Ionic Liquid-Promoted Three-Component Domino Reaction of Propargyl Alcohols, Carbon Dioxide and 2-Aminoethanols: A Thermodynamically Favorable Synthesis of 2-Oxazolidinones

Xia, Shu-Mei; Song, Yu; Li, Xuedong; Li, Hongru; He, Liang‐Nian

doi:10.20944/preprints201810.0351.v1

Cited by 4 publications

(1 citation statement)

References 56 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…25 He and co-workers reported that [HTBD][TFE] could catalyze the reaction of propargylic alcohols with atmospheric CO 2 and 2-aminoethanol through synergistically activating the substrates and CO 2 , affording a wide range of 2-oxazolidinones along with an equal amount of α-hydroxyl ketones. 26 2.1.4. Carbonylation of o-Phenylenediamines with CO 2 .…”

Section: We Discovered That [Hdbu] + -Based Protic Ils Such As [Hdbu]...mentioning

confidence: 99%

Ionic-Liquid-Catalyzed Approaches under Metal-Free Conditions

2021

View full text Add to dashboard Cite

Conspectus Metal-free catalysis is a promising protocol to access chemicals without metal contamination. Ionic liquids (ILs) that are entirely composed of organic cations and inorganic/organic anions have emerged as promising alternatives to molecular solvents and metal catalysts due to their unique properties such as structural tunability, the coexistence of multiple interactions among ions (e.g., electrostatic interaction, hydrogen bonding, van de Waals forces, acid/base interactions, hydrophilic/hydrophobic interactions, etc.), unique affinity for a wide range of chemicals, good chemical and thermal stability, and quite low volatility. ILs have shown potential applications in various chemical processes. In this Account, we systematically described our most recent work on IL-catalyzed approaches under metal-free conditions. The first section presents the IL-catalyzed strategies toward the transformation of CO2 to value-added chemicals, focusing on the CO2-reactive IL-catalyzed CO2 transformation to various heterocycles and the IL-catalyzed reductive transformation of CO2 to chemicals. In these approaches, we designed task-specific ILs that are able to chemically capture and activate CO2 via forming anion-based carbonate/carbamate or cation-based carboxylate/carbamate intermediates, thus further accomplishing its transformation to a series of heterocycles including quinazoline-2,4(1H,3H)-diones, cyclic carbonates, 2-oxazolidinones, oxazolones, and benzimidazolones under metal-free conditions. For the IL-catalyzed approaches to reducing CO2 with hydrosilanes to chemicals, we employed ILs capable of activating the Si–H bond in hydrosilanes and the N–H bond in amine substrates via H-bonding, thus achieving the reductive transformation of CO2 to formamides, benzimidazoles, and benzothiazoles via cooperative catalysis. The second section describes our finding on the IL-catalyzed hydration of the CC bond in propargylic alcohols. Azolate anion-based ILs that can chemically capture CO2 via the formation of carbamates could serve as robust nucleophiles to attack the CC bond in propargylic alcohols and then efficiently catalyze the hydration of propargylic alcohols to produce α-hydroxy ketones with the assistance of atmospheric CO2 gas under metal-free conditions. The third section unveils the cooperative catalysis strategy of hydrogen bond donors and acceptors of ILs for chemical reactions. In the hydrogen-bonding catalysis protocols, cations of the ILs act as H-bond donors and anions, as acceptors, forming H-bonds with the reactant molecules, respectively, in opposite ways, which can cooperatively catalyze the ring-closing C–O/C–O bond metathesis reactions of aliphatic diethers to O-heterocycles, the dehydrative etherification of alcohols to ethers, and direct oxidative esterification of alcohols to esters. We believe that these IL-catalyzed metal-free processes and strategies display promising practical applications, and their commercialization would bring great benefits to the production of the as-afforded value-...

show abstract

Section: We Discovered That [Hdbu] + -Based Protic Ils Such As [Hdbu]...mentioning

confidence: 99%

Ionic-Liquid-Catalyzed Approaches under Metal-Free Conditions

2021

View full text Add to dashboard Cite

show abstract

Green Synthesis of 2-Oxazolidinones by an Efficient and Recyclable CuBr/Ionic Liquid System via CO2, Propargylic Alcohols, and 2-Aminoethanols

Gong

et al. 2021

Catalysts

View full text Add to dashboard Cite

With the aim of profitable conversion of carbon dioxide (CO2) in an efficient, economical, and sustainable manner, we developed a CuBr/ionic liquid (1-butyl-3-methylimidazolium acetate) catalytic system that could efficiently catalyze the three-component reactions of propargylic alcohols, 2-aminoethanols, and CO2 to produce 2-oxazolidinones and α-hydroxy ketones. Remarkably, this catalytic system employed lower metal loading (0.0125–0.5 mol%) but exhibited the highest turnover number (2960) ever reported, demonstrating its excellent activity and sustainability. Moreover, our catalytic system could efficiently work under 1 atm of CO2 pressure and recycle among the metal-catalyzed systems.

show abstract

Tandem Reactions Based on the Cyclization of Carbon Dioxide and Propargylic Alcohols: Derivative Applications of α-Alkylidene Carbonates

et al. 2022

View full text Add to dashboard Cite

As a well-known greenhouse gas, carbon dioxide (CO2) has attracted increasing levels of attention in areas of energy, environment, climate, etc. Notably, CO2 is an abundant, nonflammable, and renewable C1 feedstock in view of chemistry. Therefore, the transformation of CO2 into organic compounds is an extremely attractive research topic in modern green and sustainable chemistry. Among the numerous CO2 utilization methods, carboxylative cycloaddition of CO2 into propargylic alcohols is an ideal route due to the corresponding products, α-alkylidene cyclic carbonates, which are a series of highly functionalized compounds that supply numerous potential methods for the construction of various synthetically and biologically valuable agents. This cyclization reaction has been intensively studied and systematically summarized, in the past years. Therefore, attention has been gradually transferred to produce more derivative compounds. Herein, the tandem reactions of this cyclization with hydration, amination, alcoholysis, and isomerization to synthesize α-hydroxyl ketones, oxazolidinones, carbamates, unsymmetrical carbonates, tetronic acids, ethylene carbonates, etc. were systematically reviewed.

show abstract

Ionic Liquid-Promoted Three-Component Domino Reaction of Propargyl Alcohols, Carbon Dioxide and 2-Aminoethanols: A Thermodynamically Favorable Synthesis of 2-Oxazolidinones

Cited by 4 publications

References 56 publications

Ionic-Liquid-Catalyzed Approaches under Metal-Free Conditions

Ionic-Liquid-Catalyzed Approaches under Metal-Free Conditions

Green Synthesis of 2-Oxazolidinones by an Efficient and Recyclable CuBr/Ionic Liquid System via CO2, Propargylic Alcohols, and 2-Aminoethanols

Tandem Reactions Based on the Cyclization of Carbon Dioxide and Propargylic Alcohols: Derivative Applications of α-Alkylidene Carbonates

Contact Info

Product

Resources

About