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In the present paper, we described the efficient enantioselective kinetic resolution (KR) of racemic diastereocontrolled secondary alcohols bearing a quaternary stereocenter using a commercially available chiral isothiourea organocatalyst. This methodology is a general KR leading to the enantiocontrol of acyclic quaternary stereocenter with high levels of stereoselectivity (s up to 185) on a large scope. The hydroxyl function can easily serve as a traceless group by oxidation or reduction process. [ABSTRACT FROM AUTHOR]

The development of catalyst‐controlled site‐selective C(sp3)−H functionalization is a current major challenge in organic synthesis. This paper describes DFT‐guided identification of pentavalent silicate species as a novel bond‐weakening catalyst for the α‐C−H bonds of alcohols together with a photoredox catalyst and a hydrogen atom transfer catalyst. Specifically, Martin's spirosilane accelerated α‐C−H alkylation of alcohols. [ABSTRACT FROM AUTHOR]

Utilizing renewable electricity for the electrocatalytic conversion of CO2 into alcohols represents a promising avenue for generating value‐added fuels and achieving carbon neutrality. Recently, there has been growing scientific interest in achieving high‐efficiency conversion of CO2 to alcohols, with significant advancements made in mechanism understanding, reactor design, catalyst development, and more. Herein, a thorough examination of the latest advances in electrocatalytic CO2 reduction reaction (CO2RR) to alcohols is provided. General mechanisms and pathways of electrocatalytic conversion of CO2‐to‐alcohols are systematically illustrated. Subsequently, electrolyzer configurations, electrolytes, and electrocatalysts employed in CO2RR are summarized. After that, critical operating parameters (e.g., reaction pressure, temperature, and pH) that would significantly influence the CO2RR process are also analyzed. Finally, the review addresses challenges and offers perspectives in this field to guide future studies aimed at advancing CO2‐to‐alcohols conversion technologies. [ABSTRACT FROM AUTHOR]

The Front Cover shows the conversion of alcohols to an alternative jet fuel blendstock based on catalytic steps historically utilized by the petroleum refining and petrochemical industry. This pathway provides a means for producing a sustainable alternative jet fuel (SAJF) from a wide variety of resources, offering a near term opportunity for alcohol producers to enter the SAJF market and for the aviation sector to meet growing SAJF demand. In their Full Paper, S. Geleynse et al. review the technical background and evaluate selected variations of ATJ processes. Simulation and modeling is employed to assess some ATJ conversion schemes, with a particular focus on comparisons between the use of an ethanol or isobutanol intermediate. Key bottlenecks of ATJ production in the near term are discussed and recommendations are provided. More information can be found in the Full Paper by S. Geleynse et al. on page 3728 in Issue 21, 2018 (DOI: 10.1002/cssc.201801690). [ABSTRACT FROM AUTHOR]

Low‐temperature solid oxide fuel cells (LT‐SOFCs, operating temperature≤600 °C) are advantageous in potential applicability, affordability, and durability compared to conventional SOFCs (operating temperature: 800–1000 °C). Direct operation of LT‐SOFCs on liquid alcohol fuels can further improve their portability as well as accessibility to the fuel. In this review, we overview the results of LT‐SOFCs directly fueled by liquid alcohols that operate at 600 °C and below. Fundamentals regarding operation principles, losses, as well as reactions associated with liquid alcohol‐fueled LT‐SOFCs are presented. The materials, structures, and fabrication processes of cell components, namely anode, electrolyte, and cathode, are mainly reviewed. The electrochemical performances of alcohol‐fueled LT‐SOFCs are also summarized and compared with those of H2‐fueled LT‐SOFCs. Low‐temperature solid oxide fuel cells (LT‐SOFCs, operating temperature≤600 °C) directly fueled with liquid alcohol are promising candidates for next‐generation portable power sources. In this paper, recent results on direct alcohol‐fueled LT‐SOFCs are reviewed, focusing on materials, structures, and fabrication processes of the cell components. The electrochemical performances of alcohol‐fueled LT‐SOFCs are also reviewed and compared to those of H2‐fueled LT‐SOFCs. [ABSTRACT FROM AUTHOR]

The alcohol‐to‐jet (ATJ) process is a method for the conversion of alcohols to an alternative jet fuel blendstock based on catalytic steps historically utilized by the petroleum refining and petrochemical industry. This pathway provides a means for producing a sustainable alternative jet fuel (SAJF) from a wide variety of resources and offers a near‐term opportunity for alcohol producers to enter the SAJF market and for the aviation sector to meet growing SAJF demand. Herein, the technical background is reviewed and selected variations of ATJ processes evaluated. Simulation and modeling were employed to assess some ATJ conversion schemes, with a particular focus on comparisons between the use of an ethanol or isobutanol intermediate. Although the utilization of isobutanol offers a 34 % lower conversion cost for the catalytic upgrading process, the cost of alcohol production is estimated to contribute more than 80 % of the total cost at the refinery. The cost of feedstock and alcohol production has a dominant effect on the overall process economics. Ready for takeoff: The alcohol‐to‐jet process is a promising pathway for the production of alternative drop‐in jet fuels from sustainably produced alcohols. In this paper, the key engineering barriers are discussed and techno‐economic assessment is used to evaluate potential commercial implementations of this imminent alternative‐fuels process. [ABSTRACT FROM AUTHOR]

