95323-23-2

Upstream product

• 127-66-2 2-Phenyl-3-butyn-2-ol 
• 124-38-9 carbon dioxide 

Downstream Products

• 3155-01-9 3-hydroxy-3-phenyl-butan-2-one 

Relevant academic research and scientific papers

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.

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.

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.

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.

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).

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.

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

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.).

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.

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.