Visible-light-driven reductive dearomatization of<i>N</i>-arylformyl indoles in EDA complexes with a thiophenol<i>via</i>a HAT pathway

Yiping, Cai; Ma, Meng-Yue; Xu, Xinyu; Song, Qin‐Hua

doi:10.1039/d2qo02024f

Cited by 4 publications

(2 citation statements)

References 63 publications

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“…The resulting dearomatized radicals are then reduced to give the corresponding anions, followed by a rapid protonation to deliver the hydrofunctionalized indoline derivatives (Fig. 1d , top) 48 – 56 . Inspired by our continuing interest in sigmatropic rearrangements 57 – 60 , we envisage whether the incorporation of photoredox-enabled nucleophilic radical dearomatization of indoles and [3,3]-rearrangement (Ireland–Claisen type) 61 – 63 could be developed to prepare the prenylated and reverse-prenylated indolines (Fig.…”

Section: Introductionmentioning

confidence: 99%

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

et al. 2023

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

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Section: Introductionmentioning

confidence: 99%

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

et al. 2023

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“…In this case, the photocatalyst-free and milder visible light-induced generation of reactive intermediates (radical anions and cations) using electron–donor–acceptor (EDA) complexes provides a good opportunity to avoid dependence on photocatalysts, and offers an appealing strategy for the design of new reactions. 4,5…”

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confidence: 99%

A general electron donor–acceptor complex enabled cascade cyclization of alkynes to access sulfur-containing heterocycles

et al. 2023

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Decatungstate‐Photocatalyzed Diastereoselective Dearomative Hydroalkylation of Indoles

Montinho‐Inacio,

Bouchet,

et al. 2024

Eur J Org Chem

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

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Visible-light-driven reductive dearomatization ofN-arylformyl indoles in EDA complexes with a thiophenolviaa HAT pathway

Abstract: The dearomatization of N-(o-haloarylformyl)indoles has been achieved by photochemical methods with a photocatalyst or direct excitation via stepwise reduction/protonation. Herein, we report a visible light-driven dearomatization of an N-(o-haloarylformyl)indole in...

Cited by 4 publications

References 63 publications

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

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

A general electron donor–acceptor complex enabled cascade cyclization of alkynes to access sulfur-containing heterocycles

Decatungstate‐Photocatalyzed Diastereoselective Dearomative Hydroalkylation of Indoles

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