In this paper we outline how dihalohydration reactions of propargylic alcohols can be used to access a wide variety of useful halogenated building blocks. A novel procedure for dibromohydration of alkynes has been developed, and a selection of dichloro and dibromo diols and cyclic ethers were synthesized. The dihalohydration of homo‐propargylic alcohols provides a useful route to 3‐halofurans, which were shown to readily undergo cycloaddition reactions under mild conditions. Finally, a novel ring expansion of propargylic alcohols containing a cyclopropylalkyne provides access to halogenated alkenylcyclobutanes. [ABSTRACT FROM AUTHOR]

Cobalt oxide hydrate (Co(OH)x) supported on metal oxides were prepared. The oxidative cleavage of C(OH)−C bond in alcohol was catalyzed by Co(OH)x/metal oxides using molecular oxygen as the oxidant, and the corresponding product was obtained with high selectivity. The composition and characteristics of the catalysts were analyzed by X‐ray diffraction (XRD), high resolution transmission electron microscopy (HRTEM), high‐angle ring dark‐field scanning TEM (HAADF‐STEM), N2 physico‐adsorption characterization, inductively coupled plasma optical emission spectrometry (ICP‐OES), Fourier transform infrared spectrum (FTIR), X‐ray photoelectron spectroscopy (XPS) and NH3‐temperature‐programmed desorption (NH3‐TPD). Additionally, a reasonable reaction mechanism was proposed based on the characterization results and a series of controlled experiments. Notably, this heterogeneous catalytic system did not require any additives and had good recycling performance. [ABSTRACT FROM AUTHOR]

The development of new sustainable nanocatalytic systems for green chemical synthesis is a growing area in chemical science. Herein, a reusable heterogeneous N‐doped graphene‐based manganese nanocatalyst (Mn@NrGO) for selective N‐alkylation of amines with alcohols is described. Mechanistic studies illustrate that the catalytic reaction follows a domino dehydrogenation‐condensation‐hydrogenation sequence of alcohols and amines with the formation of water as the sole by‐product. The scope of the reaction is extended to the synthesis of pharmaceutically important N‐alkylated amine intermediates. The heterogeneous nature of the catalyst made it easy to separate for long‐term performance, and the recycling study revealed that the catalyst was robust and retained its activity after several recycling experiments. [ABSTRACT FROM AUTHOR]

Polyaniline (PANI)‐supported tungsten could be easily fabricated by immersing PANI into the tungsten salt solution. It was a high efficient catalyst for alcohol oxidation reaction to produce carbonyls. Notably, the selectivities of the oxidation of primary alcohols were good, affording aldehydes as the specific products. The high catalytic activity might attribute to the coordination of nitrogen in PANI with tungsten in the materials, while the unique structure afforded the catalyst high selectivity for primary alcohol oxidation. [ABSTRACT FROM AUTHOR]

One of the ultimate goals in organic synthesis is to develop metal-free, efficient and easily separable catalytic system for atom economic organic reactions in an environmental solvent. Direct substitution reaction of alcohols and hydrocarbon compounds is a significant and atom economic method for C􀀀 C bond formation. Herein, a metal-free and efficient catalytic system including recyclable pyridine-based ionic liquids with multiple active sites as the catalyst and dimethyl carbonate as the environmentally friendly solvent was developed for atom economic C3 substitution of 4-hydroxycoumarins with alcohols. Primary aromatic alcohols, secondary aliphatic and aromatic alcohols were suitable for the reaction, providing up to 99% yield. The catalytic system could be easily scaled up to gramscale with nearly quantitative yield. Coumatetralyl as commercial rodenticide could be prepared directly from commercially available 4-hydroxycoumarin and 1,2,3,4-tetrahydronaphthalen-1-ol. Racemic product derived from the reaction of (R)-1-phenylethanol and 4-hydroxycoumarin indicated the reaction was achieved through an SN1 pathway. The comparison of the activities and acidities of the ionic liquids demonstrated that there was no directly relationship between them. Control experiments showed that the reaction probably proceeded via carbocation, ether intermediate and synergistically promoted effect of hydrogen bonding between the ionic liquid with multi-active sites and substrates. [ABSTRACT FROM AUTHOR]

The transfer hydrogenation of flavanones and ortho‐hydroxychalcones catalyzed by ruthenium pincer complexes RuCl(CNNPh)(disphosphine) has allowed the synthesis of ortho‐hydroxy 1,3‐diarypropanols in 80–88 % yield, under mild reaction conditions and short reaction times (1 h) in 2‐propanol. The amount of the co‐catalyst NaOiPr has been found crucial for the selective reduction of flavanones to ortho‐hydroxy 1,3‐diarypropanols vs. flavan‐4‐ols. Preliminary results show that with pincer catalysts bearing (S,R)‐Josiphos, flavanone is reduced to the corresponding (S)‐alcohol in moderate conversion (36 %) and up to 92 % ee. [ABSTRACT FROM AUTHOR]

