- Gold(I)-catalyzed formation of 4-alkylidene-1,3-dioxolan-2-ones from propargylic tert-butyl carbonates
-
A study concerning the gold(I)-catalyzed rearrangement of propargylic tert-butyl carbonates into 4-alkylidene-1,3-dioxolan-2-ones is described. The mild reaction conditions employed allow the efficient synthesis of a variety of cyclic carbonates that would be less conveniently obtained using reported methods. Variability in the structure of the final product has been observed and is significantly dependent on the nature of the substituent attached to the alkyne moiety.
- Buzas, Andrea,Gagosz, Fabien
-
-
Read Online
- Catalytic formation of carbamates and cyclic carbonates by copper complex of 2,5,19,22-tetraaza[6,6](1,1′)ferrocenophane-1,5-diene X-ray crystal structure of [Cu(1)]PF6
-
The reaction of [Cu(MeCN)4]PF6 with a ferrocene-containing tetraazamacrocycle 2,5,19,22-tetraaza[6,6](1,1)ferrocenophane-1,5-diene (1) gives the copper(I) complex of the type [Cu(1)]PF6 (2) which crystallizes in the orthorhombic system: P212121 (#19); a = 7.597(2) A, b = 14.805(5) A, c = 24.194(4) A; Z = 4; R = 0.080; Rw = 0,083. The geometry around the central metal is a distorted tetrahedron with two pairs of differing Cu-N bond length. This complex has demonstrated the excellent catalytic activity toward the formation of cyclic carbonates and carbamates in the presence of CO2, giving almost quantitative product yields in most reactions that have been employed.
- Kim, Hak-Soo,Kim, Jeong-Won,Kwon, Soon-Chul,Shim, Sang-Chul,Kim, Tae-Jeong
-
-
Read Online
- Nickel-Catalyzed CO2Rearrangement of Enol Metal Carbonates for the Efficient Synthesis of β-Ketocarboxylic Acids
-
4-Methylene-1,3-dioxolan-2-ones underwent oxidative addition of a Ni0catalyst in the presence of Me2Al(OMe), followed by a coupling reaction with alkynes, to form δ,?-unsaturated β-ketocarboxylic acids with high regio- and stereoselectivity. The reaction proceeds by [1,3] rearrangement of an enol metal carbonate intermediate and the formal reinsertion of CO2.
- Ninokata, Ryo,Yamahira, Tatsuya,Onodera, Gen,Kimura, Masanari
-
-
Read Online
- Cu(I)/ionic liquids promote the conversion of carbon dioxide into oxazolidinones at room temperature
-
Recently, the efficient chemical fixation of carbon dioxide (CO2) into high value chemicals without using noble metal catalysts has become extremely appealing from the viewpoint of sustainable chemistry. In this work, a one-pot three component reaction of propargylic alcohols, anines and CO2 that can proceed in an atom economy and environmentally benign manner by combination of CuI and tetrabutylphosphonium imidazol ([P4444][Im]) as a catalyst was described. Catalysis studies indicate that this catalytic system is an effective catalyst for the conversion of CO2 into oxazolidinones at room temperature and ambient pressure without any solvent. The results provide a useful way to design novel noble metal-free catalyst systems for the transformation of CO2 into other valuable compounds.
- Qiu, Jikuan,Zhao, Yue,Zhao, Yuling,Wang, Huiyong,Li, Zhiyong,Wang, Jianji,Jiao, Tiantian
-
-
Read Online
- Ag Nanoparticles Supported on a Resorcinol-Phenylenediamine-Based Covalent Organic Framework for Chemical Fixation of CO2
-
Covalent organic frameworks are a new class of crystalline organic polymers possessing a high surface area and ordered pores. Judicious selection of building blocks leads to strategic heteroatom inclusion into the COF structure. Owing to their high surface area, exceptional stability and molecular tunability, COFs are adopted for various potential applications. The heteroatoms lining in the pores of COF favor synergistic host–guest interaction to enhance a targeted property. In this report, we have synthesized a resorcinol-phenylenediamine-based COF which selectively adsorbs CO2 into its micropores (12 ?). The heat of adsorption value (32 kJ mol?1) obtained from the virial model at zero-loading of CO2 indicates its favorable interaction with the framework. Furthermore, we have anchored small-sized Ag nanoparticles (≈4–5 nm) on the COF and used the composite for chemical fixation of CO2 to alkylidene cyclic carbonates by reacting with propargyl alcohols under ambient conditions. Ag@COF catalyzes the reaction selectively with an excellent yield of 90 %. Recyclability of the catalyst has been demonstrated up to five consecutive cycles. The post-catalysis characterizations reveal the integrity of the catalyst even after five reaction cycles. This study emphasizes the ability of COF for simultaneous adsorption and chemical fixation of CO2 into corresponding cyclic carbonates.
- Chakraborty, Debanjan,Shekhar, Pragalbh,Singh, Himan Dev,Kushwaha, Rinku,Vinod,Vaidhyanathan, Ramanathan
-
-
Read Online
- CO2-Sourced α-Alkylidene Cyclic Carbonates: A Step Forward in the Quest for Functional Regioregular Poly(urethane)s and Poly(carbonate)s
-
Described is a robust platform for the synthesis of a large diversity of novel functional CO2-sourced polymers by exploiting the regiocontrolled ring-opening of α-alkylidene carbonates by various nucleophiles. The reactivity of α-alkylidene carbonates is dictated by the exocyclic olefinic group. The polyaddition of CO2-sourced bis(α-alkylidene carbonate)s (bis-αCCs) with primary and secondary diamines provides novel regioregular functional poly(urethane)s. The reactivity of bis-αCCs is also exploited for producing new poly(β-oxo-carbonate)s by organocatalyzed polyaddition with a diol. This synthesis platform provides new functional variants of world-class leading polymer families (polyurethanes, polycarbonates) and valorizes CO2 as a chemical feedstock.
- Gennen, Sandro,Grignard, Bruno,Tassaing, Thierry,Jér?me, Christine,Detrembleur, Christophe
-
-
Read Online
- Room-Temperature Synthesis of a Hollow Microporous Organic Polymer Bearing Activated Alkyne IR Probes for Nonradical Thiol-yne Click-Based Post-Functionalization
-
This work shows that hollow microporous organic polymer (H-MOP-A) with activated internal alkynes as IR probes can be prepared by template synthesis based on acyl Sonogashira-Hagihara coupling at room temperature. The H-MOP-A is a versatile platform in the main chain PSM based on nonradical thiol-yne click reaction. Moreover, an IR peak of internal alkynes in the H-MOP-A is very intense and could be utilized in the monitoring of thiol-yne click-based main chain PSM. The functionalized H-MOP-A with carboxylic acids (H-MOP-CA) showed efficient adsorption toward Ag+ ions. The resultant H-MOP-CA-Ag showed excellent performance in the CO2 fixation to α-alkylidene cyclic compounds.
