Baeyer—Villiger Oxidation in Supercritical CO2 with Potassium Peroxomonosulfate Supported on Acidic Silica Gel.

Supercritical carbon dioxide (scCO2) is an efficient reaction medium to perform the Baeyer-Villiger oxidation with hydrated silica-supported potassium peroxomonosulfate (h-SiO2.KHSO5) under flow-through conditions. Hydration modulates the reactivity of the active surface by softening the acidity of the KHSO4 present in the supported reagent. The reaction in scCO2 is much more efficient than in n-hexane under similar conditions, which is attributed to better transport and solvating properties of the supercritical medium with regard to n-hexane.

Cover Picture: Measuring the Relative Reactivity of the Carbon–Hydrogen Bonds of Alkanes as Nucleophiles (Angew. Chem. Int. Ed. 42/2018)

Epoxidation of Olefins with a Silica-Supported Peracid in Supercritical Carbon Dioxide under Flow Conditions

Anhydrous 2-percarboxyethyl-functionalized silica (2b), a recyclable supported peracid, is a suitable reagent to perform the epoxidation of alkenes 1 in supercritical carbon dioxide at 250 bar and 40 °C under flow conditions. This procedure simplifies the isolation of the reaction products and uses only carbon dioxide as a solvent under mild conditions. The solid reagent 2b can be easily recycled by a reaction with 30% hydrogen peroxide in an acid medium.

Catalytic Functionalization of Methane and Light Alkanes in Supercritical Carbon Dioxide

International audience; The development of catalytic methods for the effective functionalization of methane yet remains a challenge. The best system known to date is the so-called Catalytica Process based on the use of platinum catalysts to convert methane into methyl bisulfate with a TOF rate of 10−3 s. In this contribution, we report a series of silver complexes containing perfluorinated tris(indazolyl)borate ligands that catalyze the functionalization of methane into ethyl propionate upon reaction with ethyl diazoacetate (EDA) by using supercritical carbon dioxide (scCO2) as the reaction medium. The employment of this reaction medium has also allowed the functionalization of ethane, prop…

Silica-Immobilized NHC-Gold(I) Complexes: Versatile Catalysts for the Functionalization of Alkynes under Batch and Continuous Flow Conditions

Immobilized sterically demanding NHC-Au(I) complexes silica-[(IPrR)Au]Cl and silica-[(IAdPrR)Au]Cl are synthesized and characterized. These complexes are suitable catalysts in typical homogeneous Au(I)-catalyzed alkyne reactions such as hydration, hydroamination, hydroarylation, or cycloisomerization. The results obtained with the immobilized catalysts in reactions in batch are comparable to those obtained with their homogeneous counterparts with the advantage of easily recovered and recycled in successive reactions. Their catalytic activity decreases when reused in batch reactions, probably because of crushing that is associated with magnetic stirring. In contrast, these immobilized cataly…

Supercritical Carbon Dioxide: A Promoter of Carbon-Halogen Bond Heterolysis

as the leaving groupdeparts from the carbon atom prior to the entrance of thenucleophile. Polar protic solvents with high dielectric con-stants promote polar bond heterolysis by providing effectiveH-bonding and electron-pair donation interactions to theleaving group and the incipient carbocation, respectively.Then, the solvent captures the carbocation intermediate togive the corresponding S

Analysis of hybrid silica materials with the aid of conventional NMR and GC/MS.

Two simple and straightforward procedures for determining the organic content of hybrid silica materials by means of conventional NMR and GC/MS techniques are described. The methods involve dissolving the hybrid material either in a concentrated solution of sodium hydroxide in deuterated water containing a suitable reference or in a solution of hydrogen fluoride in water and extracting with methylene chloride. These methods constitute useful routine techniques for obtaining immediate information concerning both the amount and chemical composition of the organic compounds on the silica surface.

A Quantitative Model for Alkane Nucleophilicity Based on C−H Bond Structural/Topological Descriptors

A first quantitative model for calculating the nucleophilicity of alkanes is described. A statistical treatment was applied to the analysis of the reactivity of 29 different alkane C−H bonds towards in situ generated metal carbene electrophiles. The correlation of the recently reported experimental reactivity with two different sets of descriptors comprising a total of 86 parameters was studied, resulting in the quantitative descriptor‐based alkane nucleophilicity (QDEAN) model. This model consists of an equation with only six structural/topological descriptors, and reproduces the relative reactivity of the alkane C−H bonds. This reactivity can be calculated from parameters emerging from th…

Titelbild: Measuring the Relative Reactivity of the Carbon–Hydrogen Bonds of Alkanes as Nucleophiles (Angew. Chem. 42/2018)

Oxidation of alcohols to carbonyl compounds with CrO3.SiO2 in supercritical carbon dioxide.

