Aqueous CO2 Reduction with High Efficiency Using α‐Co(OH)2‐Supported Atomic Ir Electrocatalysts

Electrochemical reduction of CO₂ into energy‐dense chemical feedstock and fuels provides an attractive pathway to sustainable energy storage and artificial carbon cycle. Herein, we report the first work to use atomic Ir electrocatalyst for CO₂ reduction. By using α‐Co(OH)₂ as the support, the faradaic efficiency of CO could reach 97.6 % with a turnover frequency (TOF) of 38290 h^?1 in aqueous electrolyte, which is the highest TOF up to date. The electrochemical active area is 23.4‐times higher than Ir nanoparticles (2 nm), which is highly conductive and favors electron transfer from CO₂ to its radical anion (CO₂^.?). Moreover, the more efficient stabilization of CO₂^.? intermediate and easy charge transfer makes the atomic Ir electrocatalyst facilitate CO production. Hence, α‐Co(OH)₂‐supported atomic Ir electrocatalysts show enhanced CO₂ activity and stability.     

Comparison of different extraction methods for the determination of α‐ and β‐thujone in sage (Salvia officinalis L.) herbal tea

Salvia officinalis L. (sage) is an important industrial plant used both for food and pharmaceutical purposes. The terpene fraction of this plant is responsible for many of its therapeutic and culinary properties. We used different extraction methods Tenax TA® purge and trap, headspace (HS) solid‐phase microextraction, HS sorptive extraction, and stir bar sorptive extraction to analyze the terpene fraction extracted from sage tea by GC–MS. Twenty compounds were identified, including α‐, β‐thujone, and several other oxygenated monoterpenes (1,8‐cineole, linalool, camphor, boneol, and bornyl acetate) and oxygenated sesquiterpenes (caryophyllene oxide, viridiflorol, humulene epoxide I, II, and III). Tenax TA® and HS sorptive extraction extracted a lower number of identified compounds, whereas HS solid‐phase microextraction allowed the complete extraction of volatiles with particular reference to α‐ and β‐thujone. The importance of the determination of thujones content in sage herbal tea is also discussed.     

Palladium(II)‐Catalyzed ortho‐CH Arylation/Alkylation of N‐Benzoyl α‐Amino Ester Derivatives

The palladium‐catalyzed arylation/alkylation of ortho‐C?H bonds in N‐benzoyl α‐amino ester derivatives is described. In such a system both the NH‐amido and the CO₂R groups in the α‐amino ester moieties play a role in successful C?H activation/C?C bond formation using iodoaryl coupling partners. A wide variety of functional groups and electron‐rich/deficient iodoarenes are tolerated. The yields obtained range from 20 to 95 %.     

Syntheses of α‐Amino Acids by Using CO2 as a C1 Source

The incorporation of CO₂ into organic compounds is currently one of the most active research topics in organic chemistry, because CO₂ is an abundant, inexpensive, nontoxic, and renewable C1 source. However, CO₂ is also a thermodynamically stable and kinetically inert gaseous compound, and as such, special strategies are required to activate CO₂ and incorporate it into organic compounds. In particular, because the carbon atom adjacent to the nitrogen atom of amine derivatives is positively charged, umpolung carboxylation, which is a difficult chemical process, should be considered for the production of α‐amino acids by using CO₂. In this Minireview, we summarize recent synthetic methods for α‐amino acids that use CO₂ as a carboxylic acid unit.     

Achieving High‐Temperature Stability of Metastable α‐MoC1‐x by Suppressing Phase Transformation with Mounted Atoms for Lithium Storage Performance

Despite a significant advancement in preparing metastable materials, one common problem is the strict and precious reaction conditions due to their metastable structures. Herein, we achieved the preparation of high‐temperature stabilized metastable α‐MoC_1?x by mounting zinc atoms into its lattice structure. Such a structural construction could suppress the phase transformation from α‐MoC_1?x to β‐Mo₂C through restricting the displacement of Mo atoms upon increased temperature. The resultant metastable α‐MoC_1?x can be stabilized up to 1000 °C and this stability temperature is the highest for the metastable α‐MoC_1?x so far. Synchrotron X‐ray absorption spectroscopy (XAS) and X‐ray photoelectron spectroscopy (XPS) confirm the structure of Zn‐mounted α‐MoC_1?x. Density functional theory (DFT) calculations reveal that the introduction of the Zn atoms in the lattice structure of α‐MoC_1?x could significantly decrease the energy difference (ΔE) between α‐MoC_1?x and β‐Mo₂C, thus effectively suppressing the phase transformation from α‐MoC_1?x to β‐Mo₂C and accordingly maintaining the high‐temperature stability of α‐MoC_1?x. This novel strategy can be used as a universal method to be extended to synthesize metastable α‐MoC_1?x from different precursors or other mounted elements. Moreover, the optimal product exhibits excellent lithium storage performances in terms of the cycling stability and rate performance.     

