Two Photocatalytic Pathways for Reductive Dearomatizations of N‐Arylformylindoles by a Visible‐Light Triplet Organocatalyst DOI

Meng‐Yue Ma,

Cai Yiping, Qin‐Hua Song

и другие.

Advanced Synthesis & Catalysis, Год журнала: 2024, Номер 366(20), С. 4228 - 4237

Опубликована: Авг. 14, 2024

Abstract A visible‐light triplet photocatalyst 5‐acetyl‐2‐mercapto‐benzoic acid methyl ester (AcBSH) was developed through introducing acetyl into benzenethiolate to improve the efficiency of intersystem crossing (ISC) and using o ‐methoxyformyl increase molar extinction coefficient. In photocatalytic system AcBSH, reductive dearomatization N ‐arylformylindoles is achieved afford desired indolines in moderate excellent yields, including both indoles without ( 1 ) with 2‐substituent 2 ). The a steric hindrance for conjugation between benzoyl indole moiety, makes exhibit different reduction potentials E red energy levels ΔE T Thereby, two kinds substrates undergo primarily pathways: i) successive SET/protonation pathway, which merging photosensitization via triplet‐triplet transfer (EnT) photoinduced SET , ii) single electron (SET) from concerted hydrogen atom (HAT) process .

Язык: Английский

Recent Advances in Visible Light Induced Palladium Catalysis DOI
Sumon Sarkar, Kelvin Pak Shing Cheung, Vladimir Gevorgyan

и другие.

Angewandte Chemie International Edition, Год журнала: 2023, Номер 63(9)

Опубликована: Ноя. 14, 2023

Visible light-induced Pd catalysis has emerged as a promising subfield of photocatalysis. The hybrid nature radical species enabled wide array radical-based transformations otherwise challenging or unknown via conventional chemistry. In parallel to the ongoing pursuit alternative, readily available precursors, notable discoveries have demonstrated that photoexcitation can alter not only oxidative addition but also other elementary steps. This Minireview highlights recent progress in this area.

Язык: Английский

Процитировано

50

Photochemical dearomative skeletal modifications of heteroaromatics DOI Creative Commons
Peng Ji, Kuaikuai Duan, Menglong Li

и другие.

Chemical Society Reviews, Год журнала: 2024, Номер 53(12), С. 6600 - 6624

Опубликована: Янв. 1, 2024

Dearomatization has emerged as a powerful tool for rapid construction of 3D molecular architectures from simple, abundant, and planar (hetero)arenes. The field evolved beyond simple dearomatization driven by new synthetic technology development. With the renaissance photocatalysis expansion activation mode, last few years have witnessed impressive developments in innovative photochemical methodologies, enabling skeletal modifications dearomatized structures. They offer truly efficient useful tools facile highly complex structures, which are viable natural product synthesis drug discovery. In this review, we aim to provide mechanistically insightful overview on these innovations based degree alteration, categorized into dearomative functionalization editing, highlight their utilities.

Язык: Английский

Процитировано

14

Decatungstate‐Photocatalyzed Diastereoselective Dearomative Hydroalkylation of Indoles DOI Creative Commons

Emeric Montinho‐Inacio,

Damien Bouchet, Wei‐Yang Ma

и другие.

European Journal of Organic Chemistry, Год журнала: 2024, Номер 27(22)

Опубликована: Апрель 16, 2024

Abstract In this study, we present an efficient and straightforward dearomative hydroalkylation of indoles. By utilizing alkanes or ethers as alkyl radical sources employing TBADT a cost‐effective photocatalyst for direct hydrogen atom transfers (HAT), achieved successful conversion these heterocyclic derivatives into 2‐alkylindolines with good to excellent yields high diastereoselectivity under mild reaction conditions.

Язык: Английский

Процитировано

8

Photoredox-catalyzed diastereoselective dearomative prenylation and reverse-prenylation of electron-deficient indole derivatives DOI Creative Commons

Xuexue Chang,

Fangqing Zhang,

Shibo Zhu

и другие.

