Homogeneous Metal-Based Catalysis in Supercritical Carbon Dioxide as Reaction Medium

Olmos, Andrea; Asensio, Gregorio; Pérez, Pedro J.

doi:10.1021/acscatal.6b00848

Cited by 49 publications

(25 citation statements)

References 174 publications

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“…[30] Presently,m any examples of synthesis of different compounds as well as the separation of products from the reaction system by using scCO 2 have been reported and offer ac hance to make processes environmentally friendly by reduction of volatile organic solvents ande liminationo fs eparation steps. [31] The solubilityo fc ompounds in scCO 2 mainly depends on their polarity,volatility,and molecular weight. Moreover,different functional groups attachedt ot he compounds can influence their solubility in this green solvent.…”

Section: Hydroboration Of Terminal Alkynes Under Optimized Conditionsmentioning

confidence: 99%

An Effective Catalytic Hydroboration of Alkynes in Supercritical CO₂ under Repetitive Batch Mode

et al. 2018

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A facile method for the synthesis of unsaturated organoboron compounds by hydroboration of terminal and internal alkynes in supercritical (sc) CO2 has been presented for the first time. The reactions performed in scCO2 in the presence of Ru catalysts (selectivity, productivity) are compared with those in a traditionally used solvent or without it. Moreover, the catalytic systems based on the application of scCO2 have been successfully tested for the processes under repetitive batch conditions. This strategy permitted us to obtain boryl‐substituted olefins with high yields and selectivities up to the 16th catalytic cycle if using Ru(CO)Cl(H)(PPh3)3 as a catalyst. The process applied the self‐dosing catalyst, which is gradually released to the reaction mixture under supercritical conditions in the individual batch. Such an approach has a positive impact on process sustainability and economy.

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Section: Hydroboration Of Terminal Alkynes Under Optimized Conditionsmentioning

confidence: 99%

An Effective Catalytic Hydroboration of Alkynes in Supercritical CO₂ under Repetitive Batch Mode

et al. 2018

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“…[a] EntryC atalyst Ligand Yield of 1 [%] [b] Yield of 2 [%] [b] 1Z ChemSusChem 2017ChemSusChem , 10,1501ChemSusChem -1508 www.chemsuschem.org the reactions ystem in situ as the standard reactionc onditions. [24] Like MeCN, CO 2 behaves as asolvent that diluted the components of the reactions ystem. Even if ac atalyst and ligand are employed,h igh temperatures (> 100 8C) are often required for carbamate synthesis directly from an amine, CO 2 ,a nd TMOS.…”

Section: Resultsmentioning

confidence: 99%

“…The low yield of 1 at high CO 2 pressures suggested that ah igh-density CO 2 condensate formed from the gas phase. [24] Like MeCN, CO 2 behaves as asolvent that diluted the components of the reactions ystem. [25] Figure2 shows that the best resultsw ere obtained at aC O 2 pressureo f5MPa, whichp rovided the highest yield and selectivity.…”

Section: Resultsmentioning

confidence: 99%

A Simple Zinc Catalyst for Carbamate Synthesis Directly from CO₂

et al. 2017

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Several zinc salts were employed as catalysts for the synthesis of carbamates directly from aromatic amines, CO , and silicate esters. Zn(OAc) offered the best performance among the salts tested. The addition of an N-donor ligand such as 1,10-phenanthroline increased the yield. The best catalytic performance of Zn(OAc) can be explained by carboxylate-assisted proton activation. The interaction between the substrate and the catalyst can be observed by chemical shifts in H and N NMR spectra. Isocyanate was a key intermediate, which was generated from amine and CO . Silicate ester was finally converted to siloxane, which was determined by Si NMR. The commercially available catalyst system could be reused. The yield of isolated carbamate could reach up to 96 % with various substrates, and the catalytic reaction was amine-selective in the presence of other functional groups.

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“…In this regard, a substantial research effort has been made to replace these conventional harmful solvents by sustainable media . The sustainable media applied for synthetic organic processes are principally supercritical carbon dioxide, bio‐based solvents such as glycerol, poly(ethylene glycol)s, ionic liquids, and deep eutectic solvents …”

Section: Optimization Of the Reaction Conditions On The Model Reactionmentioning

confidence: 99%

ZnCl₂/Urea Eutectic Solvent as Stable Carbonylation Source for Benign Synthesis of 2–Benzimidazolones and 2–Imidazolones: An Effective Strategy for Preventing NH₃ Gas Evolution

et al. 2019

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The synthesis of 2‐benzimidazolone and 2‐imidazolone derivatives from urea as an inexpensive widely available carbonyl source is usually performed in high boiling organic solvents accompanied by ammonia evolution, due to urea decomposition. In this paper, a sustainable method has been introduced for the synthesis of these N,N‐heterocycles by employing zinc chloride:urea (1 : 3.5) type IV eutectic mixture under mild reaction conditions. No urea was used directly in the reaction owing to the fact that the eutectic mixture (containing urea itself) suffice to provide the carbonylation source. This new concept allowed the smooth conversion of a range of arene‐1,2‐diamines and benzoins to the corresponding N,N‐heterocycle in efficient yields. The remarkable advantage of this green protocol over other conventional heating procedures is that all reactions are conducted under open‐vessel conditions due to the absorption of the evolved ammonia by the eutectic mixture during the reaction process. (© WILEY‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

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Homogeneous Metal-Based Catalysis in Supercritical Carbon Dioxide as Reaction Medium

Cited by 49 publications

References 174 publications

An Effective Catalytic Hydroboration of Alkynes in Supercritical CO₂ under Repetitive Batch Mode

An Effective Catalytic Hydroboration of Alkynes in Supercritical CO₂ under Repetitive Batch Mode

A Simple Zinc Catalyst for Carbamate Synthesis Directly from CO₂

ZnCl₂/Urea Eutectic Solvent as Stable Carbonylation Source for Benign Synthesis of 2–Benzimidazolones and 2–Imidazolones: An Effective Strategy for Preventing NH₃ Gas Evolution

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Homogeneous Metal-Based Catalysis in Supercritical Carbon Dioxide as Reaction Medium

Cited by 49 publications

References 174 publications

An Effective Catalytic Hydroboration of Alkynes in Supercritical CO2 under Repetitive Batch Mode

An Effective Catalytic Hydroboration of Alkynes in Supercritical CO2 under Repetitive Batch Mode

A Simple Zinc Catalyst for Carbamate Synthesis Directly from CO2

ZnCl2/Urea Eutectic Solvent as Stable Carbonylation Source for Benign Synthesis of 2–Benzimidazolones and 2–Imidazolones: An Effective Strategy for Preventing NH3 Gas Evolution

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An Effective Catalytic Hydroboration of Alkynes in Supercritical CO₂ under Repetitive Batch Mode

An Effective Catalytic Hydroboration of Alkynes in Supercritical CO₂ under Repetitive Batch Mode

A Simple Zinc Catalyst for Carbamate Synthesis Directly from CO₂

ZnCl₂/Urea Eutectic Solvent as Stable Carbonylation Source for Benign Synthesis of 2–Benzimidazolones and 2–Imidazolones: An Effective Strategy for Preventing NH₃ Gas Evolution