Substrate-Controlled Divergent Reductive Cyclization of 2-Arylanilines Using CO₂ as a Switching Reagent

Organic Letters, Journal Year: 2024, Volume and Issue: 27(1), P. 510 - 516

Published: Dec. 30, 2024

Capturing CO2 is highly valued in the field of organic synthesis, especially underdeveloped dual-CO2 conversion. In this study, we detail a novel reductive cyclization 2-indolylanilines with dual as difunctional reagent presence PMHS [poly(methylhydrosiloxane)], delivering methyl-substituted quinoxalines. Furthermore, another chemoselective 2-pyrrolylanilines also realized by converting mono-CO2. Mechanistic investigations shed light upon fact that substrate-controlled divergence mainly depends on formation N-diacylative intermediates.

Language: Английский

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DFT Study of Functional Reduction of CO₂ with BH₃NMe₃: The Real Role of Organic Catalyst TBD

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(9), P. 6149 - 6158

Published: April 18, 2024

The detailed mechanism of transition metal-free-catalyzed monomethylation 2-naphthyl acetonitrile (1a) with CO2 in the presence triazabicyclodecene (TBD) and BH3NMe3 was investigated using density functional theory. C-methylation process proved to generate formaldehyde followed by formation product via an alcohol rather than a methoxyborane intermediate. During reaction, is activated form TBD-CO2 adduct changed into TBD-BH2 (IM2) TBD. IM2 plays real reducing role within system due unique coordination capability B atom. In addition enhancing nucleophilicity 1a through deprotonation tBuOK, our research also indicates that generated tBuOH not only assists proton transfer intermediate but promotes regeneration

Language: Английский

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Advances in Three-Component Coupling Reactions Involving CO₂

Chinese Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 44(5), P. 1506 - 1506

Published: Jan. 1, 2024

Carbon dioxide (CO2) is the attractive green and renewable C1 resource, its direct participation in organic synthesis reactions as a reaction feedstock or promoter, which research direction advocated by chemistry.On other hand, three-component coupling considered to be one of most strategies synthetic chemistry, capable synthesizing complex molecules directly from simple readily available raw materials.Based on this, this paper reviews systems involving CO2 material categorizes them according types products generated: carboxyl, ester, carbonyl, haloalkyl, cyano compounds well promoter.An outlook development such also given.Keywords carbon dioxide; chemistry; coupling; promoter 众所周知, 二氧化碳(CO 2 )是主要的温室气体之一, 全球 CO 的排放量巨大并且呈现逐年激增的态势 [1] .同 时, 也是地球上储量最丰富、廉价、无毒的气 体 [2][3][4] .从有机化学合成的角度来看, 可以作为合成 有机化合物的可再生 来源, 从环保、经济和可持续 发展的角度看, 这种 的应用策略相比传统的捕获和 存储 模式更具吸引力 [5][6] .利用 参与有机合成 反应, 通过形成 C-C 和 C-O 等化学键, 能够高效构筑 一系列具有良好生物活性的分子骨架和具有高附加价 值的功能材料等, 且这些有价值的有机化合物具有工业 生产的潜力 [7] .因此, 基于 这一 源的化学转化一 直备受关注, 目前为止也取得了很多研究成果: 例如, 通过 与光催化 [8] 、电催化 [9] 和连续流 [10] 等反应方式 的结合, 实现多种羧基化、羰基化等产物的合成; 对 C O 的 还 原 , 实 现化 合 物 烷 基化 、 氰 基 化的 转 化 [11][12] .另一方面, 多组分反应(MCR)是三种或多种反应物 反应生成单一产物的反应体系.MCR 为生成具有结构 多样性和分子复杂性的复杂分子提供了一种便捷的合 成途径.这些类型的反应具有原子效率高, 反应快速简 单, 省时省能等主要优点, 并且通常对环境友好.因此, MCR 在生物医学、有机合成和工业化学等各个研究领 域发挥着重要作用 [13] .在多组分反应中, 众所周知的人 名反应, Mannich 反应 [14] Strecker [15] Ugi [16]

Language: Английский

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A Lewis Acid‐Base Pair Catalyzed Dearomative Transformation of Unprotected Indoles via B−H Bond Activation

Chemistry - An Asian Journal, Journal Year: 2023, Volume and Issue: 18(23)

Published: Oct. 9, 2023

A sustainable and metal-free protocol has been described for the reduction of unprotected indoles. The catalytic system consists B(C6 F5 )3 THF as a Lewis acid-base pair that can activate B-H bond pincolborane (HBpin). encompasses broad substrate scope. Control experiments were conducted to understand possible intermediates involved during present protocol.

Language: Английский

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