- Park, Jong In,Jang, June Young,Ko, Yoon-Joo,Lee, Sang Moon,Kim, Hae Jin,Jang, Hye-Young,Ko, Kyoung Chul,Son, Seung Uk
-
-
Read Online
- Synthesis Cu(I)–CN-based MOF with in-situ generated cyanogroup by cleavage of acetonitrile: Highly efficient for catalytic cyclization of propargylic alcohols with CO2
-
Developing a highly effective process for synthesis a cyano-bridged compound to avoid toxic organic or inorganic cyanides is very significant method for alleviating cyanides pollution. Here, a CN-based MOF catalyst (Cu(I)–CN–BPY) was synthesized by using copper ions coupled with Na4W10O32 in CH3CN under solvothermal conditions. The cyano-groups are generated in situ from the cleavage of C(sp3)–C(sp) in CH3CN. Because Cu(I) sites have ability to activate π-activate internal alkynes of carbon–carbon triple bonds for carboxylic cyclization reactions, which was applied in the cyclization of propargylic alcohols with CO2 and exhibited high efficiency with >95 % yields. For seeking out the active sites of MOF structure in carboxylic cyclization, we also synthesized two MOFs of Cu(I)–Cl–BPY and Cu(I)–I–BPY, and investigated for this reaction.
- Han, Qiuxia,Huang, Laikuan,Jiao, Jiachen,Li, Mingxue,Shi, Zhuolin,Xiao, Yang
-
-
Read Online
- PHOSPHINE CATALYSED SYNTHESIS OF UNSATURATED CYCLIC CARBONATES FROM CARBON DIOXIDE AND PROPARGYLIC ALCOHOLS
-
A new route to α-methylene cyclic carbonates is reported, by direct reaction of carbon dioxide with α-ethynyl alcohols in the presence of a catalytic amount of a phosphine.
- Furnier, Jean,Bruneau, Christian,Dixneuf, Pierre H.
-
-
Read Online
- Copper-catalysed synthesis of α-alkylidene cyclic carbonates from propargylic alcohols and CO2
-
We report a N-heterocyclic carbene copper(i) complex-catalysed formal cycloaddition between readily available propargylic alcohols and carbon dioxide at room temperature. By using the combination of a sterically demandingBPDPrCuCl complex (BPDPr = 1,3-bis(2,6-diisopropylphenyl)-1,3-diazonine-2-ylidene) and CsF, as catalytic system, primary propargylic alcohols are efficiently converted to the corresponding α-alkylidene cyclic carbonates. Gram scale (up to 89% yield) and reusability experiments (74% global yield, turnover number value = 103) showcase the robustness of the catalytic system. This practically simple protocol also tolerates secondary and tertiary propargylic alcohols under CO2at atmospheric pressure, enabling the direct synthesis of substituted and unsubstituted α-alkylidene cyclic carbonates at room temperature.
- Cervantes-Reyes, Alejandro,Farshadfar, Kaveh,Rudolph, Matthias,Rominger, Frank,Schaub, Thomas,Ariafard, Alireza,Hashmi
-
supporting information
p. 889 - 897
(2021/02/09)
-
- Highly efficient synthesis of alkylidene cyclic carbonates from low concentration CO2using hydroxyl and azolate dual functionalized ionic liquids
-
A highly efficient catalytic system was developed for the reaction between CO2 and propargylic alcohols for alkylidene cyclic carbonates. Ionic liquids (ILs) with different anions and cations were designed as cocatalysts, in order to find out the effect of the cation and the anion on this reaction. The results indicated that the effect of the cation was significant, especially the hydroxyl group on the cation played an important role due to the presence of a hydrogen bond. It was also found that the basicity of the anion was important for its catalytic activity, where the anion with moderate basicity gave the best activity. Moreover, this hydroxyl and azolate dual functionalized catalytic system showed excellent reusability and generality. It is worth mentioning that at a low concentration of CO2, this dual functionalized catalytic system showed excellent catalytic activity even in a gram-scale reaction, indicating its potential in carbon capture and utilization processes.
- Shi, Guiling,Zhai, Ran,Li, Haoran,Wang, Congmin
-
supporting information
p. 592 - 596
(2021/01/28)
-
- Synthesis of α-alkylidene cyclic carbonatesviaCO2fixation under ambient conditions promoted by an easily available silver carbamate
-
The simple and cost-effective compound [Ag(O2CNEt2)], in combination with PPh3, works as an effective catalytic precursor in the carboxylation of propargyl alcohols at ambient temperature and atmospheric CO2pressure, and in most cases under solventless conditions. The silver carbamate revealed a better performance than commercial silver oxide, Ag2O, and allowed to obtain a series of α-alkylidene cyclic carbonates in high yields.
- Bresciani, Giulio,Bortoluzzi, Marco,Ghelarducci, Claudia,Marchetti, Fabio,Pampaloni, Guido
-
p. 4340 - 4346
(2021/03/15)
-
- Noble metal-free Cu(i)-anchored NHC-based MOF for highly recyclable fixation of CO2under RT and atmospheric pressure conditions
-
The utilization of CO2as a C1 feedstock for the synthesis of high-value chemicals and fuels is an important step towards mitigating the increasing concentration of atmospheric carbon dioxide as well as the production of value-added chemicals. Herein, we demonstrate the development of an efficient recyclable catalyst for the conversion of CO2into oxazolidinones, which are important commodity chemicals for antibiotics, by utilizing an N-heterocyclic carbene (NHC)-based metal-organic framework (MOF). The NHC-centers lined in the pore walls of the MOF were utilized to anchor catalytically active Cu(i) ions by post-synthetic modification (PSM). The Cu(i)-embedded MOF showed highly recyclable and selective CO2uptake properties with a high heat of interaction energy of 43 kJ mol?1. The presence of a high density of CO2-philic NHC and catalytic Cu(i) sites in the 1D channels of the MOF render highly efficient catalytic activity for fixation of CO2into α-alkylidene cyclic carbonates and oxazolidinones at RT and atmospheric pressure conditions. Notably, Cu(i)@NHC-MOF showed excellent recyclability for up to 10 cycles of regeneration with retention of catalytic activity as well as chemical stability. To the best of our knowledge, Cu(i)@NHC-MOF is the first example of a noble metal-free MOF-based heterogeneous catalyst for the utilization of CO2to synthesize important value-added chemicals under mild conditions.
- Das, Rajesh,Nagaraja, C. M.
-
supporting information
p. 5195 - 5204
(2021/07/29)
-
- A green and recyclable CuSO4·5H2O/ionic liquid catalytic system for the CO2-promoted hydration of propargyl alcohols: an efficient assembly of α-hydroxy ketones
-
α-Hydroxy ketones are important building blocks in biological, pharmaceutical and synthetic chemistry. In this work, diverse α-hydroxy ketones were efficiently constructed through the CO2-promoted hydration process of propargyl alcohols, which was catalyzed by a system consisted of economical CuSO4·5H2O and a green 1-butyl-3-methylimidazolium acetate ionic liquid. Particularly, this catalytic system exhibited excellent activity under atmospheric CO2 or even mimetic flue gas (20 vol% of CO2). Moreover, this system employed the lowest metal loading ever reported (0.004–0.25 mol%) meanwhile reached the highest turnover number (11700) for the target hydration reaction. Additionally, this is the first reported Cu catalytic system with reliable recyclability, which could be easily reused at least 6 times with yields higher than 85%.