Addition of Electrophilic Radicals to 2‐Benzyloxyglycals: Synthesis and Functionalization of Fluorinated α‐C‐Glycosides and Derivatives

A new method for the synthesis of fluorinated α‐C‐glycosides is described. The reactions between highly electrophilic radicals (fluorinated or unfluorinated) and a 2‐benzyloxyglucal or galactal provide 2‐keto‐D ‐arabino‐ or 2‐keto‐D ‐lyxo‐hexopyranosides through an addition/fragmentation process. Sodium borohydride mediated or Meerwein–Ponndorf–Verley (MPV) reduction of these compounds provides α‐C‐glycosides that feature appropriate anchoring groups for further synthetic elaboration. The presence of CF₂CO₂iPr or CF₂Br groups at the pseudo‐anomeric position allows efficient reduction/olefination or Br/Li‐exchange/nucleophilic‐addition sequences. These transformations open the way for the synthesis of fluorinated C‐glycosidic analogues of glycoconjugates.     

PPh3⋅HBr‐DMSO Mediated Expedient Synthesis of γ‐Substituted β,γ‐Unsaturated α‐Ketomethylthioesters and α‐Bromo Enals: Application to the Synthesis of 2‐Methylsulfanyl‐3(2 H)‐furanones

An efficient chemoselective general procedure for the synthesis of γ‐substituted β,γ‐unsaturated α‐ketomethylthioesters from α,β‐unsaturated ketones has been achieved through an unprecedented PPh₃?HBr‐DMSO mediated oxidative bromination and Kornblum oxidation sequence. The newly developed reagent system serves admirably for the synthesis of α‐bromoenals from enals. Furthermore, AuCl₃‐catalyzed efficient access to 3(2H)‐furanones from the above intermediates under extremely mild conditions are described.     

Effect of cosolvent on solid phase transitions of α‐ to β‐form crystal of syndiotactic polystyrene occurred in supercritical Co2 containing solvent

The solid phase transition mechanism of α‐ to β‐form crystal upon specific treating with supercritical CO₂ + cosolvent on original pure α and mixed (α+β) form syndiotactic polystyrene (sPS) was investigated, using wide angle X‐ray diffraction and differential scanning calorimetry measurements as a function of temperature, pressure, and cosolvent content. As in the supercritical CO₂, sPS in supercritical CO₂ + cosolvent underwent solid phase transitions from α‐ to β‐form, and higher temperature or higher pressure favored this transformation. Due to the higher dipole moment of acetone, small amounts of acetone used as cosolvent with CO₂ made the transition of α‐ to β‐form occur at lower temperature and pressure than in supercritical CO₂, and made the α‐form crystal completely transform to β‐form in the original mixed (α+β) form, whereas ethanol did not. The original β‐form crystal in the original mixed (α+β) form sample acted as the nucleus of new β‐form crystal in the presence of cosolvent as it did in supercritical CO₂, when compared with the original pure α‐form sample. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1625–1636, 2007     

Spectroscopic and thermal characterization of the host–guest interactions between α‐, β‐ and γ‐cyclodextrins and vanadocene dichloride

Host–guest interactions between α‐, β‐ and γ‐cyclodextrins and vanadocene dichloride (Cp₂VCl₂) have been investigated by a combination of thermogravimetric analysis, differential scanning calorimetry, powder X‐ray diffraction and solid‐state and solution electron paramagnetic resonance (EPR) spectroscopy. The solid‐state results demonstrated that only β‐ and γ‐cyclodextrins form 1:1 inclusion complexes, while α‐cyclodextrin does not form an inclusion complex with Cp₂VCl₂. The β‐ and γ‐CD–Cp₂VCl₂ inclusion complexes exhibited anisotropic electron‐⁵¹V (I = 7/2) hyperfine coupling constants whereas the α‐CD–Cp₂VCl₂ system showed only an asymmetric peak with no anisotropic hyperfine constant. On the other hand, solution EPR spectroscopy showed that α‐cyclodextrin (α‐CD) may be involved in weak host–guest interactions in equilibrium with free vanadocene species. Copyright © 2008 John Wiley & Sons, Ltd.     

