Supporting Electrolyte‐Free Electrochemical Oxidative C−H Sulfonylation and Thiocyanation of Fused Pyrimidin‐4‐Ones in an All‐Green Electrolytic System DOI
Sumit Biswas, Subhadeep Ghosh, Indrajit Das

et al.

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 30(6)

Published: Nov. 7, 2023

An electrooxidative C-H functionalization is a widely accepted route to obtain sulfur-containing arenes and heteroarenes. However, this process often involves using non-recyclable supporting electrolytes, (co)solvents like hexafluoroisopropanol, additives acid, or catalysts. The use of additional reagents can increase costs waste, reducing atom efficiency. Moreover, unlike other nitrogen-containing heterocycles, there have only been sporadic reports electrochemical in fused pyrimidin-4-ones, an electrolyte-free has yet be developed. This work demonstrates that such anodic coupling reactions performed all-green electrolytic system without electrolytes HFIP, maintaining high economy. strategy utilizes inexpensive sodium sulfinates ammonium thiocyanate as sulfonylating thiocyanating agents undivided cell at constant current, mixture CH

Language: Английский

Highly Atom‐Economic and Efficient Electrochemical Selenylative Annulation of 2‐Alkynyl Biaryls DOI
Nilanjana Mukherjee, Tanmay Chatterjee

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(13), P. 2255 - 2263

Published: May 31, 2023

Abstract A catalyst‐ and oxidant‐free, highly efficient, scalable, sustainable synthetic method is developed for the selenylative annulation of 2‐alkynyl biaryls or 2‐heteroaryl‐substituted alkynyl benzenes with readily available diselenides under electrochemical conditions to synthesize a wide variety selanyl polycyclic aromatic hydrocarbons heteroaromatics in high excellent yield up 99% at room temperature short time (2‐5 h). The transformation required only electricity as green reagent produces hydrogen gas innocuous byproduct. Notably, chemistry metrics protocol are found excellent. Mechanistic studies revealed radical pathway being initiated by situ generation corresponding selenyl from conditions. Significantly, direct comparison approach that our previously iodine‐catalyzed chemical not but also more energy‐efficient, high‐yielding, sustainable, practical.

Language: Английский

Citations

27
Photoinduced Copper-Catalyzed 1,2-Difunctionalization of 1,3-Dienes with Aryl Diselenides DOI

Shengkun Guo,

Xiaoyu Shen, Xiaoyun Chen

et al.

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(22), P. 15969 - 15974

Published: Oct. 30, 2023

Described herein is a photoinduced copper-catalyzed 1,2-difunctionalization of 1,3-dienes. The selenium atom radical was generated by the visible light irradiation diselenides, triggering addition with 1,3-dienes to form allyl intermediate. Subsequent rapid Z/E isomerization allowed for thermodynamically favorable intermediate formation and enabled copper catalyzed stereoselective functionalization various nucleophiles.

Language: Английский

Citations

11
Electrochemical Regioselective C(sp2)-H Bond Chalcogenation of Pyrazolo[1,5-a]pyrimidines via Radical Cross Coupling at Room Temperature DOI Creative Commons

Abhinay S. Chillal,

Rajesh T. Bhawale,

Siddharth Sharma

et al.

Published: April 9, 2024

In this report, we disclose an electrochemical approach for the C(sp2)-H chalcogenation of pyrazolo[1,5-a]pyrimidines at room temperature via radical cross-coupling reaction. The reaction takes place within undivided cell employing graphite electrodes, with TBABF4 acting as supporting electrolyte. This technique offers a rapid, oxidant-free, and environmentally conscious protocol achieving regioselective specifically C3 position pyrazolo[1,5-a]pyrimidines. Furthermore, procedure uses only 0.5 equivalents diaryl chalcogenides which underscores atom economy protocol. Key attributes methodology include mild conditions, short time, utilization cost-effective electrode materials, reliable achievement yields ranging from good to excellent friendly conditions. Cyclic voltammetry studies quenching experiments suggest pathway mechanism.

Language: Английский

Citations

2
Electrochemical Regioselective C(sp2)–H Bond Chalcogenation of Pyrazolo[1,5-a]pyrimidines via Radical Cross-Coupling at Room Temperature DOI

Abhinay S. Chillal,

Rajesh T. Bhawale,

Siddharth Sharma

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(19), P. 14496 - 14504

Published: Sept. 16, 2024

Herein, we disclose an electrochemical approach for the C(sp

Language: Английский

Citations

1
Electrochemical Synthesis of 4‐Selenylated Oxazolones via Oxyselenylation of Ynamides DOI Open Access
Jinhui Cai,

Kaili Cen,

Weishuang Li

et al.

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 19, 2024

Abstract Electrosynthesis of selenylated‐oxazolone derivatives via cascade selenylation/cyclization ynamides was disclosed. A series diaryl diselenides, dialkyl and heteroaryl‐substituted tolerated in this protocol delivered 4‐selenyloxazolones 28–83% yields. The scale‐up reaction the oxidation performed to showcase practicability method. Furthermore, mechanistic experiments indicated that a cationic pathway instead radical probably involved.

Language: Английский

Citations

1
Supporting Electrolyte‐Free Electrochemical Oxidative C−H Sulfonylation and Thiocyanation of Fused Pyrimidin‐4‐Ones in an All‐Green Electrolytic System DOI
Sumit Biswas, Subhadeep Ghosh, Indrajit Das

et al.

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 30(6)

Published: Nov. 7, 2023

An electrooxidative C-H functionalization is a widely accepted route to obtain sulfur-containing arenes and heteroarenes. However, this process often involves using non-recyclable supporting electrolytes, (co)solvents like hexafluoroisopropanol, additives acid, or catalysts. The use of additional reagents can increase costs waste, reducing atom efficiency. Moreover, unlike other nitrogen-containing heterocycles, there have only been sporadic reports electrochemical in fused pyrimidin-4-ones, an electrolyte-free has yet be developed. This work demonstrates that such anodic coupling reactions performed all-green electrolytic system without electrolytes HFIP, maintaining high economy. strategy utilizes inexpensive sodium sulfinates ammonium thiocyanate as sulfonylating thiocyanating agents undivided cell at constant current, mixture CH

Language: Английский

Citations

3