- Chen, Cheng,Chen, Yiyun,Hu, Jia,Huang, Leilei,Verpoort, Francis,Wang, Yu,Yuan, Ye,Zhao, Yufeng,Zheng, Jiayun
-
-
- Alternative Synthetic Routes to Dioxolanes and Thiadiazines
-
Abstract: The hydrolysis of 2-methylbut-3-yn-2-yl carbamate gave4,4-dimethyl-5-methylidene-1,3-dioxo-lan-2-one, whereas 2-methylbut-3-yn-2-olwas converted under similar conditions to 3-hydroxy-3-methylbutan-2-one.2-[2-Amino(hydrazinyl)-6H-1,3,4-thiadiazin
- Abdullaev, T. Kh.,Isobaev, M. D.,Jumaeva, M. I.,Mavlonov, B. G.,Pulatov, E. Kh.,Turdialiev, M. Z.
-
p. 369 - 375
(2021/07/02)
-
- A dual-functional urea-linked conjugated porous polymer anchoring silver nanoparticles for highly efficient CO2conversion under mild conditions
-
A dual-functional urea-linked conjugated porous polymer (UCPP) assembled by enol-imine with ordered unit arrays that act as potential anchoring sites in the networks was fabricated, and was further applied as a support for Ag nanoparticles by the coordinate interaction between them. The UCPP not only can well confine the Ag particle size and facilitate high dispersion, but also can afford special CO2-philic moieties to enhance the adsorption properties. The resulting Ag?UCPP as a heterogeneous catalyst exhibited excellent activity for the carboxylative cyclization of propargyl alcohols with CO2 under mild conditions, together with good recyclability, which is probably attributed to the synergistic effect of the UCPP on the adsorption and activation of CO2 and the immobilization of Ag nanoparticles. This work affords possible opportunities for the design and synthesis of a heterogeneous catalyst toward CO2 conversion.
- Li, Lin,Li, Wang,Li, Yuting,Liu, Xiaozhen,Wang, Jianxin,Wang, Liping,Wang, Xiaoji,Zhu, Jie
-
p. 13052 - 13059
(2020/10/13)
-
- Solvent-Dependent Assembly and Magnetic Relaxation Behaviors of [Cu4I3] Cluster-Based Lanthanide MOFs: Acting as Efficient Catalysts for Carbon Dioxide Conversion with Propargylic Alcohols
-
Two structurally similar metal-organic frameworks (MOFs) [Dy2Cu4I3(IN)7(DMF)2]·DMF (1) and [Dy2Cu4I3(IN)7(DMA)2]·DMA (2) (HIN = isonicotinic acid) feathering different coordinated solvent molecules were successfully isolated by tuning the types of solvents in the reaction system. Structural tests indicate that 1 and 2 are both built from 1D Dy(III) chains and copper iodide clusters [Cu4I3], generating into three-dimensional frameworks with an open 1D channel along the a axis. 1 and 2 display extensive and excellent solvent stability. Magnetic studies of 1 and 2 indicate that they exhibit interesting solvent-dependent magnetization dynamics. Importantly, 1 and 2 can act as highly effective catalysts for the carboxylic cyclization of propargyl alcohols with carbon dioxide (CO2) under ambient operating conditions. Additionally, the substrate scope was further explored over compound 1 based on the optimal conditions, and it exhibits efficient cyclic carboxylation of various terminal propargylic alcohols with CO2. This research offers an effective approach for the solvent-guided synthesis of MOFs materials and also presents the great application value of MOFs in CO2 chemical conversion.
- Wu, Zhi-Lei,Gu, Ai-Ling,Gao, Ning,Cui, Hui-Ya,Wang, Wen-Min,Cui, Jian-Zhong
-
supporting information
p. 15111 - 15119
(2020/11/02)
-
- Thermodynamic favorable CO2 conversion via vicinal diols and propargylic alcohols: A metal-free catalytic method
-
Organocatalysis represents a promising field in chemical fixation of CO2. Herein, a facile metal-free strategy was reported for the one-pot preparation of cyclic carbonates and α-hydroxy ketones from vicinal diols, propargylic alcohols and CO2. Wide scope of vicinal diols and propargylic alcohols was demonstrated to be efficient under the DBU-catalyzed conditions. A plausible mechanism was proposed, which included detailed main and side reactions under the metal-free conditions.
- Han, Li-Hua,Li, Jing-Yuan,Song, Qing-Wen,Zhang, Kan,Zhang, Qian-Xia,Sun, Xiao-Fang,Liu, Ping
-
supporting information
p. 341 - 344
(2019/07/04)
-
- Tubular metal organic frameworks from the curvature of 2D-honeycombed metal coordination
-
A tubular MOF with adequate active sites is prepared by the bending of metal-coordinated honeycombed frameworks via titration and shows fast catalytic kinetics with lower catalytic loading for CO2 conversion. The TON is observed to be 2300 and the corresponding TOF of up to 173 h-1 is achieved for the first time.
- Bao, Junhui,Chen, Yaju,Huang, Liping,Huang, Zhegang,Ji, Hongbing,Kim, Jehan,Wu, Shanshan,Xu, Xin,Zhang, Liwei,Zhou, Xiantai
-
supporting information
p. 2403 - 2406
(2020/03/05)
-
- Highly Efficient Fixation of Carbon Dioxide at RT and Atmospheric Pressure Conditions: Influence of Polar Functionality on Selective Capture and Conversion of CO2
-
The rapid increase in the concentration of atmospheric carbon dioxide (CO2) has resulted in undesirable environmental issues. Hence, selective CO2 capture and utilization as C1 feedstock for the preparation of high-value chemicals and fuels has been considered as a promising step toward mitigating the growing concentration of atmospheric CO2. In this direction, herein we report rational construction of a Ag(I)-anchored sulfonate-functionalized UiO-66 MOF named as MOF-SO3Ag composed of CO2-philic sulfonate functionality and catalytically active alkynophilic Ag(I) sites for chemical fixation of carbon dioxide. The MOF-SO3Ag exhibits selective as well as recyclable adsorption of CO2 with a high heat of adsorption energy (Qst) of 37.8 kJ/mol. On the other hand, the analogous MOF, UiO-66 doped with Ag(I), showed a lower Qst value of 30 kJ/mol, highlighting the importance of the sulfonate group for stronger interaction with CO2. Furthermore, the MOF-SO3Ag acts as an efficient heterogeneous catalyst for cyclic carboxylation of propargylic alcohols to generate α-alkylidene cyclic carbonates in >99percent yield at mild conditions of RT and 1 bar CO2. More importantly, one-pot synthesis of oxazolidinones by a three-component reaction between CO2, propargylic alcohol, and primary amine has also been achieved using MOF-SO3Ag catalyst under the mild conditions. The MOF is highly recyclable and retains its superior catalytic activity even after several cycles. To the best of our knowledge, MOF-SO3Ag is the first example of MOF reported for RT chemical fixation of CO2 to oxazolidinones by aminolysis of α-alkylidene cyclic carbonates under the environment-friendly mild conditions.
- Das, Rajesh,Nagaraja, C. M.