Deuterium labeling is an interesting process that leads to compounds of use in different fields. We describe the transfer hydrogenation of aldehydes and the selective C1 deuteration of the obtained alcohols in D2O, as the only deuterium source. Different aromatic, alkylic and α,β-unsaturated aldehydes were reduced in the presence of [RuCl(p-cymene)(dmbpy)]BF4, (dmbpy=4,4'-dimethyl-2,2'-bipyridine) as the pre-catalyst and HCO2Na/HCO2H as the hydrogen source. Moreover, furfural and glucose, were selectively reduced to the valuable alcohols, furfuryl alcohol and sorbitol. The processes were carried out in neat water or in a biphasic water/toluene system. The biphasic system allowed easy recycling, higher yields, and higher selective D incorporation (using D2O/toluene). The deuteration took place due to an efficient effective M-H/D+ exchange from D2O that allows the inversion of polarity of D+ (umpolung). DFT calculations that explain the catalytic behavior in water are also included. [ABSTRACT FROM AUTHOR]

Swelling is the most fundamental property of graphite oxides (GO). Here, a structural study of Brodie graphite oxide (BGO) swelling in a set of long chain 1‐alcohols (named C11 to C22 according to the number of carbons) performed using synchrotron radiation X‐ray diffraction at elevated temperatures is reported. Even the longest of tested alcohols (C22) is found to intercalate BGO with enormous expansion of the interlayer distance from ≈6Å up to ≈63Å, the highest expansion of GO lattice ever reported. Swelling transitions from low temperature α‐phase to high temperature β‐phase are found for BGO in all alcohols in the C11–C22 set. The transitions correspond to decrease of inter‐layer distance correlating with the length of alcohol molecules, and change in their orientation from perpendicular to GO planes to layered parallel to GO (Type II transitions). These transitions are very different compared to BGO swelling transitions (Type I) found in smaller alcohols and related to insertion/de‐insertion of additional layer of alcohol parallel to GO. Analysis of general trends in the whole set of 1‐alcohols (C1 to C22) shows that the 1‐alcohol chain length defines the type of swelling transition with Type I found for alcohols with C<10 and Type II for C>10. [ABSTRACT FROM AUTHOR]

The Cover shows a micro‐kinetic model being applied to benzylic alcohol oxidation over metal nanoparticles. In their new Full Paper, A. Savara et al. report the first micro‐kinetic modeling of liquid phase benzylic alcohol oxidation over transition metal nanoparticles. The micro‐kinetic model was applied to palladium nanoparticles and enabled applying the concept of a sticking coefficient in solution. The kinetic simulations were able to reproduce the 18 trends observed in the responses of the six products when varying the alcohol concentration, oxygen pressure, and temperature. The mechanism used was based on surface science knowledge and an earlier study published in ChemCatChem. More information can be found in the Full Paper by A. Savara et al. et al. on page 2482 in Issue 15, 2016 (DOI: 10.1002/cctc.201600368). [ABSTRACT FROM AUTHOR]

The alkylation of heterocyclic compounds is important for the synthesis of various biologically active compounds. In this paper, we present the development of a Pd/C-catalyzed alkylation of heterocyclic compounds using alcohols as the alkylating agents. This method gives the corresponding alkylated heterocyclic compounds in high yields (up to 99%). The commercially available catalyst can be recovered and reused five times without significant loss of catalytic efficiency, and the turnover number (TON) was as high as 900. Moreover, the reaction could be scaled up. [ABSTRACT FROM AUTHOR]

Herein, we report the manganese catalyzed coupling of alcohols with phosphorus ylides. The selectivity in the coupling of primary alcohols with phosphorus ylides to form carbon‐carbon single (C−C) and carbon‐carbon double (C=C) bonds can be controlled by the ligands. In the conversion of more challenging secondary alcohols with phosphorus ylides the selectivity towards the formation of C−C vs. C=C bonds can be controlled by the reaction conditions, namely the amount of base. The scope and limitations of the coupling reactions were thoroughly evaluated by the conversion of 21 alcohols and 15 ylides. Notably, compared to existing methods, which are based on precious metal complexes as catalysts, the present catalytic system is based on earth abundant manganese catalysts. The reaction can also be performed in a sequential one‐pot reaction generating the phosphorus ylide in situ followed manganese catalyzed C−C and C=C bond formation. Mechanistic studies suggest that the C−C bond was generated via a borrowing hydrogen pathway and the C=C bond formation followed an acceptorless dehydrogenative coupling pathway. [ABSTRACT FROM AUTHOR]

The inside cover picture, provided by Feng Li and co ‐ workers, illustrates the direct synthesis of α ‐ alkylated arylacetamides from arylacetonitriles and primary alcohols. In the presence of a rhodium complex [Rh(cod)Cl]2/triphenylphosphine/potassium hydroxide system, the desired α ‐ alkylated arylacetamides were obtained in 74 – 92% yield under microwave conditions. The experimental results in this paper are in sharp contrast with previous reports, where the coupling of arylacetonitriles and primary alcohols produced the α ‐ alkylated arylacetonitriles. Notably, this research shows the potential of developing completely atom ‐ economical reactions that involve the hydrogen autotransfer (or hydrogen borrowing) process. Details can be found in the full paper on pages 1405 – 1415 (F. Li, X. Zou, N. Wang, Adv. Synth. Catal. 2015, 357, 1405 – 1415; DOI: 10.1002/adsc.201401013). [ABSTRACT FROM AUTHOR]

