CH‐Functionalization of Heterocycles with the Formation of C−O, C−N, C−S/Se, and C−P Bonds by Intermolecular Addition of Heteroatom‐Centered Radicals

Advanced Synthesis & Catalysis, Год журнала: 2023, Номер 365(11), С. 1714 - 1755

Опубликована: Апрель 12, 2023

Abstract In the last decade, free radicals have found a wide application in functionalization of unsaturated compounds, such as alkenes, alkynes, and arenes, via free‐radical addition to carbon‐carbon π‐bonds. these processes, intermolecular attack on aromatic substrates represents challenge due relatively high resistance π‐system reactions comparison alkene C=C bonds. The heterocycles is especially interesting diversity their structures chemical properties well importance for medicinal chemistry, agrochemistry, materials science. Addition C‐centered widely known Minisci‐type well‐reviewed. this paper, we summarized main achievements less explored group processes: by heteroatom‐centered (O‐, N‐, S‐/Se‐, P‐radicals) with emphasis papers published after 2010. Literature analysis revealed strong trend towards usage electrochemistry photoredox‐catalysis generation recent years. remaining fundamental problem field lack experimental support proposed mechanisms frequent existence several plausible reaction pathways. progress mechanistic studies can significantly improve prediction optimal conditions depending structure.

Язык: Английский

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Visible-Light-Induced Regio-selective Oxidative Coupling of Quinoxalinones with Pyrrole Derivatives

Chinese Journal of Organic Chemistry, Год журнала: 2023, Номер 43(2), С. 697 - 697

Опубликована: Янв. 1, 2023

a 王洁慧 王 磊 * ,a,b ( 台州学院高等研究院和药学院 浙江台州 318000) b 中国科学院上海有机化学研究所 金属有机化学国家重点实验室 上海 200032) 摘要 发展了一种区域选择性的喹喔啉酮 3-位氧化偶联富电子吡咯衍生物的方法.以 + 4 Mes-Acr-Me ClO -(3 mol%)为 光敏剂, 空气氧为氧化剂, 高收率得到喹喔酮与吡咯衍生物的氧化偶联产物.该方法底物的官能团适用范围广, 反应 高效绿色, 可快速构建基于喹喔啉酮-吡咯衍生物的药物分子库. 相同测试条件下的 Stern

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Photoinitiated Deaminative Alkylation of Quinoxalin‐2(1H)‐ones via Electron Catalysis

Advanced Synthesis & Catalysis, Год журнала: 2023, Номер 365(6), С. 865 - 870

Опубликована: Фев. 28, 2023

A visible-light initiated deaminative C3 alkylation of quinoxalin-2(1H)-ones with Katritzky salts is reported. This radical process provides an approach to a range alkylated quinoxalin-2(1H)-one derivatives in 40–96% yields under metal- and external photocatalyst-free conditions. The reaction enabled by the deprotonation acidic aminyl intermediates generate corresponding anions, which act as single electron transfer reducing reagents sustain chain. late-stage functionalization drug-based amines further demonstrates value this approach. As service our authors readers, journal supporting information supplied authors. Such materials are peer reviewed may be re-organized for online delivery, but not copy-edited or typeset. Technical support issues arising from (other than missing files) should addressed Please note: publisher responsible content functionality any Any queries content) directed author article.

Язык: Английский

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Research Progress of Visible Light Promoted C—N Bond Fracture to Construct C—C Bond

Chinese Journal of Organic Chemistry, Год журнала: 2023, Номер 43(8), С. 2591 - 2591

Опубликована: Янв. 1, 2023

In recent years, the photochemical organic transformation promoted by visible light has aroused interest of chemists.Compared with traditional methods, photoredox catalysis using as renewable energy been proved to be a mild and powerful tool, which can promote activation molecules single electron transfer (SET) process.There are lot amino functional groups in structures many natural products, also important structural units some drug materials.Therefore, activating C-N bond these substances carrying out coupling reactions C-C formation, structure compounds effectively modified, so obtain various functionalization.Therefore, this study become an research field synthesis.The results breaking its application formation reaction years reviewed, representative examples mechanisms discussed.