-
supporting information
(2020/07/21)
-
- Reduced Graphene Oxide Supported Ag Nanoparticles: An Efficient Catalyst for CO2 Conversion at Ambient Conditions
-
A highly efficient carboxylative cyclization of propargylic alcohols with CO2 under atmospheric pressure catalyzed by silver (0) nanoparticles decorated reduced graphene oxide (Ag-rGO) is reported. Ag-rGO was fully characterized by scanning electron microscope spectra (SEM), transmission electron microscopy (TEM), Fourier transform infrared (FT-IR) spectra, Raman spectra and X-ray photoelectron spectroscopy (XPS). Notably, Ag-rGO can be also applied to the construction of other value-added chemicals (β-oxopropylcarbamates and 2-oxazolidinones) from CO2 at ambient conditions. In addition, Ag-rGO is stable and reusable, which shows the potential for the practical application for CO2 capture and utilization (CCU).
- Zhang, Xiao,Chen, Kai-Hong,Zhou, Zhi-Hua,He, Liang-Nian
-
p. 4825 - 4830
(2020/08/10)
-
- A highly stable polyoxovanadate-based Cu(i)-MOF for the carboxylative cyclization of CO2with propargylic alcohols at room temperature
-
A novel polyoxovanadate-based copper(i)-organic framework, [CuI(bib)]4{VV4O12} (V-Cu-MOF, bib = 1,4-bis(1H-imidazoly-1-yl)benzene), is facilely synthesized under mild hydrothermal conditions. The structure of the V-Cu-MOF is constructed from a cyclic {V4O12}4- polyanion cluster and a 1D chain Cu(i)-MOF ([CuI(bib)]+). The presence of the {V4O12}4- cluster stabilizes the Cu(i)-MOF with Cu(i) as the center, thereby improving the stability of the V-Cu-MOF and enabling it to stably exist in various solvents and pH = 2-12 solutions. Additionally, the V-Cu-MOF as a heterogeneous catalyst can catalyze the carboxylative cyclization of CO2 and propargylic alcohols to high value-added α-alkylidene cyclic carbonates at room temperature, and the conversion and selectivity are almost 100%. More importantly, no obvious decrease in the yield of the α-alkylidene cyclic carbonate is observed after ten cycles. These results indicate the excellent catalytic activity and sustainability of the V-Cu-MOF. Research on the mechanism of the catalytic reaction suggests that the high-density Cu(i) sites in the V-Cu-MOF are the catalytically active centers for activating the CC bonds of propargylic alcohols. To the best of our knowledge, this is the first example of polyoxometalate-based metal-organic framework catalyst for catalyzing the conversion of CO2 to value-added α-alkylidene cyclic carbonates at room temperature. This journal is
- Dang, Tian-Yi,Li, Zhuo,Liu, Shu-Mei,Liu, Shu-Xia,Lu, Ying,Tian, Hong-Rui,Zhang, Zhong
-
supporting information
p. 7513 - 7520
(2020/11/23)
-
- Selective Conversion of CO 2 and Switchable Alcohols into Linear or Cyclic Carbonates via Versatile Zinc Catalysis
-
It is promising and challenging to achieve the effective construction of carbonates using CO 2 and a non-noble metal catalyst. Herein, selective catalytic conversion of CO 2 and switchable alcohol candidates to produce linear or cyclic carbonates and α-hydroxy ketones via effective zinc catalyst was developed. A series of primary alcohols and cyclohexanol, 1,2-diols, and water can serve as nucleophiles to give alkyl or aryl 2-substituted-3-oxobutan-2-yl carbonates, substituted 1,3-dioxolan-2-ones, 3-substituted 3-hydroxybutan-2-ones, respectively with excellent selectivity and high yields.
- Song, Qing-Wen,Zhao, Qing-Ning,Li, Jing-Yuan,Zhang, Kan,Liu, Ping
-
p. 739 - 746
(2019/01/23)
-
- PROCESS FOR PREPARING CYCLIC CARBONATES
-
The present invention relates to a process for preparing cyclic carbonates of formula Ia or Ib or mixtures thereof (Ia) (Ib) comprising the process step: a) reacting a propargylic alcohol of formula II (II) with carbon dioxide in the presence of at least one transition metal catalyst TMC1, which comprises a transition metal selected from metals of groups 10, 11 and 12 of the periodic table of the elements according to IUPAC and at least one bulky ligand.
- -
-
Page/Page column 26-28
(2019/03/05)
-
- Zinc (II) incorporated porous organic polymeric material (POPs): A mild and efficient catalyst for synthesis of dicoumarols and carboxylative cyclization of propargyl alcohols and CO2 in ambient conditions
-
Zinc (II) incorporated porous organic polymer catalyst, Zn@BBAPA has been designed, synthesized and characterized thoroughly by XRD, EDX, SEM, HR-TEM, FTIR spectra, UV–vis spectra, TGA and N2 absorption desorption isotherm. An eco-friendly porous Zn@BBAPA catalyst exhibits highly efficient catalytic performance for the production of α-alkylidene cyclic carbonates by using propargylic alcohols viaCO2 fixation.In addition the catalyst shows outstanding efficiency for the synthesis of various dicoumarol derivatives in green solvent medium (water)from 4-hydroxycoumarin and aromatic aldehydes. Presence of super hydrophobic nature and electron-donation characterof NH2 groups of BBA framework with high surface area is main aspect to be responsible for elevated catalytic performance as well as improvement in catalyst stability and enabling a good recyclability.
- Islam, Sk Safikul,Salam, Noor,Molla, Rostam Ali,Riyajuddin, Sk,Yasmin, Nasima,Das, Debasis,Ghosh, Kaushik,Islam, Sk Manirul
-
-
- A novel crystalline azine-linked three-dimensional covalent organic framework for CO2 capture and conversion
-
The targeted synthesis of three-dimensional covalent organic frameworks (3D COFs) is a great challenge, especially those synthesized by using a new kind of organic linkage. Herein, for the first time, a novel 3D azine-linked COF (3D-HNU5) has been synthesized and characterized. It is shown that the obtained 3D COF has a 2-fold interpenetrated diamond topology, and shows good chemical/thermal stability and a narrow pore size distribution, which exhibits excellent performance in the selective uptake of CO2 over N2. Moreover, the 3D-HNU5 is found to be an efficient catalyst for the cycloaddition of propargylic alcohols with CO2 into carbonates with excellent catalytic activity under mild conditions.
