomeric position. is viable for unprotected TFPy thioglycoside, route ketonyl sugars. concise six-step assembly both configurated C-glucogallins from commercially cheap glucose pentaacetate their antioxidant reactivity investigations underline promising medicinal relevance our current protocols. mechanism was investigated through trapping experiment, oxocarbenium fluorescence quenching Stern–Volmer analysis, confirming that major glycosyl intermediates are generated thioglycoside donors, whose effectively quench excited Ir(ppy)3 oxidative process, complementary product, accounting examples moderate selectivities.

Language: Английский

Photoinduced intermolecular hydrogen atom transfer reactions in organic synthesis DOI Creative Commons
Hui Cao, Xinxin Tang,

Haidi Tang

et al.

Chem Catalysis, Journal Year: 2021, Volume and Issue: 1(3), P. 523 - 598

Published: May 24, 2021

Language: Английский

Citations

323
Iron-Catalyzed C(Sp3)–H Borylation, Thiolation, and Sulfinylation Enabled by Photoinduced Ligand-to-Metal Charge Transfer DOI
Jia‐Lin Tu,

Ao-Men Hu,

Lin Guo

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(13), P. 7600 - 7611

Published: March 23, 2023

Catalytic C(sp3)-H functionalization has provided enormous opportunities to construct organic molecules, facilitating the derivatization of complex pharmaceutical compounds. Within this framework, direct hydrogen atom transfer (HAT) photocatalysis becomes an appealing approach goal. However, viable substrates utilized in these protocols are limited, and site selectivity shows preference activated thermodynamically favored bonds. Herein, we describe development undirected iron-catalyzed borylation, thiolation, sulfinylation reactions enabled by photoinduced ligand-to-metal charge (LMCT) process. These exhibit remarkably broad substrate scope (>150 examples total), most importantly, all three show unconventional regioselectivity, with occurrence preferentially at distal methyl position. The procedures operationally simple readily scalable provide access high-value products from hydrocarbons one step. Mechanistic studies control experiments indicate that afforded is not only relevant HAT species but also largely affected use boron- sulfone-based radical acceptors.

Language: Английский

Citations

116
Radical approaches to C–S bonds DOI
Zijun Wu, Derek A. Pratt

Nature Reviews Chemistry, Journal Year: 2023, Volume and Issue: 7(8), P. 573 - 589

Published: June 21, 2023

Language: Английский

Citations

52
Dynamic Reversible Oxidation‐Reduction of Iodide Ions for Operationally Stable Perovskite Solar Cells under ISOS‐L‐3 Protocol DOI

Xiaoyi Lü,

Kexuan Sun,

Yaohua Wang

et al.

Advanced Materials, Journal Year: 2024, Volume and Issue: 36(25)

Published: April 5, 2024

Despite rapid advancements in the photovoltaic efficiencies of perovskite solar cells (PSCs), their operational stability remains a significant challenge for commercialization. This instability mainly arises from light-induced halide ion migration and subsequent oxidation into iodine (I

Language: Английский

Citations

28
Light-activated hypervalent iodine agents enable diverse aliphatic C–H functionalization DOI
Zhipeng Lu, John Putziger, Song Lin

et al.

Nature Chemistry, Journal Year: 2025, Volume and Issue: 17(3), P. 365 - 372

Published: Feb. 24, 2025

Language: Английский

Citations

2
Selective deoxygenative alkylation of alcohols via photocatalytic domino radical fragmentations DOI Creative Commons
Hongmei Guo, Xuesong Wu

Nature Communications, Journal Year: 2021, Volume and Issue: 12(1)

Published: Sept. 10, 2021

Abstract The delivery of alkyl radicals through photocatalytic deoxygenation primary alcohols under mild conditions is a so far unmet challenge. In this report, we present one-pot strategy for deoxygenative Giese reaction with electron-deficient alkenes, by using xanthate salts as alcohol-activating groups radical generation visible-light photoredox in the presence triphenylphosphine. convenient and high reactivity sequential C–S/C–O bond homolytic cleavage enable efficient primary, secondary tertiary diverse functionality structure to generate corresponding radicals, including methyl radical. Moreover, chemoselective monodeoxygenation diols achieved via selective formation salts.

Language: Английский

Citations

82
A photoexcited halogen-bonded EDA complex of the thiophenolate anion with iodobenzene for C(sp3)–H activation and thiolation DOI Creative Commons
Tao Li, Kangjiang Liang,

Jiaying Tang

et al.

Chemical Science, Journal Year: 2021, Volume and Issue: 12(47), P. 15655 - 15661

Published: Jan. 1, 2021

Thiophenol was discovered to form an EDA complex with iodobenzene through halogen bonding interactions upon treatment KOH. A direct photochemical thiolation of C(sp3)-H bond-containing etheric, allylic, and benzylic substrates thiophenol developed. The reaction proceeded on the basis in situ generation a thiyl radical aryl single electron transfer between photoexcited thiophenolate anion iodide complex. Then C(sp3) centred-radical formed by radical-mediated hydrogen atom products were delivered via radical-radical cross-coupling radical.

Language: Английский

Citations

67
Boron, silicon, nitrogen and sulfur-based contemporary precursors for the generation of alkyl radicals by single electron transfer and their synthetic utilization DOI
Vincent Corcé, Cyril Ollivier, Louis Fensterbank

et al.

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(4), P. 1470 - 1510

Published: Jan. 1, 2022

Recent developments in the use of boron, silicon, nitrogen and sulfur derivatives single-electron transfer reactions for generation alkyl radicals are described. Photoredox catalyzed, electrochemistry promoted or thermally-induced oxidative reductive processes discussed highlighting their synthetic scope discussing mechanistic pathways.

Language: Английский

Citations

66
Visible-Light-Driven C–S Bond Formation Based on Electron Donor–Acceptor Excitation and Hydrogen Atom Transfer Combined System DOI Creative Commons
Tatsuhiro Uchikura,

Yurina Hara,

Kazushi Tsubono

et al.

ACS Organic & Inorganic Au, Journal Year: 2021, Volume and Issue: 1(1), P. 23 - 28

Published: June 22, 2021

Developed herein is a visible-light-driven synthesis of sulfides by an electron donor-acceptor/single transfer and hydrogen atom combined system without transition metals strong oxidants. This reaction proceeds through the excitation donor-acceptor complex between thiolate aryl halide, followed from alkane to generated radical.

Language: Английский

Citations

61
Divergent functionalization of aldehydes photocatalyzed by neutral eosin Y with sulfone reagents DOI Creative Commons
Jianming Yan,

Haidi Tang,

Eugene Jun Rong Kuek

et al.

Nature Communications, Journal Year: 2021, Volume and Issue: 12(1)

Published: Dec. 10, 2021

Abstract While aldehydes represent a classic class of electrophilic synthons, the corresponding acyl radicals are inherently nucleophilic, which exhibits umpolung reactivity. Generation typically requires noble metal catalysts or excess oxidants to be added. Herein, we report convenient and green approach access radicals, capitalizing on neutral eosin Y-enabled hydrogen atom transfer (HAT) photocatalysis with aldehydes. The generated underwent SOMOphilic substitutions various functionalized sulfones (X–SO 2 R’) deliver value-added products. merger Y sulfone-based SOMOphiles provides versatile platform for wide array aldehydic C–H functionalizations, including fluoromethylthiolation, arylthiolation, alkynylation, alkenylation azidation. present protocol features characteristics, such as being free metals, harmful additives; step-economic; redox-neutral; amenable scale-up assisted by continuous-flow technology.

Language: Английский

Citations

61