Conformational analysis of the disaccharide methyl α‐d‐mannopyranosyl‐(1→3)‐2‐O‐acetyl‐β‐d‐mannopyranoside monohydrate

The crystal structure of methyl α‐d ‐mannopyranosyl‐(1→3)‐2‐O‐acetyl‐β‐d ‐mannopyranoside monohydrate, C₁₅H₂₆O₁₂·H₂O, ( II ), has been determined and the structural parameters for its constituent α‐d ‐mannopyranosyl residue compared with those for methyl α‐d ‐mannopyranoside. Mono‐O‐acetylation appears to promote the crystallization of ( II ), inferred from the difficulty in crystallizing methyl α‐d ‐mannopyranosyl‐(1→3)‐β‐d ‐mannopyranoside despite repeated attempts. The conformational properties of the O‐acetyl side chain in ( II ) are similar to those observed in recent studies of peracetylated mannose‐containing oligosaccharides, having a preferred geometry in which the C2—H2 bond eclipses the C=O bond of the acetyl group. The C2—O2 bond in ( II ) elongates by ～0.02 Å upon O‐acetylation. The phi (?) and psi (ψ) torsion angles that dictate the conformation of the internal O‐glycosidic linkage in ( II ) are similar to those determined recently in aqueous solution by NMR spectroscopy for unacetylated ( II ) using the statistical program MA′AT, with a greater disparity found for ψ (Δ = ～16°) than for ? (Δ = ～6°).     

A Highly Efficient Gold‐Catalyzed Photoredox α‐C(sp3)H Alkynylation of Tertiary Aliphatic Amines with Sunlight

A new α‐C(sp³)? H alkynylation of unactivated tertiary aliphatic amines with 1‐iodoalkynes as radical alkynylating reagents in the presence of [Au₂(μ‐dppm)₂]²⁺ in sunlight provides propargylic amines. Based on mechanistic studies, a C? C coupling of an α‐aminoalkyl radical and an alkynyl radical is proposed for the C(sp³)? C(sp) bond formation. The mild, convenient, efficient, and highly selective C(sp³)? H alkynylation reaction shows excellent regioselectivity and good functional‐group compatibility. A scale‐up to gram quantities is possible with sunlight used as a clean and sustainable energy source.     

Mechanism and Kinetics of Carbon Dioxide Capture Using Activated 2‐Amino‐2‐methyl‐1,3‐propanediol

The continued use of fossil fuels as primary sources of energy in industry and other applications stands the test of time, due to their availability and relatively lower cost than alternative sources of energy. In view of this perspective, obtaining an advanced bulk carbon dioxide (CO₂) capture medium becomes an urgent necessity so as to mitigate their effect, especially in global warming, as the use of fossil fuels produces a high rate of CO₂. In this work, the mechanism and kinetics of CO₂ capture using aqueous piperazine (PZ) as an activator to 2‐amino‐2‐methyl‐1,3‐propanediol (AMPD) were investigated. The termolecular mechanism was used to model the kinetics of the system. Reaction kinetics of the single pure amines was first obtained. The reaction rate constant, the k value of AMPD, was 77.2 m³/kmol·s, with a reaction order, n, of 1.25 at 298 K. while that of PZ was equal to 11,059 m³/kmol·s and n as 1.49 at 298 K. Blending of 0.05 kmol/m³ of PZ with 0.5 kmol/m³ of AMPD gave a rate constant, k, value of 23,319 m³/kmol·s and n equal to 1.23 at 298 K. The result obtained for the blended system is more than twice the value of the summation of the corresponding pure amines; in addition, it is comparably higher than the rate constant of monoethanolamine (MEA) in use as a commercial solvent for CO₂ capture. Therefore, an aqueous blend of PZ with AMPD deserves more comprehensive study as a solvent for commercial CO₂ capture. AMPD like other sterically hindered amines absorbs CO₂ in an equimolar ratio that is significantly higher than that of MEA. PZ serves as a promoter in the amine mixture and is required in a very small proportion.     

