Dual Photoredox/Copper-Catalyzed Three-Component Alkylcyanation of Alkenes and 1,4-Alkylcyanation of 1,3-Enynes Employing Sulfoxonium Ylides as the Carbon Radical Precursors DOI
Zixuan Yang,

Xue-Cen Xu,

Bowen He

et al.

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

Published: Dec. 3, 2024

A novel dual photoredox/copper-catalyzed three-component alkylcyanation of alkenes and 1,4-alkylcyanation 1,3-enynes have been developed. In this radical cyanoalkylation reaction, the photoredox induced alkyl from sulfoxonium ylides adds to carbon-carbon double bonds styrenes or 1,3-enynes, generated benzylic allenyl radicals couple with a Cu(II) cyanide complex achieve selective cyanation. The reaction exhibits high chemo- regioselectivity wide substrate scope, providing an efficient method for synthesis nitriles in single step.

Language: Английский

Photocatalytic Thio/Selenosulfonylation–Bicyclization of Indole-Tethered 1,6-Enynes Leading to Substituted Benzo[c]pyrrolo[1,2,3-lm]carbazoles DOI
Hang‐Dong Zuo, Xi Chen, Yue Zhang

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(18), P. 3828 - 3833

Published: April 29, 2024

The photocatalyzed radical-triggered thio/selenosulfonylation–bicyclization of indole-tethered 1,6-enynes has been established for the first time, enabling synthesis various previously unreported thio/selenosulfonylated benzo[c]pyrrolo[1,2,3-lm]carbazoles with moderate to good yields under mild conditions. reaction pathway was proposed, consisting energy transfer, homolytic cleavage, radical addition, 5-exo-dig, coupling, and a Mallory cascade. This approach exhibits wide substrate compatibility excellent tolerability toward functional groups is characterized by its remarkable efficiency in both bond formation annulation.

Language: Английский

Citations

11
The Case for Poly(ylides) as a Class of Charge-Neutral, Hydrophilic Polymers with Applications in Biomaterials Science DOI Creative Commons
Kevin Neumann

Biomaterials Science, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

Many applications of biomaterials require hydrophilic polymers as building blocks, including hydrogels and nanomedicinal devices. Besides enabling sufficient swelling properties in aqueous environments, provide hydration layers, which are considered a major requirement when designing non-fouling surfaces materials. For the last few decades, polyethylene glycol has been seen gold standard for such applications. However, reports on its stability immunogenicity have urged chemists to identify alternatives with comparable or superior properties. In addition biopolymers, zwitterionic gained increasing attention by effectively offering an overall charge-neutral scaffold capable forming strong layers. Driven enhanced understanding structure-property relationship materials, poly(ylides) emerged new class polymers. By having negative charge adjacent positive charge, ylides offer not only minimal dipole moment but also maintain their nature. Despite some early synthesis during 1980s, polymeric were largely overlooked polymers, utility unique blocks design tools remained elusive. recent years, several groups reported

Language: Английский

Citations

5
Deoxygenative Cyclopropanation of Aldehydes with Acyl‐Stabilized Sulfur Ylides DOI Open Access

Xinzhen Ling,

Quansheng Zhao, Xinyu Liu

et al.

Chemistry - A European Journal, Journal Year: 2025, Volume and Issue: unknown

Published: March 5, 2025

Herein, we described a novel [1+1+1] deoxygenative cyclopropanation between sulfur ylides and aldehydes, which is distinctive from traditional epoxidation reactions. The method offers straightforward approach for the synthesis of highly stereoselective, functionalized, structurally diverse tertiary cyclopropyl thioethers. reaction demonstrates broad substrate scope excellent compatibility with various functional groups, rendering it particularly suitable late-stage modifications pharmaceuticals natural products, as well compounds. Additionally, β,β-disubstituted enals can also engage in reaction, instead undergoing classic through Michael addition reaction-induced cyclization ylides, thus yielding synthetically important vinylcyclopropanes chemoselectivity diastereoselectivity.

Language: Английский

Citations

0
Remote Catalytic C(sp3)–H Alkylation via Relayed Carbenoid Transfer upon Olefin Chain Walking DOI
Qing Wang, Jeonguk Kweon, Dongwook Kim

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(45), P. 31114 - 31123

Published: Oct. 30, 2024

Transition metal carbenes have emerged as versatile intermediates for various types of alkylations. While reactions carbene species with alkenes been extensively studied, most examples focus on cyclopropanation and allylic C-H insertion. Herein, we present the first example a catalytic strategy carbene-involved regioselective remote alkylation internal olefins by synergistically combining two iridium-mediated reactivities olefin chain walking carbenoid migratory The method, utilizing sulfoxonium ylides bench-stable robust precursor, was found to be effective series tethered alkyl chains, heteroatom substituents, complex biorelevant moieties. Combined experimental computational studies revealed that reversible iridium hydride-mediated proceeds lead terminal alkyl-Ir intermediate, which then forms final insertion, resulting in terminal-alkylated products.

