A Computational Study of Photoinduced Borylation for Selected Boron Sources DOI Creative Commons

Ka Wa Fan,

Hoi Ling Luk, David Lee Phillips

и другие.

ChemistryOpen, Год журнала: 2024, Номер 13(7)

Опубликована: Март 8, 2024

Abstract This research article uses density functional theory (DFT) to study photoinduced borylation. work examined the electron donor‐acceptor complex (EDA) of bis(catecholato)diboron with different redox‐active leaving groups and bis(pinacol)diboron aryl N‐hydroxyphthalimide. The results these DFT studies show ratio B 2 cat N, N‐dimethylacetamide (DMA) should be 1 : which is consistent experimental in literature. We further proposed a reaction mechanism calculated energies associated each step.

Язык: Английский

Sulfonium Salts as Acceptors in Electron Donor‐Acceptor Complexes DOI Creative Commons
Leendert van Dalsen,

Rachel E. Brown,

James A. Rossi‐Ashton

и другие.

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(29)

Опубликована: Март 24, 2023

Abstract The photoactivation of electron donor‐acceptor complexes has emerged as a sustainable, selective and versatile strategy for the generation radical species. Electron (EDA) complexation, however, imposes electronic constraints on donor acceptor components this can limit range radicals that be generated using approach. New EDA complexation strategies exploiting sulfonium salts allow to from native functionality. For example, aryl salts, formed by activation arenes, serve in due their electron‐deficient nature. This “sulfonium tag” approach relaxes parent substrate dramatically expands complexation. In review, these new applications will introduced areas chemical space rendered accessible through innovation highlighted.

Язык: Английский

Процитировано

98

Synthetic Applications of Sulfonium Salts as Aryl Radical Precursors DOI Open Access

Xinyin Wu,

Pan Gao, Feng Chen

и другие.

European Journal of Organic Chemistry, Год журнала: 2023, Номер 26(43)

Опубликована: Сен. 13, 2023

Abstract The utilization of aryl radicals as open‐shelled intermediates has become an essential tool for both conventional and state‐of‐the‐art synthetic chemistry. However, the current methods generating are still inefficient, greatly impeding their practical applications. Encouragingly, sulfonium salts have emerged appealing sources a wide range transformations aimed at creating novel chemical bonds driven by distinctive structural attributes tendencies. This review primarily focuses on specific reaction mechanisms underlying cleavage C−S in salts, leading to generation corresponding within diverse conditions.

Язык: Английский

Процитировано

40

Thianthrene Radical Cation as a TransientSETMediator: Photoinduced Thiocyanation and Selenocyanation of Arylthianthrenium Salts DOI

Xiao‐Yue Chen,

Xin Kuang,

Yichen Wu

и другие.

Chinese Journal of Chemistry, Год журнала: 2023, Номер 41(16), С. 1979 - 1986

Опубликована: Апрель 5, 2023

Comprehensive Summary A novel transient SET mediator approach has been developed for the photoinduced radical‐radical cross coupling reaction. Using in‐situ generated thianthrene radical cation as mediator, thiocyanation and selenocyanation of aryl thianthrenium salts have realized under mild conditions without need photocatalyst or single electron donor. In comparison with enabled process, protocol features conditions, simple manipulation, a broad substrate scope, excellent functional group heterocycle tolerance. Due to feasible accessibility salts, this method also applied in efficient synthesis bioactive molecule, late‐stage functionalization complex arenes.

Язык: Английский

Процитировано

27

Generation and Application of Aryl Radicals Under Photoinduced Conditions DOI
Anupam Das, K. R. Justin Thomas

Chemistry - A European Journal, Год журнала: 2024, Номер 30(31)

Опубликована: Март 28, 2024

Abstract Photoinduced aryl radical generation is a powerful strategy in organic synthesis that facilitates the formation of diverse carbon‐carbon and carbon‐heteroatom bonds. The synthetic applications photoinduced complex compounds, including natural products, physiologically significant molecules, functional materials, have received immense attention. An overview current developments production methods their uses given this article. A generalized idea how to choose reagents approach for radicals described, along with techniques associated mechanistic insights. Overall, article offers critical assessment results as well selection reaction parameters specific context cascades, cross‐coupling reactions, functionalization, selective C−H functionalization substrates.