- Guan, Pengxin,Qiu, Jikuan,Zhao, Yuling,Wang, Huiyong,Li, Zhiyong,Shi, Yunlei,Wang, Jianji
-
supporting information
p. 12459 - 12462
(2019/10/23)
-
- Copper(i) iodide cluster-based lanthanide organic frameworks: Synthesis and application as efficient catalysts for carboxylative cyclization of propargyl alcohols with CO2 under mild conditions
-
Two metal-organic frameworks (MOFs), namely, [Dy2Cu4I4(NA)6(DMF)2]n (1) and [Gd2Cu2I2(IN)6(DMF)4]·5DMF (2) (HNA = nicotinic acid, HIN = isonicotinic acid), constructed based on lanthanide ions and copper iodide clusters ([Cu4I4] and [Cu2I2]) were successfully synthesized and characterized. Compound 1 has a three-dimensional framework and compound 2 displays a two-dimensional plane with sql topology, respectively. Both of them exhibit high thermostability and solvent stabilities. Additionally, catalytic explorations reveal that 1 displays higher catalytic activity than 2 for the carboxylic cyclization of propargyl alcohols. More importantly, 1 also exhibits excellent catalytic performance in the carboxylation reactions of CO2 and terminal propargylic alcohols with various substituents. To the best of our knowledge, this is the first example of non-noble metal based MOF catalysts for the carboxylative cyclization of propargyl alcohols with CO2 under atmospheric pressure and at room temperature, which provides a highly promising approach for MOFs in the catalytic conversion of CO2 to valuable chemicals.
- Bai, Guoyi,Lan, Xingwang,Li, Meng,Wu, Zhilei,Zhang, Yaxin
-
supporting information
p. 11063 - 11069
(2019/08/01)
-
- Isolable CO2 Adducts of Polarized Alkenes: High Thermal Stability and Catalytic Activity for CO2 Chemical Transformation
-
Various CO2 adducts of tetra-hydropyrimidin-2-ylidene (THPE) derived from the commercially available 1, 5-diazabicyclo[4.3.0]non-5-ene (DBN) were firstly synthesized. X-ray single crystal analysis revealed the bent geometry of the binding CO2 having an O?C?O angle of 127.50~129.51° for THPE?CO2 adducts. In situ FTIR experiments demonstrated that THPE?CO2 adducts had unprecedented thermal stability in DMSO, even at 100 °C without decomposition. It was found that the THPE?CO2 adducts were highly active in catalyzing the carboxylative cyclization of CO2 with propargylic alcohols under mild conditions, significantly higher than the previously reported organocatalysts. Various internal and terminal functionalized propargylic alcohols were tolerated in these processes to afford the corresponding α-alkylidene cyclic carbonates in moderate to good yields with complete (Z)-stereoselectivity. Isotope labeling, in combination with in-situ FTIR and stoichiometric experiments, reveal that the catalytic reaction tends to proceed via the THPE?CO2-mediated basic ionic pair mechanism. (Figure presented.).
- Zhou, Hui,Zhang, Rui,Lu, Xiao-Bing
-
supporting information
p. 326 - 334
(2019/01/04)
-
- Silver-Catalyzed Carboxylative Cyclization of Primary Propargyl Alcohols with CO2
-
By using silver complexes with bulky ligands such as DavePhos or N-heterocyclic carbenes, propargylic alcohols are smoothly converted with CO2 into a unique class of unexplored cyclic alkylidene carbonates. These systems, for the first time, also achieve the direct carboxylative cyclization of primary propargylic alcohols. The silver-DavePhos catalyst is further applied for the bis-carboxylative cyclization of primary propargyl derivatives, thereby providing an effective route to a series of previously inaccessible and industrially relevant α-alkylidene cyclic carbonates.
- Dabral, Saumya,Bayarmagnai, Bilguun,Hermsen, Marko,Schie?l, Jasmin,Mormul, Verena,Hashmi, A. Stephen K.,Schaub, Thomas
-
supporting information
(2019/03/07)
-
- Silver-Catalyzed Carboxylative Cyclization of Primary Propargyl Alcohols with CO2
-
By using silver complexes with bulky ligands such as DavePhos or N-heterocyclic carbenes, propargylic alcohols are smoothly converted with CO2 into a unique class of unexplored cyclic alkylidene carbonates. These systems, for the first time, also achieve the direct carboxylative cyclization of primary propargylic alcohols. The silver-DavePhos catalyst is further applied for the bis-carboxylative cyclization of primary propargyl derivatives, thereby providing an effective route to a series of previously inaccessible and industrially relevant α-alkylidene cyclic carbonates.
- Dabral, Saumya,Bayarmagnai, Bilguun,Hermsen, Marko,Schie?l, Jasmin,Mormul, Verena,Hashmi, A. Stephen K.,Schaub, Thomas
-
supporting information
p. 1422 - 1425
(2019/03/08)
-
- A rose bengal-functionalized porous organic polymer for carboxylative cyclization of propargyl alcohols with CO2
-
A Rose bengal-functionalized porous organic polymer (RB-POP) was prepared with a specific surface area of up to 562 m2 g-1. In the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene, RB-POP supported Ag(0) nanoparticles exhibited excellent performance for catalyzing cyclization of propargyl alcohols with CO2 at 30 °C, achieving a TOF of 5000 h-1, the highest value among the reported ones.
- Yu, Xiaoxiao,Yang, Zhenzhen,Zhang, Fengtao,Liu, Zhenghui,Yang, Peng,Zhang, Hongye,Yu, Bo,Zhao, Yanfei,Liu, Zhimin
-
supporting information
p. 12475 - 12478
(2019/10/23)
-
- Synthesis of Α-hydroxy ketones by copper(I)-catalyzed hydration of propargylic alcohols: CO2 as a cocatalyst under atmospheric pressure
-
Inexpensive and efficient Cu(I) catalysis is reported for the synthesis of α-hydroxy ketones from propargylic alcohols, CO2, and water via tandem carboxylative cyclization and nucleophilic addition reaction. Notably, hydration of propargylic alcohols can be carried out smoothly under atmospheric CO2 pressure, generating a series of α-hydroxy ketones efficiently and selectively. This strategy shows great potential for the preparation of valuable α-hydroxy ketones by using CO2 as a crucial cocatalyst under mild conditions.
- Zhou, Zhi-Hua,Zhang, Xiao,Huang, Yong-Fu,Chen, Kai-Hong,He, Liang-Nian
-
p. 1345 - 1351
(2019/08/07)
-
- A Noble-Metal-Free Metal–Organic Framework (MOF) Catalyst for the Highly Efficient Conversion of CO2 with Propargylic Alcohols
-
Cyclization of propargylic alcohols with CO2 is an important reaction in industry, and noble-metal catalysts are often employed to ensure the high product yields under environmentally friendly conditions. Herein a porous noble-metal-free framework 1 with large 1D channels of 1.66 nm diameter was synthesized for this reaction. Compound 1 exhibits excellent acid/base stability, and is even stable in corrosive triethylamine for one month. Catalytic studies indicate that 1 is an effective catalyst for the cyclization of propargylic alcohols and CO2 without any solvents under mild conditions, and the turnover number (TON) can reach to a record value of 14 400. Furthermore, this MOF catalyst also has rarely seen catalytic activity when the biological macromolecule ethisterone was used as a substrate. Mechanistic studies reveal that the synergistic catalytic effect between CuI and InIII plays a key role in the conversion of CO2.
