Photocatalytic Cyclization Cascades by Radical Relay toward Pyrrolo[1,2-a]indoles: Synthesis, Mechanism, and Application

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(5), P. 3509 - 3524

Published: Feb. 16, 2024

A photocatalytic annulation cascade of unactivated N-alkene-linked indoles with Langlois' reagent by a radical relay is developed at room temperature under blue LED irradiation. The reaction afforded series tri/difluoromethylated pyrrolo[1,2-a]indoles in moderate to good yields. DFT study suggests that the ascribed rhodamine 6G-induced cyclization involving vinyl addition-radical and hydrogen-atom-abstraction (HAA) processes, interestingly, are applied as fluorescent dyes into fluorescence spectrum live-cell imaging. This paper represents an initial example on cascades HAA process.

Language: Английский

---

Copper-Catalyzed Fluoroalkylphosphorothiolation of Alkynes for the Synthesis of (E)-β-Fluoroalkyl Vinyl Phosphorothioates

Organic Letters, Journal Year: 2023, Volume and Issue: 25(46), P. 8296 - 8301

Published: Nov. 10, 2023

A convenient copper-catalyzed three-component radical-based fluoroalkylphosphorothiolation of terminal alkynes with (iPrO)2P(O)SH and fluoroalkylation reagent for the synthesis a variety (E)-β-fluoroalkyl vinyl phosphorothioates excellent regioselectivity stereoselectivity has been developed. All starting materials used in this reaction are highly stable readily available. Thus, process features mild conditions, simple operation good functional group tolerance (>40 examples). Furthermore, modular system allows late-stage functionalization bioactive molecules.

Language: Английский

---

Ni-Catalyzed Reductive Fluoroalkylthiolation of Alkynes toward Fluoroalkylated Vinylthioethers

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

Published: Jan. 1, 2025

A Ni-catalyzed protocol for the regioselective and stereoselective three-component fluoroalkylthiolation of alkynes with fluoroalkyl halides thiosulfonates is presented. This reductive difunctionalization provides an efficient strategy rapid construction fluoroalkyl-incorporated vinylthioethers under mild conditions in moderate to good yields.

Language: Английский

---

Visible-light-promoted trifluoromethylation/arylation of unactivated alkenes with Togni-CF3 for the synthesis of trifluoromethylated pyrrolo[1,2–a]indoles

Tetrahedron Letters, Journal Year: 2025, Volume and Issue: unknown, P. 155468 - 155468

Published: Jan. 1, 2025

Language: Английский

---

Nickel-Catalyzed Three-Component Carboamination/Cyclization of Alkynes To Access 2,3-Disubstituted Quinolines

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

Published: Jan. 23, 2025

Presented herein is a nickel-catalyzed chemo- and regioselective three-component tandem carboamination cyclization of terminal alkynes with organoboronic acids anthranils for facile modular access to 2,3-substituted quinolines. In this process, anthranil has dual roles: serving as an electrophilic aminating reagent redox buffer suppress the generation off-cycle Ni(0) complex. Moreover, anionic acetylacetonate (acac) ligand was found be vital ensure productive Ni(I)-Ni(III)-Ni(I) catalytic cycle.

Language: Английский

---

Three‐Component 1,2‐Methylamidation of Alkynes via Coordinating Activation Strategy

ChemistryOpen, Journal Year: 2025, Volume and Issue: unknown

Published: April 17, 2025

The selective functionalization of carbon–carbon triple bonds with methyl groups remains a challenging task. Herein, the successful development novel copper‐catalyzed three‐component 1,2‐methylamidation bond is reported. readily available coupling partners, picolinamides and alkynes dicumyl peroxide, serve as both source oxidant in this difunctional strategy to access methylated enamides; substrate scope broad, demonstrating good functional group compatibility. synthetic utility reaction also demonstrated through via late‐stage substrates bearing biologically relevant molecules.

Language: Английский

---

Visible-Light-Induced Stereoselective Radical trans-Iodoalkylation of Terminal Alkyne with Iodoform

Organic Letters, Journal Year: 2024, Volume and Issue: 26(39), P. 8400 - 8404

Published: Sept. 25, 2024

We describe herein a novel stereoselective

Language: Английский

---

Visible-light-driven graphitic carbon nitride-catalyzed ATRA of alkynes: highly regio- and stereoselective synthesis of (E)-β-functionalized vinylsulfones

Green Chemistry, Journal Year: 2023, Volume and Issue: 26(1), P. 323 - 329

Published: Oct. 17, 2023

A visible-light-driven g-C 3 N 4 -catalyzed atom transfer radical addition (ATRA) of alkynes to synthesize valuable ( E )-β-thio/seleno vinylsulfones is accomplished. can be recovered and reused in five runs without loss catalytic activity.

Language: Английский

---

Visible Light-Induced Copper-Catalyzed Regio- and Stereoselective Difluoroalkylthiocyanation of Alkynes

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(12), P. 9118 - 9124

Published: June 6, 2024

The first regio- and stereoselective difluoroalkylthiocyanation of alkynes with BrCF

Language: Английский

---

Coordinating activation strategy enables 1,2-alkylamidation of alkynes

Chemical Science, Journal Year: 2023, Volume and Issue: 14(41), P. 11466 - 11473

Published: Jan. 1, 2023

The radical 1,2-difunctionalization reaction of alkynes has been evolved into a versatile approach for expeditiously increasing the complexity common feedstock alkyne. However, intermolecular 1,2-carboamidation with general alkyl groups is an unsolved problem. Herein, we show that coordinating activation strategy could act as efficient tool enabling 1,2-alkylamidation alkynes. With employment diacyl peroxides both alkylating reagents and internal oxidants, large library β-alkylated enamides constructed in three-component manner from readily accessible amides This protocol exhibits broad substrate scope good functional group compatibility amenable late-stage functionalization natural molecules biologically compounds.

Language: Английский

---