TMSN3 Initiated Electrochemical Mono-Dealkylation of Tertiary Amides DOI

Anjun Ding,

Meixia Liu,

Yunxiang Jiang

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 13, 2024

N-Dealkylation of amides is a general process in living organisms and organic synthetic chemistry, but an efficient chemical approach for this transformation has not been explored. Herein, we report electrochemical method the monodealkylation wide range tertiary amides, including benzamides, alkyl lactams, sulfonamides. The reaction proceeds smoothly under mild conditions using TMSN3 as initiator limited to deethylation or demethylation. This protocol enables large synthesis, providing valuable tool chemistry.

Language: Английский

Electrochemical Synthesis of 2-Amino-1,3-benzoxazines via TBAI-mediated Desulfurative Cyclization of Isothiocyanates and 2-Aminobenzyl Alcohols DOI
Fengkai Sun,

Man Miao,

Yu Huang

et al.

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

Published: Feb. 5, 2025

An efficient one-step protocol has been developed to access a variety of 2-amino-1,3-benzoxazine derivatives via tetrabutylammonium iodide-mediated electrochemical desulfurative cyclization isothiocyanates and 2-aminobenzyl alcohols. The reaction proceeds through cycle involving in situ iodine generation, cyclization, iodide regeneration, efficiently forming intermolecular C–O C–N bonds affording 2-amino-1,3-benzoxazines moderate excellent yields. practical utility this strategy is evidenced by its broad substrate scope, good functional group compatibility, scalability gram-scale synthesis, metal- oxidant-free conditions.

Language: Английский

Citations

3
B(C6F5)3/Chiral Phosphoric Acid Promoted Asymmetric C-3 gem-Difluoroalkylation of Quinoxalin-2-ones with Difluoroenoxysilanes DOI

Jia Li,

Ting Wang, Jingchao Chen

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(31), P. 6551 - 6555

Published: July 30, 2024

The asymmetric Mannich-type reaction of quinoxalin-2-ones with difluoroenoxysilanes has been developed for the synthesis chiral gem-difluoroalkylated quinoxalin-2-ones. worked in presence phosphoric acid CPA 1 and B(C6F5)3 THF at room temperature. exhibited a good substrate scope furnishing products yields (up to 97%) up 96% ee.

Language: Английский

Citations

3
Advances in Photoinduced Minisci-like Reactions DOI

Mario Martos,

Irene Bosque, José C. González‐Gómez

et al.

Synthesis, Journal Year: 2024, Volume and Issue: unknown

Published: July 29, 2024

Abstract The Minisci reaction, which has been around for more than five decades, is still the preferred tool straightforward alkylation of basic heteroarenes. recent developments in photocatalysis have opened novel pathways radical generation under milder and sustainable conditions. Implementing this approach into reaction renewed interest transformation, attractive per se Medicinal Chemistry. Aspects such as sacrificial oxidants, catalysts, specific conditions should be carefully examined to evaluate practicability protocol. This short review focuses on advances (2020 February 2024) photoinduced Minisci-type reactions, emphasizing sustainability. 1 Introduction 2 Using Noble-Metal-Based Photocatalysts 3 Noble-Metal-Free Methods Sacrificial Oxidants 4 Without 5 Conclusions Perspectives

Language: Английский

Citations

3
Site-selective α-C(sp3)–H arylation of dialkylamines via hydrogen atom transfer catalysis-enabled radical aryl migration DOI Creative Commons
Jie Xu, Ruihan Li,

Yijian Ma

et al.

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

Published: Aug. 8, 2024

Site-selective C(sp3)–H arylation is an appealing strategy to synthesize complex arene structures but remains a challenge facing synthetic chemists. Here we report the use of photoredox-mediated hydrogen atom transfer (HAT) catalysis accomplish site-selective α-C(sp3)–H dialkylamine-derived ureas through 1,4-radical aryl migration, by which wide array benzylamine motifs can be incorporated medicinally relevant systems in late-stage installation steps. In contrast previous efforts, this C–H protocol exhibits specific site-selectivity, proforming predominantly on sterically more-hindered secondary and tertiary α-amino carbon centers, while functionalization less-hindered N-methyl group effectively circumvented most cases. Moreover, diverse range multi-substituted piperidine derivatives obtained with excellent diastereoselectivity. Mechanistic computational studies demonstrate that rate-determining step for methylene initial H abstraction, whereas radical ipso cyclization bears highest energy barrier functionalization. The relatively lower activation free energies compared methylic bond lead exceptional site-selectivity. authors migration.

Language: Английский

Citations

3
One‐Step Nickel‐Catalyzed Synthesis of Alpha‐Arylidene and Gamma Hydroxy‐Substituted N‐Methyl‐2‐Pyrrolidones DOI

Robin Prakash Sirvin Rajan,

Jungwi Mok,

Junseong Lee

et al.

Asian Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 13(6)

Published: March 25, 2024

Abstract This study describes a method to synthesize compounds with an arylidene group at the alpha position of N ‐methyl‐2‐pyrrolidone (NMP) and alcohol gamma in single‐step reaction using NMP aldehyde. The highest yields were obtained Ni(glyme)Cl 2 as nickel catalyst tert ‐butyl hydroperoxide oxidant, various aryl aldehydes reacted under optimal conditions yield target compounds.

Language: Английский

Citations

0
Electrochemical Cross-Dehydrogenative of Amides and Heteroarenes DOI
Paul Richardson

Synfacts, Journal Year: 2024, Volume and Issue: 20(05), P. 0464 - 0464

Published: April 15, 2024

Key words electrochemistry - hydrogen atom transfer amides heteroarenes quinolines coumarins

Language: Английский

Citations

0
HAT‐Mediated Electrochemical C(sp2)−H Alkoxylation of Pyrido[1,2‐a]pyrimidin‐4‐ones with Aliphatic Alcohols DOI
Subhadeep Ghosh, Sumit Biswas, Indrajit Das

et al.

ChemCatChem, Journal Year: 2024, Volume and Issue: unknown

Published: July 29, 2024

Abstract A direct alkoxylation of the electron‐deficient olefinic C(sp 2 )−H bond in pyrido[1,2‐ a ]pyrimidin‐4‐ones using aliphatic alcohols has been developed under transition metal and external chemical oxidant‐free electrochemical conditions. Azidotrimethylsilane (TMSN 3 ) is utilized as hydrogen atom transfer (HAT) reagent to enable homolytic cleavage unfunctionalized O−H alcohols, thereby generating electrophilic alkoxy radicals. Moreover, effectiveness this method demonstrated with d 4 ‐methanol (CD OD), leading synthesis ‐methoxylated N ‐heterocycles good yields sustainable The proposed mechanism, based on or trideuteromethoxy radicals, substantiated by control experiments cyclic voltammetry (CV) studies.

Language: Английский

Citations

0
TMSN3 Initiated Electrochemical Mono-Dealkylation of Tertiary Amides DOI

Anjun Ding,

Meixia Liu,

Yunxiang Jiang

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 13, 2024

N-Dealkylation of amides is a general process in living organisms and organic synthetic chemistry, but an efficient chemical approach for this transformation has not been explored. Herein, we report electrochemical method the monodealkylation wide range tertiary amides, including benzamides, alkyl lactams, sulfonamides. The reaction proceeds smoothly under mild conditions using TMSN3 as initiator limited to deethylation or demethylation. This protocol enables large synthesis, providing valuable tool chemistry.

Language: Английский

Citations

0