Heterograft copolymers of poly(ε‐caprolactone) prepared by combination of ATRA “grafting onto” and ATRP “grafting from” processes

This paper aims at reporting on the synthesis of a heterograft copolymer by combining the “grafting onto” process based on atom transfer radical addition (ATRA) and the “grafting from” process by atom transfer radical polymerization (ATRP). The statistical copolymerization of ε‐caprolactone (εCL) and α‐chloro‐ε‐caprolactone (αClεCL) was initiated by 2,2‐dibutyl‐2‐stanna‐1,3‐dioxepane (DSDOP), followed by ATRA of parts of the chlorinated units of poly(αClεCL‐co‐εCL) on the terminal double bond of α‐MeO,ω‐CH₂?CH? CH₂? CO₂‐poly(ethylene oxide) (PEO). The amphiphilic poly(εCL‐g‐EO) graft copolymer collected at this stage forms micelles as supported by dynamic light scattering (DLS) and transmission electron microscopy (TEM). The unreacted pendant chloro groups of poly(εCL‐g‐EO) were used to initiate the ATRP of styrene with formation of copolymer with two populations of randomly distributed grafts, that is PEO and polystyrene. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6015–6024, 2006     

Highly Efficient CO2 Utilization via Aqueous Zinc– or Aluminum–CO2 Systems for Hydrogen Gas Evolution and Electricity Production

Atmospheric carbon dioxide (CO₂) has increased from 278 to 408 parts per million (ppm) over the industrial period and has critically impacted climate change. In response to this crisis, carbon capture, utilization, and storage/sequestration technologies have been studied. So far, however, the economic feasibility of the existing conversion technologies is still inadequate owing to sluggish CO₂ conversion. Herein, we report an aqueous zinc– and aluminum–CO₂ system that utilizes acidity from spontaneous dissolution of CO₂ in aqueous solution to generate electrical energy and hydrogen (H₂). The system has a positively shifted onset potential of hydrogen evolution reaction (HER) by 0.4 V compared to a typical HER under alkaline conditions and facile HER kinetics with low Tafel slope of 34 mV dec^?1. The Al–CO₂ system has a maximum power density of 125 mW cm^?2 which is the highest value among CO₂ utilization electrochemical system.     

Microwave‐assisted synthesis of α‐hydroxy‐benzylphosphonates and ‐benzylphosphine oxides

A series of α‐hydroxy‐benzylphosph‐ onates and ‐benzylphosphine oxides was synthesized by the Na₂CO₃‐catalyzed microwave‐assisted addition of dialkyl phosphites and dipenylphosphine oxide to P‐substituted benzaldehydes. The solventless reaction provided the products in short reaction times and in 71–88% yield. © 2010 Wiley Periodicals, Inc. Heteroatom Chem 22:15–17, 2011; View this article online at wileyonlinelibrary.com . DOI 10.1002/hc.20649     

From α‐carbamoyl‐α‐cyano­oxiranes to 3‐halogenopyruv­amides

The crystal structures of the first stable α‐diol from the α‐halogenopyruv­amide series, 3‐chloro‐2,2‐di­hydroxy‐3‐phenyl­propan­amide, C₉H₁₀­ClNO₃, and three products [3‐(4‐chloro­phenyl)‐2‐cyano‐2,3‐epoxy­propan­amide, C₁₀H₇­ClN₂O₂, 3‐bromo‐2‐cyano‐2‐hydroxy‐3‐p‐tolyl­propan­amide, C₁₁H₁₁Br­N₂O₂, 3‐bromo‐2‐oxo‐3‐p‐tolyl­propan­amide, C₁₀H₁₀­BrNO₂] obtained during the systematic synthesis of α‐halogenopyruv­amides are reported. The crystal structures are dominated by hydrogen bonds involving an amide group. The stability of the geminal diol could be ascribed to hydrogen bonds which involve both hydroxyl groups.     