A direct synthesis of α-alkylated arylacetamides from arylacetonitriles and primary alcohols has been accomplished for the first time. In the presence of the rhodium complex [Rh(cod)Cl]2/triphenylphosphine/potassium hydroxide system, the desired α-alkylated arylacetamides were obtained in 74-92% yield under microwave conditions. The experimental results in this paper are in sharp contrast with previous reports, where the coupling of arylacetonitriles and primary alcohols produced the α-alkylated arylacetonitriles. Mechanistic investigations show that arylacetonitriles are first α-alkylated with primary alcohols to produce α-alkylated arylacetonitriles, which are further hydrated with the water resulting from the α-alkylation step to produce α-alkylated arylacetamides. More importantly, this research shows the potential of developing completely atom-economical reactions that involve the hydrogen autotransfer (or hydrogen borrowing) process. [ABSTRACT FROM AUTHOR]

The oxidant-free dehydrogenation of n-pentanol over copper based catalysts was investigated in this paper. The effect of metal modification on the activity and stability of the copper catalyst supported on γ-Al2O3 and La2O3 (Cu/ γ-Al2O3-La2O3) was clarified and a Cr modified Cu/Al2O3-La2O3 (Cu-Cr/ γ-Al2O3-La2O3) showed the best catalytic performance. The conversion of n-pentanol was 70.0% and the selectivity for n-pentanal increased to 97.1% over Cu-Cr/ γ-Al2O3-La2O3. X-ray diffraction and temperature programmed reduction of H2 indicated that the addition of Cr favors the formation and reduction of the copper oxide, and the dispersion of the active Cu0 species, accounting for the good activity and stability of this catalyst. Furthermore, the lower amount of acidic sites in Cu-Cr/ γ-Al2O3-La2O3 is suggested to suppress the dehydration in oxidant-free dehydrogenation of n-pentanol, accounting for the higher selectivity for n-pentanal. [ABSTRACT FROM AUTHOR]

Electron-deficient propargylic alcohols (EWG = CN, C(O)Ph, CO2Me, C(O)NH2) under catalyst-free mild conditions are annulated with Δ1-pyrrolines to afford functionalized hexahydropyrrolo[ 2,1-b]oxazoles, mostly in 19–93 % yield. The synthesis is stereoselective with respect to disposition of functionalized ethenyl group relative to the condensed heterocyclic system thus formed in most cases. This methodology provides a simple one-pot access to a novel family of synthetically and pharmaceutically prospective. [ABSTRACT FROM AUTHOR]

Alcohols are one of the most common organic compound classes among natural and synthetic products. Thus, methods for direct removal of C−OH groups without the need for wasteful pre‐functionalization are of great synthetic interest to unlock the full synthetic potential of the compound class. Herein, electroreductive C−OH bond activation and subsequent deoxygenative C−H and C−C bond formation of benzylic and propargylic alcohols are demonstrated along with mechanistic insights. Experimental and theoretical studies indicate that the reductive C−OH bond cleavage furnishes an open shell intermediate that undergoes a radical‐polar crossover to the corresponding carbanion that subsequently undergoes protonation to furnish alkane products. Furthermore, we demonstrate that the carbanion can be trapped with CO2 to form arylacetic acids. The cathodic transformations are efficiently balanced by the anodic oxidation of sub‐stoichiometric borohydride additives, a strategy that serves as a highly attractive alternative to the use of sacrificial metal anodes. [ABSTRACT FROM AUTHOR]

The Cover shows an industrial landscape, where Au nanoparticles are used as catalysts for oxidation reactions.In their Full Paper, L. M. D. R. de Sousa Martins et al. demonstrate an efficient single‐pot oxidative functionalization of cyclohexane and benzyl and methylbenzyl alcohols under mild conditions with high selectivity, catalyzed by reusable Au nanoparticles on Al2O3, Fe2O3, ZnO, and TiO2. Au nanoparticles on Fe2O3 led to an unusual almost exclusive formation of cyclohexanol by control of reaction time, but Au nanoparticles on TiO2 had a remarkable catalytic effect on acetophenone yield. [ABSTRACT FROM AUTHOR]

The Cover shows the catalytic conversion of biomass hydrolysate into renewable alkanes over a Ru/C catalyst with aqueous phosphoric acid (Ru/C+H3PO4), in which a high yield of C5/C6 alkanes was obtained.In their Full Paper, Y. Weng et al. investigated the mechanism of the sorbitol hydrodeoxygenation (HDO) reaction into alkanes over a Ru/C+H3PO4 catalyst by using a trickle‐bed reactor. Higher HDO performance might be a result of the bifunctional role of the catalytic system. These findings suggest that the downstream process of biomass hydrolysis could be directly conducted in acid aqueous phase at low reaction temperature, reducing the amount of acid waste. [ABSTRACT FROM AUTHOR]

We report herein a novel iron‐catalyzed cascade dehydrative coupling/Friedel–Crafts cyclization of two different alcohols, providing a variety of indanes, which are ubiquitous substructures found in natural products, pharmaceuticals, and functional materials. Importantly, the developed approach is highly atom‐economic and environmentally benign, as it employs readily available alcohols as substrates and generates water as the only byproduct. A novel iron‐catalyzed cascade dehydrative coupling/Friedel–Crafts cyclization of two different alcohols to indanes has been developed. This approach is highly atom‐economic and environmentally benign, as it employs readily available alcohols as substrates and generates only water as byproduct. [ABSTRACT FROM AUTHOR]