Supercritical carbon dioxide (scCO2) is an effective reaction medium to perform the oxidation of primary and secondary aliphatic alcohols to the corresponding carbonyl compounds with chromium trioxide supported on silica. These reactions were performed by flowing a solution of the alcohol in scCO2 through a column containing the supported reagent and recovering the product by depressurization. This method avoids the use of organic solvents and the contamination of the products with chromium species.

Favoring alkane primary carbon-hydrogen bond functionalization in supercritical carbon dioxide as reaction medium

The selectivity of a catalytic alkane functionalization process can be modified just changing the reaction medium from neat alkane to supercritical carbon dioxide (scCO2). A silica supported copper complex bearing an Nheterocyclic carbene ligand promotes the functionalization of carbon-hydrogen bonds of alkanes by transferring the CHCO2Et group from N2=CHCO2Et (ethyl diazoacetate, EDA). In neat hexane only 3% of the primary C-H bonds (ethyl heptanoate being the product) are functionalized in that manner, whereas the same reaction carried out in scCO2 provides a 30% yield in this linear ester. Such effect seems to be induced by an electronic density flux from the NHC ligand to the surroundin…

ChemInform Abstract: FeCl3·6H2O-Catalyzed Mukaiyama-Aldol Type Reactions of Enolizable Aldehydes and Acetals.

A general procedure for the title condensation of dimethylacetals derived from enolizable aldehydes with silyl enol ethers is developed using FeCl3 as the catalyst.

Functionalization of CnH2n+2Alkanes: Supercritical Carbon Dioxide Enhances the Reactivity towards Primary Carbon-Hydrogen Bonds

The functionalization of the primary sites of alkanes is one of the more challenging areas in catalysis. In this context, a novel effect has been discovered that is responsible for an enhancement in the reactivity of the primary C-H bonds of alkanes in a catalytic system. The copper complex Cu(NCMe) (=hydrotris{[3,5-bis(trifluoromethyl)-4-bromo]-pyrazol-1-yl}borate) catalyzes the functionalization of CnH2n+2 with ethyl diazoacetate upon inserting the CHCO2Et unit into C-H bonds. In addition, the selectivity of the reaction toward the primary sites significantly increased relative to that obtained in neat alkane upon using supercritical carbon dioxide as the reaction medium. This was attribu…

ChemInform Abstract: Epoxidation of Olefins with a Silica-Supported Peracid in Supercritical Carbon Dioxide under Flow Conditions.

Anhydrous 2-percarboxyethyl-functionalized silica (2b), a recyclable supported peracid, is a suitable reagent to perform the epoxidation of alkenes 1 in supercritical carbon dioxide at 250 bar and 40 °C under flow conditions. This procedure simplifies the isolation of the reaction products and uses only carbon dioxide as a solvent under mild conditions. The solid reagent 2b can be easily recycled by a reaction with 30% hydrogen peroxide in an acid medium.

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

Above 31.1 °C and 73.8 bar, carbon dioxide reaches the supercritical state, being transformed into a fluid (scCO2) that has attracted interest in the last few decades as reaction medium for several transition-metal-catalyzed organic transformations. The main feature of this fluid rests on its capability to dissolve large amounts of other gases such as hydrogen, carbon monoxide, ethylene, or even methane and light alkanes. In this manner, very high concentrations of these reactants are available for catalysis. In this contribution a review of the main achievements of the use of transition-metal complexes as catalysts in scCO2 is presented.

Baeyer–Villiger oxidation of ketones with a silica-supported peracid in supercritical carbon dioxide under flow conditions

[2-Percarboxyethyl]-functionalized silica reacts with ketones in supercritical carbon dioxide at 250 bar and 40 °C under flow conditions to yield the corresponding esters and lactones. The solid reagent can be easily recycled through treatment with 70% hydrogen peroxide in the presence of an acid at 0 °C. This procedure not only simplifies the isolation of the reaction products, but has the advantage of using only water and carbon dioxide as solvents under mild conditions.

Oxidation of Sulfides with a Silica-Supported Peracid in Supercritical Carbon Dioxide under Flow Conditions: Tuning Chemoselectivity with Pressure

Supercritical carbon dioxide is a convenient medium for performing the selective oxidation of sulfides 1 to either sulfoxides 2 or sulfones 3 with [2-percarboxyethyl]-functionalized silica (4) under flow conditions. The chemoselectivity of the reaction, which results from the different diffusion rates of sulfide and sulfoxide over the reagent bed, can be controlled by adjusting the pressure and the hydration of the silica surface as both the solvating power of the mobile phase and the surface activity of the stationary phase determine the migration rates of sulfide 1 and sulfoxide 2 over the supported peroxide. The results elucidate the impact of surface phenomena on the course of chemical …

Discovering Copper for Methane C–H Bond Functionalization

The copper complex Tp(CF3)2,BrCu(NCMe) (1, Tp(CF3)2,Br = hydrotris((3,5-bis(trifluoromethyl)-4-bromo)-pyrazol-1-yl)borate) catalyzes the insertion of the CHCO2Et group (from ethyl diazoacetate N2CHCO2Et, EDA) into the C–H bonds of methane, in a homogeneous process that uses supercritical carbon dioxide (scCO2) as the reaction medium. Other light alkanes such as ethane, propane, and butane have been also functionalized with this copper-based catalyst, in the first example of the derivatization of the series of C1–C4 alkanes with this metal and a soluble catalyst.