Language: Английский

Citations

3
Effective Role of Two Layers of Silica in the Performance of Fe3O4@xSiO2@ySiO2@BisPyP-Ni Core-Shell Catalyst for C-C and C-S Coupling Reactions DOI
Ebraheem Abdu Musad Saleh, Asmaa F. Kassem, Farag M. A. Altalbawy

et al.

Silicon, Journal Year: 2024, Volume and Issue: 16(9), P. 3795 - 3809

Published: April 2, 2024

Language: Английский

Citations

2
Homologation of Alkenyl Carbonyls via a Cyclopropanation/Light‐Mediated Selective C‐C Cleavage Strategy DOI Creative Commons
Tin V. T. Nguyen, Duncan K. Brownsey, André Bossonnet

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 31, 2024

We report herein our studies on the direct photoactivation of carbonyl cyclopropanes to give biradical intermediates, leading selective cleavage more substituted carbon-carbon bond. Depending substrate structure, extended alkenes were isolated or directly reacted in a photo-Nazarov process bicyclic products. Based these results, unified reductive ring-opening reaction was developed by using diphenyl disulfide as hydrogen atom transfer (HAT) reagent. By performing sequential cyclopropanation/selective ring opening reaction, we achieved CH

Language: Английский

Citations

1
Solvent-involved synthesis of pyrrolidin-5-one-2-carboxamides via a sequential Ugi/olefination reaction DOI
Na Chen,

Tianyu Long,

Han‐Han Kong

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(10), P. 2780 - 2785

Published: Jan. 1, 2024

An unprecedented multi-component reaction with solvent participation and a novel conversion of sulfur ylides was developed via Ugi/olefination to construct pyrrolidin-5-one-2-carboxamides.

Language: Английский

Citations

0
Pd‐Catalyzed [3+6+3+6] Macrocyclizations of Aryl α‐Diazo‐β‐Ketoesters DOI Creative Commons

Zhong Zhuang,

Adiran de Aguirre, Céline Besnard

et al.

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(13), P. 3029 - 3035

Published: May 7, 2024

Abstract Thanks to Pd(II)‐catalysis, an efficient synthesis of unsaturated macrocycles is achieved by [3+6+3+6] condensation cyclic ethers with aryl α‐diazo‐β‐ketoesters. The presence the electron‐rich ester moieties forbids use dirhodium complexes as these diazo decomposition catalysts provoke unforeseen intermolecular C sp 2 −H insertion reactions that derail targeted reactivity. However, Pd(acac) , using high concentration conditions (1 M), a variety 18‐membered (16 examples) afforded both and alkyl reagents. Catalyst selection for either electrophilic aromatic substitution (Rh) or ylide (Pd) pathways are explained computational approaches.

Language: Английский

Citations

0
Reactions with sulfoxonium ylides using metal-catalysis DOI
Marcio Hayashi, Viktor Saraiva Câmara,

Cristhian S. Oliveira

et al.

Advances in organometallic chemistry, Journal Year: 2024, Volume and Issue: unknown, P. 227 - 286

Published: Jan. 1, 2024

Language: Английский

Citations

0
Homologation of Alkenyl Carbonyls via a Cyclopropanation/Light‐Mediated Selective C‐C Cleavage Strategy DOI
Tin V. T. Nguyen, Duncan K. Brownsey, André Bossonnet

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 31, 2024

Abstract We report herein our studies on the direct photoactivation of carbonyl cyclopropanes to give biradical intermediates, leading selective cleavage more substituted carbon‐carbon bond. Depending substrate structure, extended alkenes were isolated or directly reacted in a photo‐Nazarov process bicyclic products. Based these results, unified reductive ring‐opening reaction was developed by using diphenyl disulfide as hydrogen atom transfer (HAT) reagent. By performing sequential cyclopropanation/selective ring opening reaction, we achieved CH 2 insertion into α,β bond both acyclic and cyclic unsaturated compounds. Our protocol provides further tool for modification carbon framework organic compounds, complementing recent progress “skeletal editing”.

Language: Английский

Citations

0