This paper focuses on a detailed evaluation of commercially available immobilized lipases and simple monohydric alcohols for the production of alkyl esters from sunflower oil by enzymatic alcoholysis. Six lipases were tested with seven alcohols, including straight and branched-chain primary and secondary alcohols. The reactions were conducted in a batch stirred reaction vessel using stoichiometric amounts of substrafes under solvent-free conditions. Dramatic differences in alcoholysis performance were observed among the different lipases. For most of the alcohols, Novozym 435 produced the highest yield of FA alkyl esters, with yields well over 90% for methanol, absolute ethanol, and 1-propanol. Overall, 96% ethanol was the preferred alcohol for all lipases except Novozym 435, and ethanolysis reactions reached the maximal conversion efficiency. Increasing the water content in the system resulted in an increased degree of conversion for all lipases except Novozym 435. The secondary alcohol 2-propanol significantly reduced the alcoholysis reaction with all lipases; however, the branch-chain isobutanol was more advantageous than linear 1-butanol for Novozym 435, Lipozyme RM IM, and Lipase PS-C. Many commercial immobilized lipases are highly efficient and promising for the production of alkyl esters, offering high reaction yields and a simple operation process. [ABSTRACT FROM AUTHOR]

In recent decades, density functional theory (DFT) calculations have been extensively employed to investigate the mechanism of transition metal‐catalyzed C−O activation reactions. These studies provide valuable insights into the structure‐reactivity/selectivity correlations via theoretical simulations and energy profile analysis. Alcohols, a category of molecules that are readily available from biomass and are low cost, represent one of the most extensively studied compounds in organic synthesis. In this review, we provide a brief overview of the DFT studies conducted since 2017 on the C−OH bond activation of alcohols catalyzed by transition metals. Specifically, the activation can be mainly divided into four categories: free radical cleavage, metal insertion, nucleophilic attack, and β‐OH elimination. We will also cover some promising strategies and give a perspective regarding future research directions in this field. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: Alcohols as among the most widely occurring organic compounds known, deoxygenative transformations of free alcohols as partners in radical addition reactions remain formidable challenges with great opportunities to achieve new and useful transformations. Herein, we report a protocol via C—O bond cleavage and C—C bond‐forming reaction of trifluoromethyl alkenes with free alcohols assisted by titanium reagents via a deoxygenative radical strategy, enabling the divergent synthesis for functional‐group‐rich organofluorinated compounds in high efficiencies. In this transformation, tertiary alcohols by Ti‐catalysis could be converted to trifluoromethyl alkanes without defluorination in acidic conditions, while benzyl alcohols are employed by Ti‐mediated activation to supply the gem‐difluoroalkenes with defluorination in the presence of a base. This protocol is applicable for a broad range of trifluoromethyl alkenes with good functional group tolerance and a variety of tertiary alcohols and benzyl alcohols (including primary, secondary, and tertiary alcohols), and is scalable to the gram level. Remarkably, the utility of this protocol is demonstrated by several derivatizations and late‐stage functionalization of drug molecules. The successful applications in scale up reactions and late‐stage functionalization of several drug molecules demonstrate its potential synthetic value in drug discovery settings. [ABSTRACT FROM AUTHOR]

Following the advances in capture technologies, CO2 utilization associated with low‐cost renewable H2 in catalytic hydrogenation is a promising strategy for reducing the carbon footprint of industrial processes by providing valuable chemicals and fuels. However, the scalability and economic viability of these processes will depend on the development of efficient catalysts. Noble metal‐based catalysts have been extensively reported in the last few years as highly effective in promoting CO2 hydrogenation to various products. Although promising, the scarcity, high cost, and environmental impact of mining make it challenging to scale up these materials from bench to plant. Developing advanced synthesis and characterization methods is essential to control and understand active sites' behavior during the reaction, providing high activity and durability. This review carefully summarizes the recently reported noble metal‐based heterogeneous catalysts for thermocatalytic conversion of CO2 into methane, carbon monoxide, methanol, formic acid, higher alcohols, C2+ hydrocarbons, and syngas through dry reforming of CH4, to draw the state‐of‐the‐art development in the field. Finally, we critically discuss the impact of these elements on catalyst properties, the challenges related to their implementation, and future research opportunities. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: Alcohols are among the most accessible functionalities. Catalytic deoxygenative functionalization of alcohols is highly synthetically appealing. While significant progress has been made on the reactions with nucleophiles, the reactions with electrophilic coupling partners remain a real challenge. This manuscript highlights the advance in this direction, which is mainly achieved by the first‐row transition metals. The low‐valent titanium catalyst has shown the unique reactivity to homolytically cleave the C—OH bonds. The formed carbon radicals could either undergo reduction to give protonation products or couple with carbon fragments to form C—C bonds. This chemistry is initially realized using a stoichiometric amount of titanium reagents and later extended to catalytic variants. Nickel features a variety of oxidation states ranging from Ni0 to NiIV, and both two‐electron oxidative addition and single‐electron process are involved in their activation of an electrophile. These properties enable nickel to catalyze reductive C—C coupling of alcohols with R–X electrophiles. The reaction is first reported on the reactions of allylic alcohols, then extended to benzylic alcohols and, very recently non‐activated alcohols. Recent effort has resulted in many invaluable methodologies that highly improve the reaction efficiency for the construction of aliphatic C—C bonds. The use of cobalt and copper catalysts not only expands the substrate scope of these reactions but also shows the new reactivity and selectivity issues. [ABSTRACT FROM AUTHOR]

