Photoiodocarboxylation of Activated C═C Double Bonds with CO2 and Lithium Iodide.

The photolysis at 254 nm of lithium iodide and olefins 1 carrying an electron-withdrawing Z-substituent in CO2-saturated (1 bar) anhydrous acetonitrile at room temperature produces the atom efficient and transition metal-free photoiodocarboxylation of the C═C double bond. The reaction proceeds well for terminal olefins 1 to form the new C-I and C-C σ-bonds at the α and ß-positions of the Z-substituent, respectively, and is strongly inhibited by polar protic solvents or additives. The experimental results suggest that the reaction channels through the radical anion [CO2•-] in acetonitrile, yet involves different intermediates in aqueous medium. The stabilizing ion-quadrupole and electron donor-acceptor interactions of CO2 with the iodide anion play a crucial role in the reaction course as they allow CO2 to penetrate the solvation shell of the anion in acetonitrile, but not in water. The reaction paths and the reactive intermediates involved under different conditions are discussed.

Photolysis of Tertiary Amines in the Presence of CO2: The Paths to Formic Acid, α-Amino Acids, and 1,2-Diamines.

The photolysis of triethylamine (1a) in the presence of carbon dioxide leads to the hydrogenation of CO2, the α-C-C coupling of 1a, and the CO2 insertion into the α-C-H σ-bond of amine 1a. This reaction is proposed to proceed through the radical ion pair [R3N•+·CO2•-] generated by the photoionization of amine 1a and the electron capture by CO2. The presence of lithium tetrafluoroborate in the reaction medium promotes the efficient and stereoselective α-C-C coupling of 1a by enhancing the production of α-dialkylamino radicals and the isomerization of N,N,N',N'-tetraethylbutane-2,3-diamine (4a).

Reactivity of Lithium ß-Ketocarboxylates: The Role of Lithium Salts.

Lithium ß-ketocarboxylates 1(COOLi), prepared by the reaction of lithium enolates 2(Li+) with carbon dioxide, readily undergo decarboxylative disproportionation in THF solution unless in the presence of lithium salts, in which case they are indefinitely stable at room temperature in inert atmosphere. The availability of stable THF solutions of lithium ß-ketocarboxylates 1(COOLi) in the absence of carbon dioxide allowed reactions to take place with nitrogen bases and alkyl halides 3 to give α-alkyl ketones 1(R) after acidic hydrolysis. The sequence thus represents the use of carbon dioxide as a removable directing group for the selective monoalkylation of lithium enolates 2(Li+). The roles of lithium salts in preventing the disproportionation of lithium ß-ketocarboxylates 1(COOLi) and in determining the course of the reaction with bases and alkyl halides 3 are discussed.

Iodide-Photocatalyzed Reduction of Carbon Dioxide to Formic Acid with Thiols and Hydrogen Sulfide.

The photolysis of iodide anions promotes the reaction of carbon dioxide with hydrogen sulfide or thiols to quantitatively yield formic acid and sulfur or disulfides. The reaction proceeds in acetonitrile and aqueous solutions, at atmospheric pressure and room temperature by irradiation using a low-pressure mercury lamp. This transition-metal-free photocatalytic process for CO2 capture coupled with H2 S removal may have been relevant as a prebiotic carbon dioxide fixation.

SN1 reactions in supercritical carbon dioxide in the presence of alcohols: the role of preferential solvation.

Ethanol () inhibits SN1 reactions of alkyl halides in supercritical carbon dioxide (scCO2) and gives no ethers as products. The unexpected behaviour of alcohols in the reaction of alkyl halides with 1,3-dimethoxybenzene () in scCO2 under different conditions is rationalised in terms of Brønsted and Lewis acid-base equilibria of reagents, intermediates, additives and products in a singular solvent characterised by: (i) the strong quadrupole and Lewis acid character of carbon dioxide, which hinders SN2 paths by strongly solvating basic solutes; (ii) the weak Lewis base character of carbon dioxide, which prevents it from behaving as a proton sink; (iii) the compressible nature of scCO2, which enhances the impact of preferential solvation on carbon dioxide availability for the solvent-demanding rate determining step.

Inverse solvent effects in the heterogeneous and homogeneous epoxidation of cis-2-heptene with [2-percarboxyethyl]-functionalized silica and meta-chloroperbenzoic acid.

