Copper-Catalyzed Cyclization and Alkene Transposition Cascade Enables a Modular Synthesis of Complex Spirocyclic Ethers DOI Creative Commons

Wan‐Xu Wei,

Yangjin Kuang,

Martin Tomanik

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 20, 2024

Complexity-generating reactions that access three-dimensional products from simple starting materials offer substantial value for drug discovery. While oxygen-containing heterocycles frequently feature unique, nonaromatic architectures such as spirocyclic rings, exploration of these chemical spaces is limited by conventional synthetic approaches. Herein, we report a copper-catalyzed annulation and alkene transposition cascade reaction enables modular preparation complex, ethers readily available alkenol substrates via transannular 1,5-hydrogen atom transfer-mediated C–H functionalization. Our transformation displays broad substrate scope, shows excellent heteroatom compatibility, constructs spirocycles varying ring sizes. The wider utility this method highlighted numerous product diversifications short synthesis the all-carbon framework spirotenuipesine A. We anticipate can significantly streamline to privileged class will find application in natural synthesis.

Language: Английский

An electrocatalytic mono-functionalization of alkenes towards alkenyl selenium sulfonates DOI

Zhiheng Zhao,

Hongyan Yan,

Lijun Gu

et al.

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

Published: Jan. 1, 2025

In this study, a straightforward and environmentally benign electrochemical mono-functionalization of alkenes has been established for the synthesis alkenyl selenium sulfonates using elemental as source.

Language: Английский

Citations

1
Electroreductive Cross-Coupling Reactions: Carboxylation, Deuteration, and Alkylation DOI
Pengfei Li, Yanwei Wang, Hanying Zhao

et al.

Accounts of Chemical Research, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 13, 2024

ConspectusElectrochemistry has been used as a tool to drive chemical reactions for more than two centuries. With the help of an electrode and power source, chemists are provided with system whose potential can be precisely dialed in. The theoretically infinite redox range renders electrochemistry capable oxidizing or reducing some most tenacious compounds. Indeed, electroreduction offers alternative generating highly active intermediates from electrophiles (e.g., halides, alkenes, etc.) in organic synthesis, which untouchable traditional reduction methods. Meanwhile, reductive coupling extensively utilized both industrial academic settings due their ability swiftly, accurately, effectively construct C–C C–X bonds, present innovative approaches synthesizing complex molecules. Nonetheless, its application is constrained by several inherent limitations: (a) requirement stoichiometric quantities agents, (b) scarce activation strategies inert substrates high potentials, (c) incomplete mechanistic elucidation, (d) challenges isolation intermediates. merging represents attractive approach address above limitations synthesis seen increasing use synthetic community over past few years.Since 2020, our group dedicated developing electroreductive cross-coupling using readily available small molecules, such arenes, CO2, D2O, value-added products. Electroreductive chemistry versatile powerful capacity precise selectivity control, allowed us develop three electrochemical modes lab: (1) An economically advantageous direct (EDR) strategy that emphasizes efficiency, achieves atom utilization, minimizes unnecessary atomic waste. (2) A class organo-mediated (EOMR) methods controlling reaction pathways. This allows modulation processes enhance efficiency selectivity. (3) metal-catalyzed (EMCR) method enables selective functionalization specific bonds functional groups under mild conditions, thereby occurrence side reactions. We commenced studies establishing organic-mediator-promoted carboxylation aryl alkyl halides. was then employed arylcarboxylation simple styrenes halides manner. electrolysis arenes epoxides CO2 carboxyl source achieved. Moreover, through adjustment we successfully accomplished deuteration olefins, unactivated enabling efficient formation D-labeled Finally, building on previous understanding developed series alkylation enable C(sp3)–C(sp3)

Language: Английский

Citations

4
Electrochemical N–H Methylsulfoxidation of Sulfoximines with DMSO DOI Open Access

Qing‐Ru Zhu,

Gen Liu, Yongxiang Wang

et al.

Chinese Journal of Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 16, 2025

Comprehensive Summary The N–H methylsulfoxidation of sulfoximines using DMSO as a methylsulfinyl source, induced by electrochemistry, has been developed. This method is the first example an electrochemical reaction in which serves source. Unlike previous reactions involving substrate, exclusively proceed via radical mechanisms, this follows S‐cation pathway. A wide range N ‐methylsulfinyl were successfully obtained.

