Опубликована: Май 15, 2024
We demonstrate 1) that halogen bonding is not critical for enabling light-driven radical generation from diaryliodonium salts and 2) radi-cals generated by this route can be captured transition-metals C–H arylation reactions. These results are the first step toward devel-oping new metal-catalyzed aryl couplings without exogenous photocatalysts.
Язык: Английский
The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(9), С. 6117 - 6125
Опубликована: Апрель 24, 2024
The first paired electrolysis-enabled arylation of quinoxalin-2(1H)-ones was achieved using cyanoarenes as the reagents. A variety 3-arylquinoxalin-2(1H)-ones with various important functional groups were obtained in moderate to good yields under metal- and chemical oxidant-free conditions. With a pair reductive oxidative processes occurring among substrates reaction intermediates, power consumption can be dramatically reduced.
Язык: Английский
Процитировано
22
Organic Letters, Год журнала: 2024, Номер 26(15), С. 3189 - 3194
Опубликована: Апрель 8, 2024
A new umpolung approach to the C3–H functionalization of indoles with diverse nucleophiles based on intermediate formation I(III) reagents is described. The 3,5-dimethylisoxazol-4-yl auxiliary allows for selective indole transfer under catalyst-free conditions, which was impossible using previously reported reagents. Combining mildness transition-metal-free conditions and high reactivity hypervalent iodine reagents, this protocol tolerates various functional groups provides access that are difficult prepare conventionally.
Язык: Английский
Процитировано
9
ChemCatChem, Год журнала: 2024, Номер 16(11)
Опубликована: Янв. 15, 2024
Abstract Visible‐light‐activated organic reactions unlock novel avenues for complex molecular transformations, impossible under standard “thermal” conditions, which makes them powerful tools in the arsenal of synthetic chemistry. However, transition metal‐based or photoredox catalysts are often used to ensure productive absorption visible light, might be not desirable medicinal chemistry and industry due toxicity, low sustainability, high cost most photocatalysts. A more environmentally economically benign approach is based on formation transient electron donor‐acceptor (EDA) complexes between two reagents a reagent an additive, that readily absorb acting as internal photosensitizers. Within EDA complex‐based arylation strategies, chemical transformations mediated by noncovalent interaction molecules, namely electron‐poor aryl halides their equivalents electron‐rich nucleophilic additives. Moreover, besides stoichiometric organocatalysis can achieved certain cases through regeneration donor molecules course reaction. Photoexcitation induces single transfer (SET) process generate radical species step. This Review will focus state‐of‐the‐art strategies utilizing halides, aryldiazonium, diaryliodonium, arylsulfonium arylphosphonium salts reactants, published mainly last five years.
Язык: Английский
Процитировано
8
Organic Letters, Год журнала: 2024, Номер 26(30), С. 6471 - 6476
Опубликована: Июль 23, 2024
Visible light-induced C-3 arylation of quinoxalin-2(1
Язык: Английский
Процитировано
7
Chemical Reviews, Год журнала: 2025, Номер unknown
Опубликована: Март 7, 2025
Constructing chemical bonds under green sustainable conditions has drawn attention from environmental and economic perspectives. The dissociation of (hetero)aryl-halide is a crucial step most arylations affording (hetero)arene derivatives. Herein, we summarize the (hetero)aryl halides activation enabling direct (hetero)arylation trapping reagents construction highly functionalized (hetero)arenes benign conditions. strategies for aryl iodides are classified into (a) hypervalent iodoarene followed by functionalization thermal/photochemical conditions, (b) aryl-I bond in presence bases with/without organic catalysts promoters, (c) photoinduced presence/absence organophotocatalysts, (d) electrochemical direct/indirect electrolysis mediated organocatalysts mediators acting as electron shuttles, (e) electrophotochemical redox-active organocatalysts. These modes result exhibiting diverse reactivity formal cations/radicals/anions aryne precursors. coupling these reactive intermediates with leads to facile selective formation C-C C-heteroatom bonds. ecofriendly, inexpensive, functional group-tolerant offer alternatives transition metal-based catalysis.
Язык: Английский
Процитировано
1
The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(14), С. 10112 - 10126
Опубликована: Июль 3, 2024
A photoredox-promoted decarboxylative C-H glycosylation for the synthesis of nonclassical heteroaryl C-glycosides is reported. This methodology characterized by an exceedingly simple reaction system, high diastereoselectivity, and good functional group tolerance. Moreover, operational procedure simple, gram-scale highlights practical applicability this protocol.
Язык: Английский
Процитировано
5
Advanced Synthesis & Catalysis, Год журнала: 2024, Номер unknown
Опубликована: Июнь 13, 2024
Abstract A visible‐light‐promoted strategy for the decarboxylative C‐3 carbamoylation of quinoxalinone scaffolds is developed. This approach initiates through formation an EDA complex between oxamic acid and quinoxalinone. Successive SET construct C−C bond. method utilizes aerial oxygen as green oxidant eradicates process from use external photocatalysts transition metals. Detailed synthetic photophysical studies enlighten reaction pathway.
Язык: Английский
Процитировано
4
Organic Letters, Год журнала: 2024, Номер 26(37), С. 7864 - 7868
Опубликована: Сен. 9, 2024
A hypervalent iodine-reagent-based C-H functionalization strategy was utilized to synthesize diaryl ethers. This method directly transforms various arenes into their corresponding diaryliodonium salts, followed by a C-O coupling reaction produce structurally diverse The efficacy of this approach in the late-stage structural modifications complex molecules demonstrated.
Язык: Английский
Процитировано
3
Green Synthesis and Catalysis, Год журнала: 2024, Номер unknown
Опубликована: Дек. 1, 2024
Язык: Английский
Процитировано
3
Chinese Journal of Chemistry, Год журнала: 2025, Номер unknown
Опубликована: Янв. 16, 2025
Comprehensive Summary Herein, we report a photo‐induced, metal‐/additive‐free protocol for the difluoromethylation of N ‐heteroaromatics with [bis(difluoroacetoxy)iodo]benzene as reagent. The affords difluoromethylated in moderate to good yield (up 91%). transformation is compatible wide range substrates and has tolerance towards various functional groups. Moreover, synthetic value this method further demonstrated by applications gram‐scale synthesis late‐stage functionalization biologically important molecules.
Язык: Английский
Процитировано
0