Visible Light‐induced Functionalization of C−H Bonds: Opening of New Avenues in Organic Synthesis

Asian Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 11(6)

Published: Feb. 14, 2022

Abstract In the last three decades, resurgence and astonishing evolution of visible light‐mediated unreactive C−H bond functionalization has led to a sustainable greener approach for introducing various moieties into imperative organic frameworks without need substrate preactivation. Unlike traditional electrophilic or nucleophilic reactions, free radical mechanism photoredox catalysis opens up new routes achieve unprecedented functionalization. this context, single‐electron transfer energy interactions among exogenous photocatalysts, i. e ., TM photocatalysts dye photosensitizers, etc., in their excited state with targeted substrate, thus generates active species, which encompasses further elusive reaction pathways. This review covers distinct generation methods via trigger cleavage through light irradiation. Herein, we provide an overview progress made five years visible‐light‐induced functionalization, may help chemists envision significant chemical transformations molecular complexity.

Language: Английский

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Photocatalyst-, metal- and additive-free regioselective radical cascade sulfonylation/cyclization of benzimidazole derivatives with sulfonyl chlorides induced by visible light

Organic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 9(14), P. 3669 - 3676

Published: Jan. 1, 2022

An environmentally friendly and practical protocol for the visible-light-triggered regioselective radical cascade sulfonylation/cyclization of unactivated alkenes towards synthesis polycyclic benzimidazoles containing sulfone group has been developed.

Language: Английский

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Perfluoroalkylation Reactions by Electron Donor‐Acceptor Complexes: Recent Advances

ChemPhotoChem, Journal Year: 2024, Volume and Issue: 8(8)

Published: May 3, 2024

Abstract This Perspective analyses the perfluoroalkylation reactions by electron donor‐acceptor (EDA) complexes since 2018, while summarizes, in Tables , vast majority of representative various classes organic compounds EDA and halogen‐bonding interactions. Numerous intriguing reaction methodologies valuable synthetic instances have emerged. We aim to delve into these new examples comprehensively, also contemplating future directions field. Subsequent sections will elaborate on (hetero)aromatic compounds, carbon‐carbon multiple bonds, carbonyl isocyanides, covering their scope mechanistic insights. Perfluoroalkylation complexes. Entry Substrate Complex Reaction conditions Product Ref. 1 [13] 2 [46] 3 R F I (3 equiv.) KOH (1.5 Blue LEDs H O, Ar, 20 h [47] 4 TEEDA CFL (25 W) THF, r.t. F− [48] 5 ICF CO Et (1.3 Na DMSO mL) rt. 427 nm LED, 16 [49] 6 TMG (2.5 23 W CFL, MeCN/Hex f (5 : 1) [42,50] 7 MeCN [51] 8 Umemoto's reagent (2 N ‐methylmorpholine DMF, [52] 9 Cs white light O r.t., [53] 10 4.5 450 laser CaCl MeNO 0 °C [3] 11 t ‐BuONa DMF Green [54] 12 or complex I−R (2.1 TMEDA DBU 24 [55,56] 13 TFE/water (1 (0.2 M) CF SO [84] bonds constrained cyclic Bu NCl, Hg lamp (6 (1.2 CH OH, 1.5 r.t, Ar [39] [57] DIPEA …….. −I Base THF 25 with DIPEA, TEEDA; [48,58,59] Bn NH [60] Base, [61] O/toluene=9 LEDs, 65 °C, [41] K PO CuCl (10 mol%) TMSNCS CN Violet (24 [37] Diphenylacetaldehyde Pyrrolidine (40 DCE mL); (0.8 eq.); White W); [44,62] DIPEA,DMA (trace air) 36–72 [63] n ‐C air, RT [64] DABCO υ (400 Watt) 50 C 2n+1 (1.8 [65–67] DCE, [27] 14 2,4,6‐trimethylpyridine MeCN, 60 Togni's [68] 15 PMDETA [69] [70,71] 17 less than % water mmol) isocyanides hydrazones. [72,73] cis ‐catalyst M (20 2,6‐lutidine (0.7 ‐10 [74] [75] phase transfer catalyst Cl/8F 18 1), [32] ambient NaOH (4.1 R.T. [76] 36 30 [77] I−C [78] [79] Imidazole [80]

Language: Английский

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Recent Progress in C–S Bond Formation via Electron Donor-Acceptor Photoactivation

Organic & Biomolecular Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

This review summarizes recent progress in EDA complex-promoted C–S bond formation using various sulfur-containing substrates under mild conditions via visible light irradiation.

