E‐Selective Radical Difunctionalization of Unactivated Alkynes: Preparation of Functionalized Allyl Alcohols from Aliphatic Alkynes

Advanced Science, Journal Year: 2024, Volume and Issue: 11(16)

Published: Feb. 13, 2024

Abstract Radical difunctionalization of aliphatic alkynes provides direct access to valuable multi‐substituted alkenes, but achieving a high level chemo‐ and stereo‐control remains formidable challenge. Herein novel photoredox neutral alkyne di‐functionalization is reported through functional group migration followed by radical‐polar crossover energy transfer‐enabled stereoconvergent isomerization alkenes. In this sequence, hydroxyalkyl an aryl are incorporated concomitantly into alkyne, leading diversely functionalized E‐allyl alcohols. The scope noteworthy, the reaction tolerates containing hydrogen donating C─H bonds that prone intramolecular atom transfer. protocol features broad compatibility, product diversity, exclusive stereoselectivity, thus providing practical strategy for elusive radical unactivated alkynes.

Language: Английский

---

Photoredox catalytic alkylarylation of alkynes with arylsulfonylacetate as bifunctional reagent

Science China Chemistry, Journal Year: 2024, Volume and Issue: 67(6), P. 2022 - 2028

Published: March 7, 2024

Language: Английский

---

Light-Induced, Cs₂CO₃ Promoted C–S Cleavage of Heteroaryl Sulfones for Benzyl Heteroarylation of [1.1.1]Propellane

Organic Letters, Journal Year: 2024, Volume and Issue: 26(29), P. 6230 - 6235

Published: July 16, 2024

In this study, we developed a light-induced difunctionalization of [1.1.1]propellane with heteroaryl sulfones acting as difunctional reagents, allowing the introduction alkyl and units across bicyclo[1.1.1]pentane frameworks. It features broad substrate scope can be used to functionalize structurally complex natural products. Mechanistic investigations indicate Cs

Language: Английский

---

1,3-Difunctionalization of [1.1.1]propellane through iron-hydride catalyzed hydropyridylation

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: July 16, 2024

Current methodologies for the functionalization of [1.1.1]propellane primarily focus on achieving 1, 3-difunctionalized bicyclo[1.1.1]pentane or ring-opened cyclobutane moiety. Herein, we report an innovative approach 3-difunctionalization [1.1.1]propellane, enabling access to a diverse range highly functionalized cyclobutanes via nucleophilic attack followed by ring opening and iron-hydride hydrogen atom transfer. To enable this method, developed efficient iron-catalyzed hydropyridylation various alkenes C - H alkylation pyridines at C4 position, eliminating need stoichiometric quantities oxidants reductants. Mechanistic investigations reveal that resulting N-centered radical serves as effective oxidizing agent, facilitating single-electron transfer oxidation reduced iron catalyst. This process efficiently sustains catalytic cycle, offering significant advantages substrates with oxidatively sensitive functionalities are generally incompatible alternative approaches. The strategy presented herein is not only mechanistically compelling but also demonstrates broad versatility, highlighting its potential late-stage functionalization.

Language: Английский

---

Energy Transfer (EnT)-Mediated Stereoselective Aryl-Heterofunctionalization of Unactivated Alkynes via Radical Rearrangement

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 5, 2025

In this study, we present a novel catalyst-free energy transfer mediated radical rearrangement strategy for the aryl-heterofunctionalization of unactivated alkynes, leading to synthesis polyfunctional olefins with exceptional stereoselectivity. This innovative approach, driven by visible light, exemplifies green chemistry principles eliminating reliance on transition metals, external oxidants, and photocatalysts. The broad applicability our method is demonstrated through successful diverse array compounds, including vinyl sulfones, selenides, sulfides. Preliminary mechanistic insights suggest an mechanism, highlighting efficiency selectivity strategy.

Language: Английский

---

Photoinduced Carbamoylarylation of Alkynes with N-Aryl Oxamic Acids

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

Published: April 2, 2025

1,2-Difunctionalization of alkynes is an attractive synthetic protocol, because it can achieve a high step economy and provide various complex organic molecules. This study demonstrates the visible-light-induced carbamoylarylation terminal using N-aryl oxamic acids as bifunctional reagents. The transformation involves addition carbamoyl radicals to alkenes, resulting in 1,4-aryl migration via C(aryl)-N bond cleavage afford corresponding arylacrylamides moderate good yields.

Language: Английский

---

Organic Peroxides in Transition-Metal-Free Cyclization and Coupling Reactions (C–C) via Oxidative Transformation

ACS Omega, Journal Year: 2025, Volume and Issue: unknown

Published: April 14, 2025

Transition-metal-free transformations are recognized as green and sustainable methods for constructing carbon-carbon bonds in organic synthesis. This review describes the application of six peroxides, including tert-butyl hydroperoxide (TBHP), di-tert-butyl peroxide (DTBP), peroxybenzoate (TBPB), benzoyl (BPO), dialauroyl (DLP), diguyl (DCP), C-C bond construction, highlighting selected examples mechanisms challenging transformations. Each section concludes with a detailed overview suitable reagents various coupling reactions strengths weaknesses reported works. work aims to inspire further innovations transition-metal-free oxidative transformations, promoting eco-friendly chemical processes paving way new peroxide-based synthesis methods.

Language: Английский

---

Access to Spirocyclic Vinyl Sulfones via Radical Cyclization and Functional Group Migration

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Spirocyclic vinyl sulfones, which incorporate the three-dimensional structure inherent to spiro compounds and Michael acceptor reactivity associated with hold promise for novel biological activities. The lack of efficient synthetic methods, however, hinders their extensive investigations in drug discovery development. In this work, we describe a practical versatile approach synthesis multi-functionalized spirocyclic sulfones from easily available materials. reaction proceeds efficiently through cascade radical cyclization followed by (hetero)aryl migration. protocol features mild photocatalytic conditions provides access diverse range products, enabling construction complex scaffolds, including medium-sized ring-fused sulfones.

Language: Английский

---

Z-selective radical difunctionalization of aromatic alkynes: synthesis of multi-substituted triarylethenes

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(37), P. 4894 - 4897

Published: Jan. 1, 2024

Described herein is a Cu-catalyzed diarylation of aromatic alkynes via radical docking-migration pathways, leading to broad range valuable triarylethenes.

Language: Английский

---

Regio- and Stereoselective β-Sulfonylamination of Alkynes via Photosensitized Bifunctional N–S Bond Homolysis

Organic Letters, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 4, 2024

Nitrogen central radicals (NCRs) are versatile synthetic intermediates for creating functional nitrogen-containing molecules. Herein, a photosensitized β-sulfonylamination of terminal alkynes as well acetylene has been established by employing N-sulfonyl heteroaromatics bifunctional reagents (BFRs) to efficiently deliver (E)-β-sulfonylvinylamines with excellent regio- and stereoselectivities. Mechanistic studies suggest base-accelerated energy transfer (EnT) photocatalysis involving aromatic NCR formation, radical addition alkynes, sulfonylation processes.

Language: Английский

---