- Hou, Sheng-Li,Dong, Jie,Jiang, Xiao-Lei,Jiao, Zhuo-Hao,Zhao, Bin
-
supporting information
p. 577 - 581
(2018/12/11)
-
- Synergistic Ag(I)/nBu4NBr-catalyzed fixation of CO2 to β-oxopropyl carbonates via propargylic alcohols and monohydric alcohols
-
Chemical fixation of carbon dioxide under mild reaction conditions e.g. atmospheric pressure and low temperature depends upon the ability of catalyst. Herein, a synergistic catalytic scheme of silver sulfadiazine/nBu4NBr was described for the three-component reaction of propargylic alcohols, CO2, and monohydric alcohols. This catalytic system was demonstrated effectively to provide β-oxopropyl carbonates in excellent yields (up to 99% yield with 5 mol% catalyst). The method tolerated a wide scope of propargylic alcohols and monohydric alcohols under atmospheric CO2 pressure and solvent-free conditions. The excellent catalytic performance was attributed to the synergistic catalysis confirmed by the careful experiments.
- Li, Jingyuan,Song, Qingwen,Zhang, Hengxuan,Liu, Ping,Zhang, Kan,Wang, Junwen,Zhang, Dengsong
-
p. 2343 - 2349
(2019/03/13)
-
- Highly regio- And stereoselective synthesis of cyclic carbonates from biomass-derived polyols: Via organocatalytic cascade reaction
-
The cascade reaction of CO2, vicinal diols, and propargylic alcohol, was firstly achieved by dual Lewis base (LB) organocatalytic systems involving LB-CO2 adducts and commercially available organic amines. This methodology could overcome the chemical inertness of CO2, providing an alternative route to various functionalized five-membered cyclic carbonates in moderate to high yields under mild reaction conditions (25 °C, 1.0 atm of CO2). More importantly, this method could also be applied for facile and efficient synthesis of chiral polycyclic carbonates from biomass-derived polyols with complete configuration retention of chiral centers. This study provides an environment-friendly, scalable and cost effective protocol to construct value-added cyclic carbonates with multi-functional groups and chiral centers.
- Zhou, Hui,Zhang, Hui,Mu, Sen,Zhang, Wen-Zhen,Ren, Wei-Min,Lu, Xiao-Bing
-
p. 6335 - 6341
(2019/12/03)
-
- Boosting the Catalytic Performance of Organic Salts for the Fast and Selective Synthesis of α-Alkylidene Cyclic Carbonates from Carbon Dioxide and Propargylic Alcohols
-
The synthesis of α-alkylidene cyclic carbonates (αCCs) by the carboxylative coupling of CO2 with propargylic alcohols is receiving increasing interest but requires the use of catalysts that are most often added in large quantities and/or lack selectivity. Herein, we describe the fine-tuning of the structure of organocatalysts of the ammonium-type that enables us to identify the important structural parameters that dictate their catalytic performance. Tetrabutylammonium oxalate was revealed to be one of the most attractive organocatalysts with a remarkably fast, complete and selective production of αCCs at a low catalyst loading (2.5 mol %) under solvent-free conditions. This study opens new avenues for the facile and selective synthesis of libraries of αCCs from CO2 and propargylic alcohol by using simple organocatalysts.
- Grignard, Bruno,Ngassamtounzoua, Charlène,Gennen, Sandro,Gilbert, Bernard,Méreau, Rapha?l,Jerome, Christine,Tassaing, Thierry,Detrembleur, Christophe
-
p. 2584 - 2592
(2018/06/27)
-
- Tetrabutylammonium Salts: Cheap Catalysts for the Facile and Selective Synthesis of α-Alkylidene Cyclic Carbonates from Carbon Dioxide and Alkynols
-
n-Tetrabutylammonium organic salts were used for the first time as catalysts for the coupling of CO2 with 2-methyl-3-butyn-2-ol to form an α-methylene cyclic carbonate. Final yields up to 98 % were reached in less than 10 h at 353 K and 3 MPa under solvent-free conditions. A particular synergistic effect between the cation and the anion of the organocatalyst was demonstrated through catalyst screening. Online kinetic studies by Attenuated Total Reflectance (ATR) IR spectroscopy correlated to DFT calculations revealed compelling evolution of solvation of the catalyst during the reaction that provided insight into the underlying reason for the observed unique kinetics and selectivity. Such in-depth fundamental mechanistic and kinetic studies enabled determination and comprehension of the key parameters favoring the design of novel, highly active and selective catalysts for valorization of CO2 as a chemical feedstock.
- Méreau, Rapha?l,Grignard, Bruno,Boyaval, Amélie,Detrembleur, Christophe,Jerome, Christine,Tassaing, Thierry
-
p. 956 - 960
(2018/02/09)
-
- CO2 transformation under mild conditions using tripolyphosphate-grafted KCC-1-NH2
-
Fibrous nanosilica (KCC-1) as a catalyst support was investigated in terms of stability, recycling, and reusability. For the first time, CO2 transformation was performed via the synthesis and application of KCC-1 together with sodium tripolyphosphate (STPP) and 3-aminopropyltriethoxysilane (APTES) as its functionalized derivative. To this goal, KCC-1/STPP NPs were applied to act as a nanocatalyst with excellent catalytic activities under green reaction conditions.
- Sadeghzadeh, Seyed Mohsen,Zhiani, Rahele,Moradi, Marjan
-
p. 535 - 544
(2018/04/26)
-
- Naturally occurring gallic acid derived multifunctional porous polymers for highly efficient CO2 conversion and I2 capture
-
Assembly of naturally occurring building blocks into functional materials is of great importance. Herein, we utilized plant-derived polyphenols as building blocks to prepare porous organic polymers (POPs) with multifunctional sites, and a typical POP (denoted as GA-azo-POP) could be achieved from gallic acid through an azo-coupling strategy. As a superior support, GA-azo-POP supported Ag nanoparticles could efficiently catalyze the carboxylative cyclization of propargyl alcohols with CO2 with a very low usage of Ag (0.14 mol%). Meanwhile, the GA-azo-POP showed a high capacity for I2 adsorption (up to 287 mg g-1), which was higher than that of the reported solid materials at a similar I2 concentration. More interestingly, after adsorbing I2, the GA-azo-POP could efficiently catalyze the formation of cyclic carbonates from CO2. The excellent performance of the GA-azo-POP resulted from the co-existence of aromatic, azo, and phenolic OH functional groups and its porous structure.
- Xie, Chao,Song, Jinliang,Wu, Haoran,Hu, Yue,Liu, Huizhen,Yang, Youdi,Zhang, Zhanrong,Chen, Bingfeng,Han, Buxing
-
p. 4655 - 4661
(2018/10/23)
-
- Upgrading CO2 by Incorporation into Urethanes through Silver-Catalyzed One-Pot Stepwise Amidation Reaction
-
One-pot two-step stepwise reaction of terminal propargylic alcohols, carbon dioxide, and primary/secondary amines for the effective synthesis of various urethanes through robust silver-catalysed C-O/C-N bond formation is reported. Catalytic activities were investigated by controlling catalyst loading, reaction pressure and time, and very high turnover number (turnover frequency) was obtained: 3350 (35 h?1) with 0.01 mol% silver catalyst under 0.1 MPa, and up to 13360 (139 h?1) with 0.005 mol% silver catalyst under 2.0 MPa at room temperature. The strategy was ingeniously regulated, and synchronously afforded a wide range of β-oxopropylcarbamate and 1,3-oxazolidin-2-one motifs in excellent yields and selectivity together with unprecedented high turnover number (TON) and turnover frequency (TOF) value.