Язык: Английский

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Visible-Light-Induced Photocatalytic Deoxygenative Benzylation of Quinoxalin-2-(1H)-ones with Carboxylic Acid Anhydrides

Organic Letters, Год журнала: 2024, Номер 26(32), С. 6841 - 6846

Опубликована: Авг. 7, 2024

A visible-light-induced photocatalytic deoxygenative benzylation of quinoxalin-2-(1H)-ones is herein described. This novel approach provides a mild, simple, and practical route to 3-benzylquinoxalin-2(1H)-ones from ubiquitous safe carboxylic acid anhydrides. wide range substrates with different substituents were well-tolerated efficiently transformed various functionalized great potential for valuable applications in drug discovery. Mechanistic investigations suggest H2O as proton source, while hydroxyl-containing quinoxalin-2(1H)-ones may be key intermediates the process.

Язык: Английский

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TfOH-catalyzed three-component synthesis of Dithiocarbamates from α-Diazoesters under continuous flow conditions

Journal of Flow Chemistry, Год журнала: 2022, Номер 13(1), С. 1 - 8

Опубликована: Дек. 12, 2022

Язык: Английский

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Regioselective Radical Cascade Cyclizations of Alkyne-Tethered Cyclohexadienones with Chalcogenides under Visible-Light Catalysis

ACS Omega, Год журнала: 2023, Номер 8(39), С. 35809 - 35821

Опубликована: Сен. 20, 2023

Herein, we demonstrated a silver/K2S2O8-mediated highly regio- and diastereoselective 6/5-exo trig radical cascade cyclization of alkyne-tethered cyclohexadienones with sulfonyl hydrazides or sodium sulfinates subsequent selenation to access 6,6-dihydrochromenone 6,5-fused tetrahydro benzofuranone derivatives. This reaction protocol features high functional group compatibility has wide substrate scope providing variety dihydrochromenones derivatives in good excellent yields. The proceeds via the attack alkyne over activated Michael acceptor. TEMPO quenching experiment implies presence intermediate. Further synthetic versatility 6,6- 5,6-fused is also showcased.

Язык: Английский

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Light Induced Diastereoselective Ketoesterification To Access 6,5-Fused Tetrahydrobenzofuranones in Batch and Continuous Flow Conditions

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(17), С. 12628 - 12638

Опубликована: Авг. 15, 2024

Ketoesterification stands as a pivotal technique in organic synthesis, particularly due to its essential role the construction of numerous natural products and bioactive compounds. In this study, we have successfully accomplished visible-light-induced cyclization diastereoselective direct ketoesterification cyclohexadienones, facilitating access cis 6,5-fused tetrahydrobenzofuranone derivatives. The utilization TEMPO radical quenching experiments has provided insights, suggesting an ionic mechanism underlying methodology. Additionally, regioselective addition 2-oxo-2-phenylacetate least hindered side cis-selective fashion makes protocol more appealing toward product development. Incorporation continuous flow reaction into batch notably bolstered efficiency rate. Furthermore, demonstration gram-scale reactions setup synthetic utility with NaOH underscore scalability practical applicability approach.

Язык: Английский

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Visible‐Light‐Induced Diastereoselective Cascade Cyclization to Construct Polycyclic Spiroindolines

Advanced Synthesis & Catalysis, Год журнала: 2024, Номер 366(15), С. 3303 - 3309

Опубликована: Июнь 15, 2024

Abstract We herein reported, a visible‐light‐induced K 2 S O 8 mediated cascade reaction of 3‐(2‐isocyanoethyl)indoles with α ‐oxocarboxylic acids leading to diastereoselective synthesis polycyclic spiroindolines bearing an N ‐formyl unit derivative utilising the alkali metal salt as mediator under mild conditions. This study offers illustration and 3‐(2‐isocyanoethyl)indoles‐based reactions it shows involvement glyoxolate ions without decarboxylation access analogue. The batch process can be extended continuous flow system using glass tube loaded placed between PFA capillary reactor, which greatly advance efficiency even promoted gram‐scale synthesis.

Язык: Английский

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