The rate constants for the epoxidation of cis-2-heptene with [2-percarboxyethyl]-functionalized silica (1a) and meta-chloroperbenzoic acid (mCPBA) (1b) in different solvents have been determined at temperatures in the -10 to 40 °C range. The heterogeneous epoxidation exhibits a dependence of the reaction rate on solvent polarity opposite to its homogeneous counterpart and anomalous activation parameters in n-hexane, which are interpreted in terms of the surface-promoted solvent structure at the solid-liquid interface. The results show that highly polar solvents can strongly inhibit heterogeneous reactions performed with silica-supported reagents or catalysts.

Epoxidation of olefins with a silica-supported peracid.

Anhydrous [2-percarboxyethyl] functionalized silica (2a) is an advantageous oxidant for performing the epoxidation of olefins 1. Epoxides 3 do not undergo the ring-opening reactions catalyzed by the acidic silica surface, except for particularly activated cases such as styrene oxide. The hydrophilic and acidic character of the silica surface does not interfere with the directing effects exerted by allylic H-bond acceptor substituents. The alkenes 1 carrying hydroxyl groups react with silica-supported peracid 2a faster than unsubstituted alkenes, thus reversing the trend known for reactions with soluble peracids. These results are attributed to the H-bond interactions of substrate 1 with the silanol and carboxylic acid groups bonded to the silica surface.

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.

Reactions at interfaces: oxygenation of n-butyl ligands anchored on silica surfaces with methyl(trifluoromethyl)dioxirane.

The oxygenation of n-butyl and n-butoxy chains bonded to silica with methyl(trifluoromethyl)dioxirane (1) revealed the ability of the silica matrix to release electron density toward the reacting C(2)-H σ-bond through the Si-C(1) and Si-O(1) σ-bonds connecting the alkyl chain to the surface (silicon ß-effect). The silica surface impedes neither the alkyl chain adopting the conformation required for the silicon ß-effect nor dioxirane 1 approaching the reactive C(2) methylene group. Reaction regioselectivity is insensitive to changes in the solvation of the reacting system, the location of organic ligands on the silica surface, and the H-bonding character of the silica surface. Reaction rates are faster for those organic ligands either within the silica pores or bonded to hydrophilic silica surfaces, which evidence the enhanced molecular dynamics of confined dioxirane 1 and the impact of surface phenomena on the reaction kinetics. The oxygenation of n-butyl and n-butoxy chains carrying trimethylsilyl, trimethoxysilyl, and tert-butyl groups with dioxirane 1 under homogeneous conditions confirms the electronic effects of the silyl substituents and the consequences of steric hindrance on the reaction rate and regioselectivity. Orthosilicic acid esters react preferentially at the methylene group adjacent to the oxygen atom in clear contrast with the reactivity of the carboxylic or sulfonic acid alkyl esters, which efficiently protect this position toward oxidation with 1.

Silver-catalyzed C-C bond formation between methane and ethyl diazoacetate in supercritical CO2.

Even in the context of hydrocarbons' general resistance to selective functionalization, methane's volatility and strong bonds pose a particular challenge. We report here that silver complexes bearing perfluorinated indazolylborate ligands catalyze the reaction of methane (CH(4)) with ethyl diazoacetate (N(2)CHCO(2)Et) to yield ethyl propionate (CH(3)CH(2)CO(2)Et). The use of supercritical carbon dioxide (scCO(2)) as the solvent is key to the reaction's success. Although the catalyst is only sparingly soluble in CH(4)/CO(2) mixtures, optimized conditions presently result in a 19% yield of ethyl propionate (based on starting quantity of the diazoester) at 40°C over 14 hours.

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.

Oppenauer oxidation of secondary alcohols with 1,1,1-trifluoroacetone as hydride acceptor.

1,1,1-Trifluoroacetone (2a) reacts as a hydride-acceptor in the Oppenauer oxidation of secondary alcohols (1) in the presence of diethylethoxyaluminum. The oxidant allows for selective oxidation of secondary alcohols in the presence of primary alcohols.

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.

Conformational mobility of thianthrene-5-oxide.