Preparative and scaled‐up separation of high‐purity α‐linolenic acid from perilla seed oil by conventional and pH‐zone refining counter current chromatography

α‐Linolenic acid is an essential omega‐3 fatty acid needed for human health. However, the isolation of high‐purity α‐linolenic acid from plant resources is challenging. The preparative separation methods of α‐linolenic acid by both conventional and pH‐zone refining counter current chromatography were firstly established in this work. The successful separation of α‐linolenic acid by conventional counter current chromatography was achieved by the optimized solvent system n‐heptane/methanol/ water/acetic acid (10:9:1:0.04, v/v), producing 466 mg of 98.98% α‐linolenic acid from 900 mg free fatty acid sample prepared from perilla seed oil with linoleic acid and oleic acid as by‐products. The scaled‐up separation in 45× is efficient without loss of resolution and extension of separation time. The separation of α‐linolenic acid by pH‐zone refining counter current chromatography was also satisfactory by the solvent system n‐hexane/methanol/water (10:5:5, v/v) and the optimized concentration of trifluoroacetic acid 30 mM and NH₄OH 10 mM. The separation can be scaled up in 180× producing 9676.7 mg of 92.79% α‐linolenic acid from 18 000 mg free fatty acid sample. pH‐zone refining counter current chromatography exhibits a great advantage over conventional counter current chromatography with 20× sample loading capacity on the same column.     

Poly[bis(μ‐benzene‐1,4‐dicarboxylato)bis[μ‐6‐(4‐pyridyl)‐5H‐imidazolo[4,5‐f][1,10]phenanthroline]dilead(II)]: an interpenetrating α‐Po net

The asymmetric unit of the title compound, [Pb₂(C₈H₄O₄)₂(C₁₈H₁₁N₅)₂]_n, contains two Pb^II atoms, two benzene‐1,4‐dicarboxylate (1,4‐bdc) dianions and two 6‐(4‐pyridyl)‐5H‐imidazolo[4,5‐f][1,10]phenanthroline (L) ligands. Each Pb^II atom is eight‐coordinated by three N atoms from two different L ligands and five carboxylate O atoms from three different 1,4‐bdc dianions. The two 1,4‐bdc dianions (1,4‐bdc₁ and 1,4‐bdc₂) show different coordination modes. Each 1,4‐bdc₁ coordinates to two Pb^II atoms in a chelating bis‐bidentate mode. Each carboxylate group of the 1,4‐bdc₂ anion connects two Pb^II atoms in a chelating–bridging tridentate mode to form a dinuclear unit. Neighbouring dinuclear units are connected together by the aromatic backbone of the 1,4‐bdc dianions and the L ligands into a three‐dimensional six‐connected α‐polonium framework. The most striking feature is that two identical three‐dimensional single α‐polonium nets are interlocked with each other, thus leading directly to the formation of a twofold interpenetrated three‐dimensional α‐polonium architecture. The framework is held together in part by strong N—H...O hydrogen bonds between the imidazole NH groups of the L ligands and the carboxylate O atoms of 1,4‐bdc dianions within different α‐polonium nets.     

Highly Enantioselective Carbonyl–Ene Reactions of 2,3‐Diketoesters: Efficient and Atom‐Economical Process to Functionalized Chiral α‐Hydroxy‐β‐Ketoesters

Carbonyl–ene reactions of 2,3‐diketoesters catalyzed by [Cu{(S,S)‐tBu‐box}](SbF₆)₂ [box=bis(oxazoline)] generate chiral α‐functionalized α‐hydroxy‐β‐ketoesters in up to 94 % yield and 97 % ee. The 2,3‐diketoesters are conveniently accessed from the corresponding α‐diazo‐β‐ketoester, and a catalyst loading as low as 1.0 mol % can be achieved.     

Reversible and Selective CO2 to HCO2− Electrocatalysis near the Thermodynamic Potential

Reversible catalysis is a hallmark of energy‐efficient chemical transformations, but can only be achieved if the changes in free energy of intermediate steps are minimized and the catalytic cycle is devoid of high transition‐state barriers. Using these criteria, we demonstrate reversible CO₂/HCO₂^? conversion catalyzed by [Pt(depe)₂]²⁺ (depe=1,2‐bis(diethylphosphino)ethane). Direct measurement of the free energies associated with each catalytic step correctly predicts a slight bias towards CO₂ reduction. We demonstrate how the experimentally measured free energy of each step directly contributes to the <50 mV overpotential. We also find that for CO₂ reduction, H₂ evolution is negligible and the Faradaic efficiency for HCO₂^? production is nearly quantitative. A free‐energy analysis reveals H₂ evolution is endergonic, providing a thermodynamic basis for highly selective CO₂ reduction.