Commercially available Ru-MACHOTM-BH is an active catalyst for the hydrogenation of several functional groups and for the dehydrogenation of alcohols. Herein, we report on the new application of this catalyst to the base-free transfer hydrogenation of carbonyl compounds. Ru-MACHOTM-BH proved to be highly active and selective in this transformation, even with α,β-unsaturated carbonyl compounds as substrates. The corresponding aliphatic, aromatic and allylic alcohols were obtained in excellent yields with catalyst loadings as low as 0.1–0.5 mol % at mild temperatures after very short reaction times. This protocol tolerates iPrOH and EtOH as hydrogen sources. Additionally, scale up to multi-gram amounts was performed without any loss of activity or selectivity. An outer-sphere mechanism has been proposed and the computed kinetics and thermodynamics of crotonaldehyde and 1-phenyl-but-2-en-one are in perfect agreement with the experiment. [ABSTRACT FROM AUTHOR]

C−H methylation is an attractive chemical transformation for C−C bonds construction in organic chemistry, yet efficient methylation of readily available (bio)alcohols in water using methanol as sustainable C1 feedstock is limited. Herein, iridium nanocatalysts encapsulated in yolk-shell-structured mesoporous carbon nanospheres (Ir@YSMCNs) were synthesized for this transformation. Monodispersed Ir clusters (ca. 1.0 nm) were encapsulated in situ and spatially isolated within YSMCNs by a silica-assisted sol-gel emulsion strategy. A selection of (bio)alcohols (19 examples) was selectively methylated in aqueous phase with good-to-high yields over the developed Ir@YSMCNs. The improved catalytic efficiencies in terms of activity and selectivity together with the good stability and recyclability were contributable to the ultrasmall Ir clusters with oxidation chemical state as a consequence of the confinement effect of YSMCNs with interconnected nanostructures. [ABSTRACT FROM AUTHOR]

A highly efficient, ligand-enhanced 2,2,6,6-tetramethylpiperidine-1-oxy (TEMPO)/Mn(NO3)2 catalyst system for the aerobic oxidation of alcohols is described. From the series of coordinating ligands studied herein, 2-picolinic acid (PyCOOH) improves the catalytic activity of TEMPO/Mn(NO3)2 remarkably. Under ambient air at room temperature in acetic acid, the ligand-enhanced catalyst converts aliphatic and benzylic primary alcohols that bear various functional groups into their respective aldehydes with near quantitative conversions. The applicability of the catalyst for convenient preparative synthesis was demonstrated by conducting oxidations on a gram scale. A change of TEMPO to the sterically less demanding 9-azabicyclo[3.3.1]nonane N-oxyl results in a Mn catalyst that is also able to oxidize secondary alcohols to ketones. Mechanistic studies showed that alcohols are oxidized by the oxoammonium cation derived from the nitroxyl radical. The active oxidant is regenerated by Mn(NO3)2, and this process is greatly promoted by the coordination of PyCOOH to Mn. [ABSTRACT FROM AUTHOR]

A new series of water-soluble Ir complexes with N-heterocyclic carbene ligands that bear ester and amide groups has been obtained and fully characterized. The new complexes are highly reactive and selective for the alkylation of amines with alcohols with a 1:1 ratio of reactants in water and in the absence of base or other additives. The catalytic system has a broad substrate scope, which allows the synthesis of a variety of primary and secondary amines in excellent yields. A tolerance to a large range of functional groups was obtained. [ABSTRACT FROM AUTHOR]

Laccase catalyzes the oxidation and polymerization of phenolic compounds in the presence of oxygen. Herein, we report for the first time that a previous PEGylation of laccase enhances the polymerase activity 3-fold compared with the reaction of the native enzyme, as confirmed by UV/Vis spectroscopy. The polymerization of catechol increased only 1.5-fold if poly(ethylene glycol) (PEG) was added to the medium reaction. Molecular-dynamics simulations suggest the formation of a miscible complex of polycatechol and PEG, which is responsible to push the reaction forward. In a negative control experiment set, all catalysts were entrapped inside polyacrylamide gels and here the native laccase showed a relatively higher activity. These results suggest that the mobility of PEG is a key feature for the enhancement of the reaction. [ABSTRACT FROM AUTHOR]

The aqueous solution of ethylene glycol (EG) is a binary liquid mixture that displays rich conformational and structural behaviour, which has not yet been adequately explored through atomistic molecular dynamics simulations. Herein, employing an accurate force field for EG, several physical properties of this solution are calculated to be in quantitative agreement with experimental data. While 79 % of molecules in neat liquid EG exist with their central OCCO dihedral in the gauche state, this fraction increases to 89 % in the dilute aqueous solution, largely in response to the increase in the static dielectric constant of the solution from that of neat liquid EG. The increase in gauche conformers increases the mean dipole moment of EG molecules in the solution which is additionally contributed by specific conformational states of the two terminal HOCC dihedral angles. [ABSTRACT FROM AUTHOR]