Language: Английский

Citations

0
Methane Bubbled Through Seawater Can be Converted to Methanol With High Efficiency DOI Creative Commons
Xiaowei Song, Chanbasha Basheer, Jinheng Xu

et al.

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

Published: Jan. 21, 2025

Partial oxidation of methane (POM) is achieved by forming air-methane microbubbles in saltwater to which an alternating electric field applied using a copper oxide foam electrode. The solubility increased putting it contact with water containing dissolved KCl or NaCl (3%). Being fully dispersed as (20-40 µm diameter), reacts more hydroxyl radicals (OH·) at the gas-water interface. voltage (100 mV) generates two synergistic POM processes dominated Cl- → Cl· + e- and O2 -• under positive negative potentials, respectively. By tuning frequency amplitude, extent path process can be precisely controlled so that than 90% methanol selectively formed compared byproducts, dichloromethane, acetic acid. conversion yield estimated 57% rate approximately 887 µM h-1. This method appears have potential for removing from air seawater converting higher-concentration sources into value-added methanol.

Language: Английский

Citations

0
Electrochemical Denitrative Cyclization Driven by Alternating Polarity DOI
Shu Zhu, Yichao Lin,

Guo-Cai Yuan

et al.

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

Published: Jan. 29, 2025

Alternating current electrolysis has emerged as a promising technique for addressing challenging redox reactions that are otherwise difficult or impossible direct electrolysis. Under mild and transition-metal-free reaction conditions, general electrochemical denitrative cyclization of nitroarenes was developed to access various cyclic sulfone-containing derivatives biological significance. The key success lies in the facile manipulation multiple events upon rapid alternating polarity switching enhance selectivity efficiency.

Language: Английский

Citations

0
A review of redox-active polymers for selective electrochemical removal of uncharged organic pollutants from water DOI
Zhen Qiu, Guo‐Liang Shen,

Wenxin Yan

et al.

Journal of environmental chemical engineering, Journal Year: 2025, Volume and Issue: unknown, P. 115774 - 115774

Published: Feb. 1, 2025

Language: Английский

Citations

0
Stirring Effects on AC-Induced Chemoselectivity in Reversible Electrochemical Reactions DOI

Yong Rui Poh,

Joel Yuen-Zhou

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

Published: Feb. 11, 2025

Language: Английский

Citations

0
Multiple active site metal-based catalysts for C-N coupling reactions and the beyond DOI

Mingzheng Shao,

Yangbo Ma, Yuecheng Xiong

et al.

Next Materials, Journal Year: 2025, Volume and Issue: 8, P. 100555 - 100555

Published: Feb. 21, 2025

Language: Английский

Citations

0
Pulsed Electrochemical Degradation of Micropollutants via In Situ Generated Sulfate Radical: Rapid Reaction Kinetics and Low Energy Requirement DOI
Zijun Zhou, Wentian Zheng,

Mengjiao Xie

et al.

ACS ES&T Engineering, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 24, 2025

Language: Английский

Citations

0
Enantioselective Multicomponent Electrochemical Difunctionalization of Terminal Alkynes DOI

Qiannan Wang,

Xinyu Wang, Yong Liu

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 25, 2025

The direct functionalization of alkyne triple bonds using a radical strategy provides an efficient platform for creating wide range substituted alkenes. However, developing multicomponent enantioselective reaction feedstock alkynes to forge all-carbon quaternary stereocenters─while addressing challenges related compatibility, selectivity, and efficiency─remains relatively rare. Here we report electrochemical nickel-catalyzed three-component cross-coupling readily available terminal alkynes, diverse racemic alkyl precursors, group transfer reagents (such as (TMS)3Si-H, RSe-SeR, RTe-TeR, CHI3), achieving excellent regio-, stereo-, enantioselectivities (more than 70 examples, up 95% ee). Electricity-mediated difunctionalizations significantly expand the scope both aliphatic aromatic demonstrating functional compatibility. key success lies in rational design anodically generated nickel-bound tertiary intermediates, which stereoselectively capture form vinyl radicals participate subsequently processes enable intermolecular anti-stereoselective difunctionalization alkynes. This approach allows transformation into structural entities with α-quaternary stereogenic centers.

Language: Английский

Citations

0