Recent advances in nucleophile-triggered CO<sub>2</sub>-incorporated cyclization leading to heterocycles

Wang, Sheng; Xi, Chanjuan

doi:10.1039/c8cs00281a

Cited by 314 publications

(102 citation statements)

References 142 publications

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“…[1] The conversion of CO 2 into valuable chemicals is one of the most promising pathways to reduce CO 2 emission and fully utilize this abundant, cheap, and nontoxic C 1 source. [4][5][6] In particular, the cycloaddition of epoxidesw ith CO 2 to form cyclic carbonates is an important and atom-economic reaction, and the resultant products are important heterocyclic compounds widely used in organic synthesis. [4][5][6] In particular, the cycloaddition of epoxidesw ith CO 2 to form cyclic carbonates is an important and atom-economic reaction, and the resultant products are important heterocyclic compounds widely used in organic synthesis.…”

Section: Introductionmentioning

confidence: 99%

Imidazolium‐Salt‐Functionalized Covalent Organic Frameworks for Highly Efficient Catalysis of CO₂ Conversion

Qiu¹,

Zhang²,

Li³

et al. 2019

ChemSusChem

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The conversion of CO2 into valuable chemicals is an ideal pathway for CO2 utilization in industry, although the development of highly efficient catalysts remains a challenge. Herein, the design and synthesis of two covalent organic frameworks (COFs) functionalized with imidazolium salts were reported as catalysts for CO2 conversion. The resultant COFs possessed highly crystalline structures, showed high stability and surface area, and contained dense catalytic active sites on the pore walls. They exhibited outstanding catalytic performances for the reaction of CO2 with epoxides without any solvent or cocatalyst under mild conditions and afforded a record turnover number of 495 000. In addition, the COFs could serve as effective catalysts in the reductive reaction of CO2 with amines. The results presented here thus demonstrate the exceptional potential of the functionalized COFs for various challenging CO2 transformations.

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Section: Introductionmentioning

confidence: 99%

Imidazolium‐Salt‐Functionalized Covalent Organic Frameworks for Highly Efficient Catalysis of CO₂ Conversion

Qiu¹,

Zhang²,

Li³

et al. 2019

ChemSusChem

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“…The product was isolated by column chromatography (hexane as eluent) as a yellow oil. Yield: 0.084 g (56%), 1 ). 13…”

Section: -(Butylselanyl)-2-phenyl-5-tosyl-45-dihydroselenopheno [2mentioning

confidence: 99%

“…Although the development of heterocycle-related field merges with that of chemistry, there are continuous improvements in their synthesis. [1] This is because heterocycle derivatives have displayed broad spectrum applications in medicine, agriculture, industry, and chemistry. [2] In this context, selenium-containing heterocycles, [3] even though not present in natural products, have been widely used in material science, as intermediaries in organic synthesis, and also searched for different biological activities.…”

Section: Introductionmentioning

confidence: 99%

“…HRMS: cald for C 28 H 28 NO 2 SSe 2 (ESI-TOF, [M + H] + ): 602.0171, found: 602.0177.1-(Butylselanyl)-8-methyl-2-phenyl-5-tosyl-4,5-dihydroselenopheno[2,3-c]quinolone (2 u):The product was isolated by column chromatography (hexane/ethyl acetate 98:2 as eluent) as a yellow solid. Yield: 0.075 g (49%); mp 96-97 0 C 1. H NMR (CDCl 3 , 400 MHz): δ (ppm) 8.44 (dd, J = 1.5 Hz, J = 0.6 Hz, 1H), 7.71 (d, J = 8.1 Hz, 1H), 7.43-7.31 (m, 5H), 7.24-7.20 (m, 2H), 7.17 (ddd, J = 8.1 Hz, J = 2.0 Hz, J = 0.8 Hz, 1H), 6.93 (dd, J = 8.6 Hz, J = 0.7 Hz, 2H), 4.94 (s, 2H), 2.41 (s, 3H), 2.27 (s, 3H), 2.12 (t, J = 7.4 Hz, 2H), 1.31 (quint, J = 7.4 Hz, 2H), 1.16 (sex.…”

mentioning

confidence: 99%

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Iron‐Mediated Cyclization of 1,3‐Diynyl Propargyl Aryl Ethers with Dibutyl Diselenide: Synthesis of Selenophene‐Fused Chromenes

2020

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The synthesis of selenophene‐fused chromene derivatives starting from 1,3‐diynyl propargyl aryl ethers is reported herein. The method is based on carbon‐carbon, carbon‐selenium, selenium‐carbon and carbon‐selenium bonds formation in a one‐pot protocol, using iron(III) chloride and dibutyl diselenide as promoters. The same reaction conditions were applied to propargyl anilines leading to the formation of 1‐(butylselanyl)‐selenophene quinolines. The results showed that the dilution and temperature of substrate addition had a crucial influence in the products obtained. When the substrates were added at room temperature, in the absence of a solvent, a mixture of products was obtained, whereas the slowly addition (15 min) of starting materials, as a dichloromethane solution, at 0 °C led to the product formation in good yields. The mechanistic study indicates that the cooperative action between iron(III) chloride and dibutyl diselenide was essential to promote the cyclization, whereas separately none of them was effective in promoting the cyclization. We proved the synthetic utility of heterocycles obtained in the Suzuki cross coupling reaction, giving the corresponding cross‐coupled products in good yields. In addition, the organoselenium moiety was removed from the structures of products by using n‐butyllithium.