In recent years, carbon dioxide (CO2) has been released into the atmosphere resulting in rising CO2 concentration, which has a great impact on climate problems such as global warming. Carbon dioxide is a rich, cheap and easily available renewable resource. The reduction of carbon dioxide as a C1 source into synthetic fuels or high‐value chemicals has aroused great interest among chemists. Over the past few decades, great progress has been made in carbon dioxide reduction and C−C, C−N, C−S bonds construction, but there are still great challenges in the hierarchical reduction of carbon dioxide coupled with the formation of C−O bonds. In this review, we summarized the research progress of carbon dioxide reduction coupled with the formation of C−O bonds to oxygenated compounds in alcohols andprospected the opportunities and challenges in this field. [ABSTRACT FROM AUTHOR]

The front cover picture shows a single metal complex that can catalyse asymmetric epoxidation of non‐functionalised olefins as well as the oxidative kinetic resolution of racemic alcohols with great ease. In this way the use of expensive homogeneous catalyst can be maximised by carrying out two asymmetric organic transformations. Details are given in the Full Paper on page 1426 by Sayed H. R. Abdi and co‐workers. [ABSTRACT FROM AUTHOR]

The Inside Cover picture shows the magic of acrolein direct synthesis by oxidative coupling of alcohols (OCA). The process starts by methanol and ethanol oxidation to formaldehyde and acetaldehyde, respectively, on a FeMoOx redox catalyst followed by the cross‐aldolization of aldehydes and dehydration to acrolein taking place on the acid/base catalyst. The alcohols involved in this process can be biosourced; therefore, this new route to produce acrolein is even more interesting as it can replace current fossil‐based production of acrolein (oxidation of propylene). In their Full Paper (DOI: 10.1002/cssc.201700230), Lilić et al. on page 1916 in Issue 9, 2017, discuss the influence of the acid/base sites on the acrolein yield. [ABSTRACT FROM AUTHOR]

Efficient catalyst: The cover image demonstrates the synthesis of low‐carbon (C2–C4) alcohols from syngas using cetyltrimethylammonium bromide‐promoted, ZnO‐supported, and Mn‐promoted Cu–Fe catalysts. Although Cu–Fe based catalysts produce a large amount of hydrocarbons, their high catalytic activity and strong ability to synthetize long‐chain alcohols still attract significant attention. This work demonstrates that the Cu species are well reduced on the ZnO support and the Cu0/Cu+ ratio on the surface increased as a result of catalyst modification. Cu–Fe3C dual active sites are generated on the flower‐shaped cetyltrimethylammonium bromide‐promoted MnCuFe/ZnO catalyst. The performance study demonstrates that the formation rate of total alcohols is enhanced (and low‐carbon alcohols even more so) at a relatively high level of catalytic activity. More details can be found in the Full Paper by Wei Li and colleagues at East China University of Science and Technology on page 557 in Issue 4, 2017 (DOI: 10.1002/ente.201600366). [ABSTRACT FROM AUTHOR]

Fluorination induces significant modulations of molecular properties. The focus herein is on quantifying its influence on the hydrogen ‐ bond (H ‐ bond) donating capacity of a vicinal OH group. Using β ‐ fluorohydrin probes, changes in H ‐ bond acidity are rationalized by subtle differences in the conformational landscape. The OH⋅⋅⋅F intramolecular H ‐ bonds form five ‐ membered rings, symbolized here by the “Anneaux de Buren” (Nantes, France), and imply a decrease of the OH H ‐ bond acidity in monofluorinated compounds. In contrast, di ‐ and trifluorination of β ‐ fluorohydrins lead to a successive increase of H ‐ bond acidity. More information can be found in the Full Paper by J. Graton, J. ‐ Y. Le Questel, B. Linclau et al. on page 2811 ff. [ABSTRACT FROM AUTHOR]

Combine and shine The cover picture shows the concept of synchrotron‐based IR and UV/Vis microspectroscopy techniques monitoring the methanol‐to‐olefins reaction on a single SAPO‐34 crystal and the spatially resolved information obtained on the retained hydrocarbon species and crystal accessibility, as projected on the two screens. In their Full Paper on p. 772 ff., Q. Qian, J. Ruiz‐Martínez, B. M. Weckhuysen et al. applied in situ synchrotron‐based IR and UV/Vis microscopy in combination with isotopic switching experiments to identify the different hydrocarbon species formed and to assess the reactivity and accessibility of individual SAPO‐34 crystals. Major differences have been observed between the methanol‐to‐olefins and ethanol‐to‐olefins processes in terms of the number of reaction stages and the formation and activity of distinct hydrocarbon species, such as alkylated mono‐ and polyaromatics. [ABSTRACT FROM AUTHOR]

Cu-Co nanocomposites with and without Cs promoter on a modified lanthanum-alumina support were prepared by the combination of two unique synthesis methods. The synthesized materials were exclusively characterized by means of XRD, BET surface area determination, H2 temperature-programmed reduction, CO2 temperature-programmed desorption, N2O frontal chromatography, X-ray photoelectron spectroscopy, high-resolution TEM, and elemental mapping techniques, and its catalytic properties were thoroughly investigated for the selective synthesis of higher alcohols in the CO hydrogenation reaction by using a H2/CO ratio of 1, a temperature range of 180-300 °C and a pressure variation of 15-60 bar. Cs incorporation and a Cu/Co ratio of three was found to be a very efficient combination to obtain alcohol selectivities up to 55 %. This was explained by the fact that Cs increases the surface area of Cu particles by migrating Cu towards the surface layer and strengthens the surface interaction of Cu and Co. The further increase in higher alcohols selectivity then results from the limited formation of methane and carbon dioxide. [ABSTRACT FROM AUTHOR]