Language: Английский

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Visible Light-Promoted Radical Relay Cyclization/C–C Bond Formation of N-Allylbromodifluoroacetamides with Quinoxalin-2(1H)-ones

The Journal of Organic Chemistry, Journal Year: 2021, Volume and Issue: 86(23), P. 17173 - 17183

Published: Nov. 6, 2021

A visible light-promoted radical relay of N-allylbromodifluoroacetamide with quinoxalin-2(1H)-ones was developed in which 5-exo-trig cyclization and C–C bond formation were involved. This protocol performed under mild conditions to facilely offer a variety hybrid molecules bearing both quinoxalin-2(1H)-one 3,3-difluoro-γ-lactam motifs. These prepared novel skeletons would expand the accessible chemical space for structurally complex heterocycles potential biological activities.

Language: Английский

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Visible‐light‐promoted Radical Cyclization/Arylation Cascade for the Construction of α,α‐Difluoro‐γ‐Lactam‐Fused Quinoxalin‐2(1H)‐Ones

Chinese Journal of Chemistry, Journal Year: 2021, Volume and Issue: 40(6), P. 713 - 718

Published: Dec. 10, 2021

Comprehensive Summary A visible‐light‐induced tandem radical intramolecular cyclization/arylation of quinoxalin‐2(1 H )‐ones with bromodifluoroacetamides is described. This protocol allows efficient access to a variety valuable α,α ‐difluoro‐ γ ‐lactam‐fused in moderate good yields under metal‐free, mild and redox neutral reaction conditions. strategy tolerant various functional groups broad range substrates. The mechanism experiments suggested an involvement 5‐ exo ‐trig cyclization process this transformation.

Language: Английский

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Photocatalytic Cyclization/Defluorination Domino Sequence to Access 3-Fluoro-1,5-dihydro-2H-pyrrol-2-one Scaffold

Organic Letters, Journal Year: 2021, Volume and Issue: 23(12), P. 4754 - 4758

Published: June 1, 2021

We herein report an unprecedented photoinduced cyclization/defluorination domino process of N-allylbromodifluoroacetamide with cyclic secondary amines. Consequently, a wide array valuable 3-fluoro-1,5-dihydro-2H-pyrrol-2-ones were facilely prepared from readily available starting materials under mild conditions. Preliminary mechanistic investigations suggest that radical chain propagation and amine-promoted defluorination pathway are presumably involved in this transformation.

Language: Английский

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Nickel-Catalyzed Cyclization/Carbonylation Reaction of N-Allylbromoacetamides with Arylboronic Acids toward 2-Pyrrolidinones

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 24, 2025

A straightforward and efficient nickel-catalyzed cyclization/carbonylation transformation of N-allylbromoacetamides toward the synthesis 2-pyrrolidinone derivatives has been developed with arylboronic acids as reaction partner. This proceeds through a sequential single-electron-transfer pathway via 5-exo-trig cyclization carbonyl insertion steps, furnishing variety in good yields. Various useful functional groups were well tolerated. Moreover, formic acid is applied CO source here nickel catalyst, which provides supplement for carbonylation chemistry heterocycle synthesis.

Language: Английский

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Stereodivergent synthesis of β-iodoenol carbamates with CO₂viaphotocatalysis

Chemical Science, Journal Year: 2021, Volume and Issue: 12(35), P. 11821 - 11830

Published: Jan. 1, 2021

Photocatalytic conversion of carbon dioxide (CO2) into value-added chemicals is great significance from the viewpoint green chemistry and sustainable development. Here, we report a stereodivergent synthesis β-iodoenol carbamates through photocatalytic three-component coupling ethynylbenziodoxolones, CO2 amines. By choosing appropriate photocatalysts, both Z- E-isomers carbamates, which are difficult to prepare using existing methods, can be obtained stereoselectively. This transformation featured mild conditions, excellent functional group compatibility broad substrate scope. The potential synthetic utility this protocol was demonstrated by late-stage modification bioactive molecules pharmaceuticals as well elaborating products access wide range valuable compounds. More importantly, strategy could provide general practical method for construction trisubstituted alkenes such triarylalkenes, represents fascinating challenge in field organic research. A series mechanism investigations revealed that might proceed charge-transfer complex formed halogen bond.

Language: Английский

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Visible-Light-Promoted Oxidative Annulation of Naphthols and Alkynes: Synthesis of Functionalized Naphthofurans

The Journal of Organic Chemistry, Journal Year: 2021, Volume and Issue: 86(23), P. 16770 - 16784

Published: Nov. 2, 2021

A visible-light-mediated site-selective oxidative annulation of naphthols with alkynes for the synthesis functionalized naphthofurans has been developed. The reaction relies on in situ formation an electron donor acceptor pair between phenylacetylene and thiophenol as light-absorbing system to obviate requirement added photocatalyst. protocol facilitates transformation 1-naphthol 2-naphthol well 1,4-naphthoquinone into a wide variety highly naphthofurans.

Language: Английский

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