Язык: Английский

Процитировано

16

Photocatalyst/metal-free sequential C–N/C–S bond formation: Synthesis of S-arylisothioureas via photoinduced EDA complex activation DOI

Guoju Guo,

Xufeng Li, Jie Ma

и другие.

Chinese Chemical Letters, Год журнала: 2024, Номер 35(11), С. 110024 - 110024

Опубликована: Май 17, 2024

Язык: Английский

Процитировано

16

Single-Electron-Transfer-Generated Aryl Sulfonyl Ammonium Salt: Metal-Free Photoredox-Catalyzed Modular Construction of Sulfonamides DOI
Fengying Yan, Qing Li,

Shanshan Fu

и другие.

ACS Catalysis, Год журнала: 2024, Номер 14(7), С. 5227 - 5235

Опубликована: Март 21, 2024

Sulfonamides are prominently featured in organic synthesis and medicinal chemistry. Yet, a general synthetic platform for the modular construction of aryl sulfonamides remains elusive. Herein, metal-free photoredox-catalyzed three-component via an sulfonyl ammonium salt intermediate, which was generated situ SET event, has been established. A variety structurally diverse primary, secondary, tertiary were synthesized rapidly from abundant amines or sodium azide under mild conditions. Notably, primary aliphatic amine, challenging Cu-catalyzed protocols, worked well this approach. Moreover, fluoride can be accessed smoothly as well, using potassium hydrogen nucleophile. The potential utility conversion is demonstrated facile three bioactive drug compounds. Preliminary mechanistic studies have revealed that radical key intermediates mechanistically innovative methodology.

Язык: Английский

Процитировано

12

Electrocatalytic Formal C(sp2)−H Alkylations via Nickel‐Catalyzed Cross‐Electrophile Coupling with Versatile Arylsulfonium Salts DOI Creative Commons
Takuya Michiyuki, Simon L. Homölle, Neeraj Kumar Pandit

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(29)

Опубликована: Май 2, 2024

Producing sp

Язык: Английский

Процитировано

11

The Strategies towards Electrochemical Generation of Aryl Radicals DOI
Xiaobao Zeng

Chemistry - A European Journal, Год журнала: 2024, Номер unknown

Опубликована: Июль 16, 2024

The advancement in electrochemical techniques has unlocked a new path for achieving unprecedented oxidations and reductions of aryl radical precursors controlled selective manner. This approach facilitates the construction aromatic carbon-carbon carbon-heteroatom bonds. In light green merits growing importance this technique chemistry, review aims to provide an overview recent advance generation radicals organized by precursor type, with focus on substrate scope, limitation, underlying mechanism, thereby inspiring future work generation.

Язык: Английский

Процитировано

10

Transition‐Metal‐Free Radical Borylation Reactions DOI

Zhi‐Hao Shang,

Jun Pan, Zeyu Wang

и другие.

European Journal of Organic Chemistry, Год журнала: 2023, Номер 26(12)

Опубликована: Фев. 13, 2023

Abstract Organoboron compounds are versatile synthons in synthetic chemistry, materials science, and medicinal chemistry. The preparation of them often requires either reactive organometallic reagents or transition metals. In recent years, transition‐metal‐free borylation methodologies using radical chemistry for C−B bond formation have attracted much attention developed rapidly, which circumvents the use preformed reagents. Various successful approaches from different precursors (such as carboxylic acids, amines alcohols, abundant nature) through thermochemical, photochemical electrochemical pathways been developed. Therefore, this review, we hope to provide an overview advances discovery, development, mechanistic study processes.

Язык: Английский

Процитировано

18

Energy-transfer-enabled photocatalytic transformations of aryl thianthrenium salts DOI Creative Commons
Kai Sun, Chang Ge, Xiaolan Chen

и другие.

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Ноя. 8, 2024

Aryl thianthrenium salts are valuable in photocatalysis but traditionally require external electron donors for activation. This study introduces an energy transfer (EnT) strategy the activation of aryl using 2,3,4,5,6-penta(carbazol-9-yl)benzonitrile (5CzBN) as a metal-free photocatalyst, eliminating need donors. Utilizing this EnT approach, we achieve C-H deuteration arenes under visible light with CDCl

Язык: Английский

Процитировано

9