The electrocatalytic oxidation of alcohols mediated by TEMPO-like nitroxyl radicals is an economically and industrially viable method that will shortly find commercial application in the synthesis of valued substances including active pharmaceutical ingredients (APIs), valued natural product derivatives, fine chemicals, and valued nanomaterials. [ABSTRACT FROM AUTHOR]

Gold(I)-catalysed intermolecular hydroalkoxylation of enantioenriched 1,3-disubstituted allenes was previously reported to occur with poor chirality transfer due to rapid allene racemisation. The first intermolecular hydroalkoxylation of allenes with efficient chirality transfer is reported here, exploiting conditions that suppress allene racemisation. A full substrate scope study reveals that excellent regio- and stereoselectivities are achieved when a σ-withdrawing substituent is present. [ABSTRACT FROM AUTHOR]

With the irradiation of visible light, α‐heteroarylation of aliphatic alcohol was selectively achieved under gentle conditions in the present of iodobenzene dichloride. The Minisci‐type cross‐dehydrogenative coupling reaction was performed in the absence of metal and acid. Readily available primary alcohols and electron‐withdrawing heteroarenes can be applied smoothly. Mechanism studies indicated that the PhICl radical and chlorine radical formed from iodobenzene dichloride were responsible for the selective hydrogen atom abstraction of alcohols. [ABSTRACT FROM AUTHOR]

Coffee berry borer (CBB), Hypothenemus hampei (Ferrari) (Coleoptera: Scolytinae), is a major pest of coffee worldwide. CBB females use berry volatiles while searching for hosts. Coffee volatiles can be used for monitoring CBB populations. The main objective of this study was to test under laboratory and field conditions bioactive compounds for H. hampei. In the laboratory, CBB females were attracted to the methanol‐ethanol blend (MEB), but not to methylcyclohexane, ethylbenzene, nonane, methyl salicylate, verbenone, α‐pinene, farnesene, and frontalin compared to clean air. In contrast, CBB females preferred clean air over linalool. Females were attracted to most of the tested compounds combined with the MEB over clean air, except farnesene, α‐pinene, and linalool. Females preferred clean air to α‐pinene or linalool, and they showed no preference for clean air or farnesene. Females also preferred the MEB over linalool, verbenone, α‐pinene, or farnesene when combined with MEB. The combination of tested compounds and the MEB did not increase the capture of CBB in the field. Interestingly, α‐pinene and linalool alone, or combined, inhibited the capture of CBB females and non‐target insects by trapping bait with the MEB. Thus, α‐pinene or linalool can be used in a push‐pull strategy considering the low impact over non‐target insects. [ABSTRACT FROM AUTHOR]

The use of benzylic and allylic alcohols in HFIP solvent together with Ti(OiPr)4 has been shown to trigger a highly stereoselective polyene cyclisation cascade. Three new carbon‐carbon bonds are made during the process and complete stereocontrol of up to five new stereogenic centers is observed. The reaction is efficient, has high functional group tolerance and is atom‐economic generating water as a stoichiometric by‐product. A new polyene substrate‐class is employed, and subsequent mechanistic studies indicate a stereoconvergent mechanism. The products of this reaction can be used to synthesize steroid‐analogues in a single step. [ABSTRACT FROM AUTHOR]

A metal and light‐free Minisci‐type acylation approach of 8‐aminoquinoline amides with general primary alcohols was demonstrated under tBu4NCl/K2S2O8 system. Simultaneously, the C2−H alkylation can be realized by accident for special benzyl alcohols bearing strong electron‐donating groups. Most N‐heterocycles were also compatible to afford corresponding acylated products. Furthermore, the mechanism investigation reveals that chlorine radical induced the original ketyl radical generation through abstracting the α‐C−H from the alcohols, then underwent nucleophilic carbon‐centered radicals addition, deprotonation, and oxidation to provide the target acylation products. [ABSTRACT FROM AUTHOR]

Aerobic Oxidation Oxidative transformations utilizing molecular oxygen as the stoichiometric oxidant are of great importance in organic synthesis. Alcohol oxidation reactions that employ O2 are scarce in homogeneous catalysis and mostly involve secondary alcohol oxidation. Moreover, catalytic systems employing O2 as the “primary” oxidant, in the absence of any additive, are rare. As reported by R. Ray, S. Chandra, D. Maiti, and G. K. Lahiri in the Full Paper on page 8814 ff., an efficient Ru ‐ catalyzed oxidation protocol has been developed that enables smooth oxidation of a wide variety of primary, as well as secondary benzylic, allylic, heterocyclic, and aliphatic, alcohols with molecular oxygen as the primary oxidant, without any base or hydrogen ‐ or electron ‐ transfer agents. Experimental evidence, including 18O labeling and kinetic studies, suggested an oxo ‐ ruthenium pathway involving a two ‐ electron hydride transfer in the redox step. [ABSTRACT FROM AUTHOR]