Measuring the Relative Reactivity of the Carbon-Hydrogen Bonds of Alkanes as Nucleophiles

We report quantitative measurements of the relative reactivities of a series of C-H bonds of gaseous or liquid CnH2n+2 alkanes (n = 1-8, 29 different C-H bonds) towards insitu generated electrophiles (copper, silver, and rhodium carbenes), with methane as the reference. This strategy surpasses the drawback of previous model reactions of alkanes with strong electrophiles suffering from C-C cleavage processes, which precluded direct comparison of the relative reactivities of alkane C-H bonds.

Baeyer−Villiger Oxidation with Potassium Peroxomonosulfate Supported on Acidic Silica Gel

[reaction: see text] Potassium peroxomonosulfate deposited onto silica SiO2 x KHSO5 efficiently reacts with ketones in dichloromethane at room temperature to give the corresponding esters or lactones in quantitative yields. This method avoids hydrolysis of the reaction products. The Baeyer-Villiger reaction is catalyzed by potassium hydrogensulfate present in the supported reagent.

FeCl3·6H2O-catalyzed Mukaiyama-aldol type reactions of enolizable aldehydes and acetals.

Mukaiyama-aldol type reactions of acetals derived from enolizable aldehydes with FeCl3·6H2O, an eco-friendly, low-cost, and stable catalyst, lead to β-methoxycarbonyl compounds with nearly quantitative yields. The methodology is extended to the parent aldehydes as starting materials, leading to the corresponding aldols with lower yields, but efficiently. Different alkyl and aryl substituted acetals and aldehydes have been tested in the reaction with linear and cyclic silyl enol ethers. Reactions are carried out in an open air atmosphere, and additives are not required. Acetals can be considered activating groups of the carbonyl moiety rather than a protecting group in this type of FeCl3·6H2…

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

Above 31.1 degrees C and 73.8 bar, carbon dioxide reaches the supercritical state, being transformed into a fluid (scCO(2)) that has attracted interest in the last few decades as reaction medium for several transition-metal-catalyzed organic transformations. The main feature of this fluid rests on its capability to dissolve large amounts of other gases such as hydrogen, carbon monoxide, ethylene, or even methane and light alkanes. In this manner, very high concentrations of these reactants are available for catalysis. In this contribution a review of the main achievements of the use of transition-metal complexes as catalysts in scCO(2) is presented.

ChemInform Abstract: Baeyer-Villiger Oxidation of Ketones with a Silica-Supported Peracid in Supercritical Carbon Dioxide under Flow Conditions.

[2-Percarboxyethyl]-functionalized silica reacts with ketones in supercritical carbon dioxide at 250 bar and 40 °C under flow conditions to yield the corresponding esters and lactones. The solid reagent can be easily recycled through treatment with 70% hydrogen peroxide in the presence of an acid at 0 °C. This procedure not only simplifies the isolation of the reaction products, but has the advantage of using only water and carbon dioxide as solvents under mild conditions.

CCDC 1037192: Experimental Crystal Structure Determination

Related Article: Riccardo Gava, Andrea Olmos, Bárbara Noverges, Teresa Varea, Eleuterio Álvarez, Tomás R. Belderrain, Ana Caballero, Gregorio Asensio, and Pedro J. Pérez|2015|ACS Catalysis|5|3726|doi:10.1021/acscatal.5b00718

CCDC 1037194: Experimental Crystal Structure Determination

Related Article: Riccardo Gava, Andrea Olmos, Bárbara Noverges, Teresa Varea, Eleuterio Álvarez, Tomás R. Belderrain, Ana Caballero, Gregorio Asensio, and Pedro J. Pérez|2015|ACS Catalysis|5|3726|doi:10.1021/acscatal.5b00718

CCDC 1037193: Experimental Crystal Structure Determination

Related Article: Riccardo Gava, Andrea Olmos, Bárbara Noverges, Teresa Varea, Eleuterio Álvarez, Tomás R. Belderrain, Ana Caballero, Gregorio Asensio, and Pedro J. Pérez|2015|ACS Catalysis|5|3726|doi:10.1021/acscatal.5b00718