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“…Non-reductive C À NB ond Forming Reactions Non-reductive C À Nb ond forming reactions of amines with CO 2 predominantly involve cyclizations, [13,14,67] which includes the synthesis of quinazoline-(2,4)-diones,o xazolidinones,d ihydroquinolinones,d ihydrobenzo-(1,3)-oxazinones, cyclic and linear ureas and their derivatives.C yclization reactions depend on carbamate salt formation in the form [BaseH][RR'NCOO],w here the carbamate anion internally cyclizes into the desired product either by acting as an ucleophile [67] via the carbamate oxygen or as an electrophile via the carbamate carbon ( Figure 12). Base catalysts promote carbamate salt formation, enhance its nucleophilicity and/or promote its dehydration to isocyanate,w hich then acts as an electrophile instead of the original carbamate anion.…”

Section: Angewandte Chemiementioning

confidence: 99%

Pivotal Role of the Basic Character of Organic and Salt Catalysts in C−N Bond Forming Reactions of Amines with CO₂

Hulla

Dyson

2019

Angew Chem Int Ed

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Organocatalysts promote a range of C−N bond forming reactions of amines with CO2. Herein, we review these reactions and attempt to identify the unifying features of the catalysts that allows them to promote a multitude of seemingly unrelated reactions. Analysis of the literature shows that these reactions predominantly proceed by carbamate salt formation in the form [BaseH][RR′NCOO]. The anion of the carbamate salt acts as a nucleophile in hydrosilane reductions of CO2, internal cyclization reactions or after dehydration as an electrophile in the synthesis of urea derivatives. The reactions are enhanced by polar aprotic solvents and can be either promoted or hindered by H‐bonding interactions. The predominant role of all types of organic and salt catalysts (including ionic liquids, ILs) is the stabilization of the carbamate salt, mostly by acting as a base. Catalytic enhancement depends on the combination of the amine, the base strength, the solvent, steric factors, ion pairing and H‐bonding. A linear relationship between the base strength and the reaction yield has been demonstrated with IL catalysts in the synthesis of formamides and quinazoline‐2,4‐diones. The role of organocatalysts in the reactions indicates that all bases of sufficient strength should be able to catalyze the reactions. However, a physical limit to the extent of a purely base catalyzed reaction mechanism should exist, which needs to be identified, understood and overcome by synergistic or alternative methods.

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Recent advances in nucleophile-triggered CO₂-incorporated cyclization leading to heterocycles

Abstract: CO2, as a sustainable, feasible, abundant one-carbon synthon, has been utilized in carboxylative cyclization, carbonylative cyclization, and reductive cyclization.

Cited by 314 publications

References 142 publications

Imidazolium‐Salt‐Functionalized Covalent Organic Frameworks for Highly Efficient Catalysis of CO₂ Conversion

Imidazolium‐Salt‐Functionalized Covalent Organic Frameworks for Highly Efficient Catalysis of CO₂ Conversion

Iron‐Mediated Cyclization of 1,3‐Diynyl Propargyl Aryl Ethers with Dibutyl Diselenide: Synthesis of Selenophene‐Fused Chromenes

Pivotal Role of the Basic Character of Organic and Salt Catalysts in C−N Bond Forming Reactions of Amines with CO₂

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Recent advances in nucleophile-triggered CO2-incorporated cyclization leading to heterocycles

Abstract: CO2, as a sustainable, feasible, abundant one-carbon synthon, has been utilized in carboxylative cyclization, carbonylative cyclization, and reductive cyclization.

Cited by 314 publications

References 142 publications

Imidazolium‐Salt‐Functionalized Covalent Organic Frameworks for Highly Efficient Catalysis of CO2 Conversion

Imidazolium‐Salt‐Functionalized Covalent Organic Frameworks for Highly Efficient Catalysis of CO2 Conversion

Iron‐Mediated Cyclization of 1,3‐Diynyl Propargyl Aryl Ethers with Dibutyl Diselenide: Synthesis of Selenophene‐Fused Chromenes

Pivotal Role of the Basic Character of Organic and Salt Catalysts in C−N Bond Forming Reactions of Amines with CO2

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Recent advances in nucleophile-triggered CO₂-incorporated cyclization leading to heterocycles

Imidazolium‐Salt‐Functionalized Covalent Organic Frameworks for Highly Efficient Catalysis of CO₂ Conversion

Imidazolium‐Salt‐Functionalized Covalent Organic Frameworks for Highly Efficient Catalysis of CO₂ Conversion

Pivotal Role of the Basic Character of Organic and Salt Catalysts in C−N Bond Forming Reactions of Amines with CO₂