- Song, Qing-Wen,Liu, Ping,Han, Li-Hua,Zhang, Kan,He, Liang-Nian
-
p. 147 - 152
(2018/01/05)
-
- Unusual Missing Linkers in an Organosulfonate-Based Primitive-Cubic (pcu)-Type Metal-Organic Framework for CO2 Capture and Conversion under Ambient Conditions
-
A noninterpenetrated organosulfonate-based metal-organic framework (MOF) with a defective primitive-cubic (pcu) topology was successfully synthesized. The unusual missing linkers, along with the highest permanent porosity (~43%) in sulfonate-MOFs, offer a versatile platform for the incorporation of alkynophilic Ag(I) sites. The cyclic carboxylation of alkyne molecules (e.g., propargyl alcohol and propargyl amine) into α-alkylidene cyclic carbonates and oxazolidinones were successfully catalyzed by the use of Ag(I)-embedded sulfonate-MOF under atmospheric pressure of CO2. In all the three catalytic reactions using CO2 as a C1 feedstock, the highly robust sulfonate-based MOF catalyst exhibit at least three-cycle reusability.
- Zhang, Guiyang,Yang, Huimin,Fei, Honghan
-
p. 2519 - 2525
(2018/03/13)
-
- A simple and robust AgI/KOAc catalytic system for the carboxylative assembly of propargyl alcohols and carbon dioxide at atmospheric pressure
-
A simple and robust AgI/KOAc system was developed for the cyclization of propargyl alcohols and carbon dioxide under mild conditions, and was identified to have excellent activities for numerous substrates, especially sterically hindered terminal alkynes and internal alkynes. Notably, the Ag loading involved was an unprecedentedly low level of 0.05 mol%.
- Yuan, Ye,Xie, Yu,Zeng, Cheng,Song, Dandan,Chaemchuen, Somboon,Chen, Cheng,Verpoort, Francis
-
p. 2933 - 2939
(2017/08/14)
-
- A chemical fixed carbon dioxide preparation five yuan cyclic carbonate method (by machine translation)
-
The invention discloses a chemical fixed carbon dioxide preparation five yuan cyclic carbonate, in the presence of carbon dioxide, in the organic phase, closed in a high pressure, in order to N - heterocyclic cabeen silver (CNT/GN - NHC - Ag) as catalyst, catalyzed alkyne propanol into five yuan cyclic carbonate, the reaction time is 4 - 28 the H; the reaction temperature is 20 - 100 °C; the reaction pressure is 0.1 - 5 mpa; the consumption of catalyst with the propargyl alcohol weight ratio of 60 - 100:45, silver loading is 5% -12%. The invention relatively mild reaction conditions, it is easy to realize, economic and environmental protection, and atom utilization rate high, high catalytic efficiency, optimal conversion rate may reach 99.9%, its selectivity can reach 100%. (by machine translation)
- -
-
Paragraph 0009; 0010; 0011-0022; 0031-0060
(2017/08/31)
-
- Method for preparing unsaturated cyclic carbonate by using carbon dioxide as raw material
-
The invention discloses a method for preparing unsaturated cyclic carbonate. The method comprises the step of performing a catalytic reaction on alkynol and CO2 in a reactor in the presence of sulfonic acid resin loaded silver nano-particles, an alkali promoter and a solvent to obtain unsaturated cyclic carbonate. According to the method, a silver nano-particle catalyst with uniform granularity and high dispersion in the sulfonic acid resin loaded silver nano-particles is utilized for the first time, the catalytic system formed by the catalyst, the alkali promoter and the solvent is utilized, and carbon dioxide and alkynol serving as raw materials are used for preparing unsaturated cyclic carbonate at normal temperature and normal pressure. The preparation method is simple. The catalyst has excellent activity, stability and recycling performance, and has a great application value.
- -
-
Paragraph 0066-0083
(2017/08/28)
-
- A recyclable AgI/OAc- catalytic system for the efficient synthesis of α-alkylidene cyclic carbonates: Carbon dioxide conversion at atmospheric pressure
-
The cyclization of carbon dioxide and propargylic alcohols, especially challenging substrates, were efficiently catalyzed by a green and recyclable AgI/OAc- system under atmospheric pressure, which is shown to be the most recyclable system with 20 recycle rounds and has the lowest loading among all the reported recyclable systems that work under atmospheric pressure.
- Yuan, Ye,Xie, Yu,Zeng, Cheng,Song, Dandan,Chaemchuen, Somboon,Chen, Cheng,Verpoort, Francis
-
supporting information
p. 2936 - 2940
(2017/07/24)
-
- One-pot carboxylative cyclization of propargylic alcohols and CO2 catalysed by N-heterocyclic carbene/Ag systems
-
A series of N-heterocyclic carbene (NHC)/Ag systems were developed for the carboxylative assembly of propargylic alcohols and carbon dioxide (CO2). With the catalysis of these catalytic systems, a variety of target α-alkylidene cyclic carbonates could be obtained smoothly under atmospheric CO2 pressure in straightforward one-pot processes. Particularly, these reactions could be performed without any stoichiometric addition of bases or additives. Further mechanistic investigation reveals that the excellent activities are attributed to the effective activations of CO2 accomplished by the NHCs via the formation of the NHC-CO2 adducts.
- Yuan, Ye,Xie, Yu,Song, Dandan,Zeng, Cheng,Chaemchuen, Somboon,Chen, Cheng,Verpoort, Francis
-
-
- Synthesis of Asymmetrical Organic Carbonates using CO2 as a Feedstock in AgCl/Ionic Liquid System at Ambient Conditions
-
Synthesis of asymmetrical organic carbonates from the renewable and inexpensive CO2 is of great importance but also challenging, especially at ambient conditions. Herein, we found that some metal salt/ionic liquid catalyst systems were highly active for the synthesis of asymmetrical organic carbonates from CO2, propargylic alcohols, and primary alcohols. Especially, the AgCl/1-butyl-3-methylimidazolium acetate ([Bmim][OAc]) system was very efficient for the reactions of a wide range of substrates at room temperature and atmospheric pressure, and the yields of the asymmetrical organic carbonates could approach 100 %. The catalyst system could be reused at least five times without changing its catalytic performance, and could be easily recovered and reused. A detailed study indicated that AgCl and [Bmim][OAc] catalyzed the reactions cooperatively, resulting in unique catalytic performance.
- Hu, Jiayin,Ma, Jun,Lu, Lu,Qian, Qingli,Zhang, Zhaofu,Xie, Chao,Han, Buxing
-
p. 1292 - 1297
(2017/03/27)
-
- AgI/TMG-Promoted Cascade Reaction of Propargyl Alcohols, Carbon Dioxide, and 2-Aminoethanols to 2-Oxazolidinones
-
Chemical valorization of CO2 to access various value-added compounds has been a long-term and challenging objective from the viewpoint of sustainable chemistry. Herein, a one-pot three-component reaction of terminal propargyl alcohols, CO2, and 2-aminoethanols was developed for the synthesis of 2-oxazolidinones and an equal amount of α-hydroxyl ketones promoted by Ag2O/TMG (1,1,3,3-tetramethylguanidine) with a TON (turnover number) of up to 1260. By addition of terminal propargyl alcohol, the thermodynamic disadvantage of the conventional 2-aminoethanol/CO2 coupling was ameliorated. Mechanistic investigations including control experiments, DFT calculation, kinetic and NMR studies suggest that the reaction proceeds through a cascade pathway and TMG could activate propargyl alcohol and 2-aminoethanol through the formation of hydrogen bonds and also activate CO2.