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Июнь 30, 2023

Abstract Prenylated and reverse-prenylated indolines are privileged scaffolds in numerous naturally occurring indole alkaloids with a broad spectrum of important biological properties. Development straightforward stereoselective methods to enable the synthesis structurally diverse prenylated indoline derivatives is highly desirable challenging. In this context, most direct approaches achieve goal generally rely on transition-metal-catalyzed dearomative allylic alkylation electron-rich indoles. However, electron-deficient indoles much less explored, probably due their diminished nucleophilicity. Herein, photoredox-catalyzed tandem Giese radical addition/Ireland–Claisen rearrangement disclosed. Diastereoselective prenylation reverse-prenylation proceed smoothly under mild conditions. An array tertiary α-silylamines as precursors readily incorporated 2,3-disubstituted high functional compatibility excellent diastereoselectivity (>20:1 d.r.). The corresponding transformations secondary provide biologically lactam-fused one-pot synthesis. Subsequently, plausible photoredox pathway proposed based control experiments. preliminary bioactivity study reveals potential anticancer property these appealing indolines.

Язык: Английский

Процитировано

17

Visible-Light-Induced Palladium-Catalyzed Construction of Polyarylfuran Skeletons via Cascade Aryl Radical Cyclization and C(sp3)–P(V) Bond Cleavage DOI
Yang Li,

Shen‐Yuan Zhang,

Xiaolong Yan

и другие.

Organic Letters, Год журнала: 2023, Номер 25(25), С. 4720 - 4724

Опубликована: Июнь 20, 2023

Herein, a novel and expedient method was established for the synthesis of polyarylfuran derivatives. The coupling allenylphosphine oxide bromophenol or bromonaphthol enabled by visible light palladium catalysis directly furnishes skeletons, which involves radical tandem cyclization cascade C(sp3)-P(V) bond cleavage. This protocol features easy operation, broad substrate scope, high step economy, affording polyarylfurans in moderate to good yields.

Язык: Английский

Процитировано

11

Visible-light-driven reductive dearomatization of N-arylformyl indoles in EDA complexes with a thiophenol via a HAT pathway DOI
Cai Yiping,

Meng‐Yue Ma,

Xiao Xu

и другие.

Organic Chemistry Frontiers, Год журнала: 2023, Номер 10(7), С. 1633 - 1642

Опубликована: Янв. 1, 2023

A visible light-driven dearomatization of an N -( o -haloarylformyl)indole in electron donor–acceptor (EDA) complex with a thiophenol. The radical reaction is terminated by concerted hydrogen atom transfer (HAT).

Язык: Английский

Процитировано

10

Palladium-Catalyzed Dearomative Heck/C(sp2)–H Activation/Decarboxylative Cyclization of C2-Tethered Indoles DOI
Shuyi Guo,

Wenbo Deng,

Xiaochang Xiao

и другие.

Organic Letters, Год журнала: 2024, Номер 26(43), С. 9389 - 9394

Опубликована: Окт. 21, 2024

Until now, palladium-catalyzed dearomative Heck reactions of indoles were largely limited to β-H elimination and nucleophilic capture the transient alkyl-Pd(II) species. Herein, we disclose a novel Heck/C(sp

Язык: Английский

Процитировано

3

Excited Pd-catalyzed dearomative 1,4-dicarbofunctionalization of nonactivated aromatic rings DOI

Kai Jiang,

Zhao Zhang, Xiaodong Yin

и другие.

Organic Chemistry Frontiers, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

1,4-difunctionalization of nonactivated arenes has been accomplished by the excited-palladium catalysis via radical generation a cyclohexadienyl-Pd( ii ) intermediate.

Язык: Английский

Процитировано

0

Advances in catalysis using Xantphos-like ligands; simplicity goes a long way DOI
Piet W. N. M. van Leeuwen, Israel Cano, Zoraida Freixa

и другие.

Coordination Chemistry Reviews, Год журнала: 2025, Номер 537, С. 216636 - 216636

Опубликована: Апрель 11, 2025

Язык: Английский

Процитировано

0

Visible-Light-Mediated Solvent-Switched Photosensitizer-Free Synthesis of Polyfunctionalized Quinolines and Pyridines DOI
Hirendra Nath Dhara, Amitava Rakshit, Tipu Alam

и другие.

Organic Letters, Год журнала: 2023, Номер 25(3), С. 471 - 476

Опубликована: Янв. 13, 2023

A solvent (2,2,2-trifluoroethanol (TFE) vs ethyl alcohol (EtOH)) switched synthesis of quinolines and pyridines is illustrated from (E)-2-(1,3-diphenylallylidene)malononitriles via a Pd(II)-catalyzed photochemical process. The active catalyst [L2Pd(0)] generated serves as an exogenous photosensitizer. process offers predominantly Z-alkenylated in TFE EtOH, respectively. Furthermore, large-scale few interesting post-synthetic modifications have been demonstrated.

Язык: Английский

Процитировано

8