[reaction: see text] Data on the apparent dipole moment of thianthrene-5-oxide (1) and (1)H NMR spectra in different solvents support the conformational mobility of 1, which flaps between two limit boat conformations with the sulfinyl group in pseudoequatorial and pseudoaxial positions, respectively. The conformational equilibrium of 1 occurs too fast for the (1)H NMR (500 MHz) time-scale even at -130 degrees C, and the equilibrium constant has not been determined. The apparent dipole moments of 1 in n-hexane and 1,4-dioxane and the (1)H NMR spectra of 1 and the model compounds cis- and trans-thianthrene-5,10-dioxides (2) and thianthrene (5) in different solvents and at various temperatures confirm that the relative position of the conformational equilibrium of 1 is solvent-dependent, and more polar solvents favor the conformation with the sulfoxide group in the pseudoaxial position (1(')(ax)). Variable-temperature (1)H NMR spectra have established the interconversion barrier of trans-2 and confirmed that the conformational equilibrium of cis-2 is strongly displaced toward the conformation with both sulfinyl groups in the pseudoequatorial position. The (1)H NMR data support the transannular interaction of the functional groups in 1 and trans-2.

Mechanism of the oxidation of sulfides by dioxiranes: conformational mobility and transannular interaction in the oxidation of thianthrene 5-oxide.

The detailed study of the oxidation of thianthrene 5-oxide (1) with methyl(trifluoromethyl)dioxirane (5b) in different solvents and in the presence of (18)O isotopic tracers is reported. Thianthrene 5-oxide (1) is a flexible molecule in solution, and this property allows for transannular interaction of the sulfoxide group with the expected zwitterionic 7 and hypervalent 10-S-4 sulfurane 9 intermediates formed in the oxidation and biases the course of the reaction toward the monooxygenation pathway.

Mechanism of the oxidation of sulfides by dioxiranes. 1. Intermediacy of a 10-S-4 hypervalent sulfur adduct.

Earlier studies established that dimethyldioxirane (1a) reacts with sulfides 2 in two consecutive concerted electrophilic oxygen-transfer steps to give first sulfoxides 3 and then sulfones 4. The same sequential electrophilic oxidation model was assumed for the reaction of sulfides 2 with the strongly electrophilic methyl(trifluoromethyl)dioxirane (1b). In this paper we report on a systematic and general study on the mechanism of the reaction of simple sulfides 2 with DMDO (1a) and TFDO (1b) which provides clear evidence for the involvement of hypervalent sulfur species in the oxidation process. In the oxidation of sulfides 2a-c, diphenyl sulfide (2d), para-substituted aryl methyl sulfides 2e-i, and phenothiazine 2k with 1b, the major product was the corresponding sulfone 4, even when a 10-fold excess of sulfide relative to 1b was used. The sulfone:sulfoxide 4:3 ratio depends among other factors on the dioxirane 1a or 1b used, the sulfide substitution pattern, the polar, protic, or aprotic character of the solvent, and the temperature. The influence of these factors and also deuterium and (18)O tracer experiments performed allow a general mechanism to be depicted for these oxidations in which the key step is the reversible cyclization of a zwitterionic intermediate, 6, to form a hypervalent sulfur species, 7. The classical sequential mechanism which establishes that sulfides are oxidized first to sulfides and then to sulfones can be enclosed in our general picture of the process and represents just those particular cases in which the zwitterionic intermediate 6 decomposes prior to undergoing ring closure to afford the hypervalent sulfurane intermediate 7.

H-Bonding Interactions in the Epoxidation of Alkenylammonium Salts with Dimethyldioxirane and m-Chloroperbenzoic Acid: A Kinetic Study.

The epoxidation rate constants for the reaction of allylic and homoallylic primary and quaternary ammonium salts with DMDO (1b) and m-CPBA (2), as well as the stereochemical outcome of these reactions, were determined. The presence of an ionic functional group in the substrate complicates the kinetic study of the reaction. However, k(0) can be determined from the k(obs) values measured in solutions with different ionic strengths. The order of magnitude of the rate constants is the same for the epoxidation of primary and quaternary homoallylic ammonium salts, while primary allylic ammonium salts react more than 10 times faster than their quaternary counterparts. High syn-diastereoselectivity is achieved in the epoxidation of the primary allylic salt 3aH(+)() while the quaternary allylic ammonium salt 5a(+)() gives equimolecular (m-CPBA) or predominantly anti(DMDO) mixtures of diastereomers. These results are consistent with the existence of hydrogen bond interaction between the protic substrates and the oxidant.