- Li, Xue-Dong,Song, Qing-Wen,Lang, Xian-Dong,Chang, Yao,He, Liang-Nian
-
p. 3182 - 3188
(2017/10/03)
-
- Alkyne Activation by a Porous Silver Coordination Polymer for Heterogeneous Catalysis of Carbon Dioxide Cycloaddition
-
The widely studied porous coordination polymers, possessing large pores to adsorb waste carbon dioxide gas and further transform it into valuable chemical products, have been attracting research interest, both industrially and academically. The active silver(I) ions endow the specific alkynophilicity to activate C≡C bonds of alkyne-containing molecules via π activation. Incorporating catalytic Ag metal sites into the porous frameworks represents a promising approach to construct heterogeneous catalysts that cyclize propargylic alcohols with CO2, which is highly desirable for the environmentally benign conversion of carbon dioxide to fine chemicals. We report the preparation of porous coordination polymers (PCPs) with active silver sites and efficient silver-silver bond formation by carefully modifying the coordination geometries of the silver sites. The decentralized silver(I) chains in the porous frameworks enable the efficient conversion of CO2 and derivatives of acetylene to α-alkylidene cyclic carbonates in a heterogeneous manner. X-ray structure analysis reveals two kinds of substrate molecules positioned within the pores of the framework, which correspond to trapping and activated modes through the multiple interactions with the functional Ag chains. The example of tandem conversion of simple alkynes and carbon dioxide to α-alkylidene cyclic carbonates is also presented. The well-positioned catalytic silver(I) sites and the crystalline properties of the frameworks facilitated the structural analyses of the intermediates of each catalytic step, providing knowledge of the synergistic nature of the σ and π activation of C≡C bonds. The successful catalysis of azide-alkyne cycloaddition and synthesis of propargylic alcohols via terminal alkynes could also give another indicator for the activation properties of Ag sites.
- Zhou, Zhen,He, Cheng,Yang, Lu,Wang, Yefei,Liu, Tao,Duan, Chunying
-
p. 2248 - 2256
(2017/08/14)
-
- Tetrabutylphosphonium-Based Ionic Liquid Catalyzed CO2 Transformation at Ambient Conditions: A Case of Synthesis of α-Alkylidene Cyclic Carbonates
-
A series of tetrabutylphosphonium ([Bu4P]+)-based ionic liquids (ILs) with multiple-site for CO2 capture and activation in their anions, which could efficiently catalyze the cyclization reaction of propargylic alcohols with CO2 at ambient conditions, are reported. Especially, the IL, [Bu4P]3[2,4-OPym-5-Ac], which has three interaction sites for attracting CO2 together with a pKa1 value of 9.13, exhibited the best performance, affording a series of α-alkylidene cyclic carbonates in moderate to good yields. The mechanism exploration demonstrated that IL served as a bifunctional catalyst with anion simultaneously activating CO2 via multiple-site cooperative interactions and the C≡C triple bond in propargylic alcohol via inductive effect, thus resulting in the production of α-alkylidene cyclic carbonates. (Chemical Equation Presented).
- Wu, Yunyan,Zhao, Yanfei,Li, Ruipeng,Yu, Bo,Chen, Yu,Liu, Xinwei,Wu, Cailing,Luo, Xiaoying,Liu, Zhimin
-
p. 6251 - 6255
(2017/09/15)
-
- Organocatalytic Coupling of CO2 with a Propargylic Alcohol: A Comprehensive Mechanistic Study
-
The metal-free coupling of a propargylic alcohol with CO2 catalysed by guanidine derivatives was investigated in detail through the combination of online kinetic studies by in situ attenuated-total reflection IR (ATR–IR) spectroscopy and DFT calculations. Bicyclic guanidines, namely 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) and 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD) are effective catalysts for the conversion of 2-methyl-3-butyn-2-ol to α-methylene cyclic carbonate and oxoalkyl acyclic carbonate under mild reaction conditions. The lower selectivity of TBD in comparison with MTBD towards the formation of α-methylene cyclic carbonate was elucidated from DFT calculations and is related to the bifunctional activity (base/H-bond donor) of TBD decreasing the Gibbs free energy of the reaction path for the formation of the acyclic carbonate.
- Boyaval, Amélie,Méreau, Rapha?l,Grignard, Bruno,Detrembleur, Christophe,Jerome, Christine,Tassaing, Thierry
-
p. 1241 - 1248
(2017/03/29)
-
- Zinc(II)-catalyzed reactions of carbon dioxide and propargylic alcohols to carbonates at room temperature
-
Carbon dioxide (CO2) is an abundant and renewable feedstock for the production of value-added chemicals. Herein, we carried out the first work to use ZnI2/NEt3 as the catalyst for the reactions of CO2 and propargylic alcohols to form α-alkylidene cyclic carbonates. It was discovered that the catalyst system could efficiently promote the reaction at room temperature under solvent-free conditions, and the yields of the target products could reach 99%. The zinc(ii) and NEt3 play excellent synergistic roles in activating both CO2 and propargylic alcohols.
- Hu, Jiayin,Ma, Jun,Zhu, Qinggong,Qian, Qingli,Han, Hongling,Mei, Qingqing,Han, Buxing
-
supporting information
p. 382 - 385
(2016/01/30)
-
- Metalated Mesoporous Poly(triphenylphosphine) with Azo Functionality: Efficient Catalysts for CO2 Conversion
-
Mesoporous poly(triphenylphosphine) with azo functionality (poly(PPh3)-azo) is reported, which was synthesized via oxidative polymerization of P(m-NH2Ph)3 at ambient conditions. This kind of polymer could strongly coordinate with metal ions (e.g., Ru3+) and could reduce Ag+ in situ to metallic form. The resultant metalated poly(PPh3)-azo (e.g., poly(PPh3)-azo-Ag or -Ru) were discovered to be highly efficient catalysts for CO2 transformation. Poly(PPh3)-azo-Ag showed more than 400 times higher site-time-yield (STY) for the carboxylative cyclization of propargylic alcohols with CO2 at room temperature compared with the best heterogeneous catalyst reported. Poly(PPh3)-azo-Ru also exhibited good activity for the methylation of amines with CO2. It was demonstrated that the high performances of the catalysts originated from the cooperative effects between the polymer and the metal species. In addition, both catalysts showed good stability and easy recyclability, thus demonstrating promising potential for practical utilization for the conversion of CO2 into value-added chemicals.
- Yang, Zhenzhen,Yu, Bo,Zhang, Hongye,Zhao, Yanfei,Chen, Yu,Ma, Zhishuang,Ji, Guipeng,Gao, Xiang,Han, Buxing,Liu, Zhimin
-
p. 1268 - 1273
(2016/02/18)
-