Alfa Chemistry

The sustainability of lithium-based energy storage or conversion systems, e.g., lithium-ion batteries, can be enhanced by establishing methods of efficient lithium extraction from harsh brines. Lai et al. describe a decoupled membrane-free electrochemical cell that cycles lithium ions between iron-phosphate electrodes and features cathode (brine) and anode (fresh water) compartments that are isolated from each other yet electrochemically connected through a pair of silver/silver-halide redox electrodes. This design is compatible with harsh brines having magnesium/lithium molar ratios of up to 3258 and lithium concentrations down to 0.15 millimolar, enabling the production of battery-grade (>99.95% pure) lithium carbonate. Energy savings of up to ~21.5% were realized by efficiently harvesting the osmotic energy of the brines. A pilot-scale cell with an electrode surface area of 33.75 square meters was used to realize lithium extraction from Dead Sea brine with a recovery rate of 84.0%.

Ferroelectric structures have spontaneous macroscopic polarization that can be inverted using external electric fields and have potential applications including information storage, energy transduction, ultralow-power nanoelectronics and biomedical devices. These functions would benefit from nanoscale control of ferroelectric structure, the ability to switch polarization with lower applied fields (low coercive field) and biocompatibility. Soft ferroelectrics based on poly(vinylidene fluoride) (PVDF) have a thermodynamically unstable ferroelectric phase in the homopolymer, complex semi-crystalline structures, and high coercive fields. Here Stupp et al. report on ferroelectric materials formed by water-soluble molecules containing only six VDF repeating units covalently conjugated to a tetrapeptide, with the propensity to assemble into the β-sheet structures that are ubiquitous in proteins. This led to the discovery of ribbon-shaped ferroelectric supramolecular assemblies that are thermodynamically stable with their long axes parallel to both the preferred hydrogen-bonding direction of β-sheets and the bistable polar axes of VDF hexamers. Relative to a commonly used ferroelectric copolymer, the biomolecular assemblies exhibit a coercive field that is two orders of magnitude lower, as the result of supramolecular dynamics, and a similar level of remnant polarization, despite having a peptide content of 49 wt%. Furthermore, the Curie temperature of the assemblies is about 40 °C higher than that of a copolymer containing a similar amount of VDF. This supramolecular system was created using a biologically inspired strategy that is attractive in terms of sustainability and that could lead to new functions for soft ferroelectrics.

The myriad nickel-catalyzed cross-coupling reactions rely on the formation of an organonickel intermediate, but limitations in forming monoalkylnickel species have limited options for C(sp3) cross-coupling. The formation of monoalkylnickel(II) species from abundant carboxylic acid esters would be valuable, but carboxylic acid derivatives are primarily decarboxylated to form alkyl radicals that lack the correct reactivity. In this work, Weix et al. disclose a facile oxidative addition and decarbonylation sequence that forms monoalkylnickel(II) intermediates through a nonradical process. The key ligand, bis(4-methylpyrazole)pyridine, accelerates decarbonylation, stabilizes the alkylnickel(II) intermediate, and destabilizes off-cycle nickel(0) carbonyl species. The utility of this new reactivity in C(sp3)-C(sp3) bond formation is demonstrated in a reaction that is challenging by purely radical methods—the selective cross-coupling of primary carboxylic acid esters with primary alkyl iodides.

The selective conversion of polyethylene (PE), polypropylene (PP), and mixtures of these two polymers to form products with high volume demand is urgently needed because current methods suffer from low selectivity, produce large quantities of greenhouse gases, or rely on expensive, single-use catalysts. The isomerizing ethenolysis of unsaturated polyolefins could be an energetically and environmentally viable route to propylene and isobutylene; however, noble-metal homogeneous catalysts and an unsaturated polyolefin are currently required and the process has been limited to PE. Hartwig et al. show that the simple combination of tungsten oxide on silica and sodium on gamma-alumina transforms PE, PP, or a mixture of the two, including postconsumer forms of these materials, to propylene or a mixture of propylene and isobutylene in greater than 90% yield at 320°C without the need for dehydrogenation of the starting polyolefins.

Hydrogen atom abstraction is an important elementary chemical process but is very difficult to carry out enantioselectively. Phipps et al. have developed catalysts, readily derived from the Cinchona alkaloid family of natural products, which can achieve this by virtue of their chiral amine structure. The catalyst, following single-electron oxidation, desymmetrizes meso-diols by selectively abstracting a hydrogen atom from one carbon center, which then regains a hydrogen atom by abstraction from a thiol. This results in an enantioselective epimerization process, forming the chiral diastereomer with high enantiomeric excess. Cyclic and acyclic 1,2-diols are compatible, as are acyclic 1,3-diols. Additionally, the viability of combining approach with carbon-carbon bond formation in Giese addition is demonstrated.

Covalent bonds share electron pairs between two atoms and make up the skeletons of most organic compounds in single, double and triple bonds. In contrast, examples of one-electron bonds remain scarce, most probably due to their intrinsic weakness. Although several pioneering studies have reported one-electron bonds between heteroatoms, direct evidence for one-electron bonds between carbon atoms remains elusive. Here Ishigaki et al. report the isolation of a compound with a one-electron σ-bond between carbon atoms by means of the one-electron oxidation of a hydrocarbon with an elongated C–C single bond. The presence of the C•C one-electron σ-bond (2.921(3) Å at 100 K) was confirmed experimentally by single-crystal X-ray diffraction analysis and Raman spectroscopy, and theoretically by density functional theory calculations. The results unequivocally demonstrate the existence of a C•C one-electron σ-bond, which was postulated nearly a century ago, and can thus be expected to pave the way for further development in different areas of chemistry by probing the boundary between bonded and non-bonded states.

The unimolecular heterolysis of covalent σ-bonds is integral to many chemical transformations, including SN1-, E1- and 1,2-migration reactions. To a first approximation, the unequal redistribution of electron density during bond heterolysis is governed by the difference in polarity of the two departing bonding partners. This means that if a σ-bond consists of two identical groups (that is, symmetric σ-bonds), its unimolecular fission from the S0, S1, or T1 states only occurs homolytically after thermal or photochemical activation. To force symmetric σ-bonds into heterolytic manifolds, co-activation by bimolecular noncovalent interactions is necessary. These tactics are only applicable to σ-bond constituents susceptible to such polarizing effects, and often suffer from inefficient chemoselectivity in polyfunctional molecules. Here Rehbein et al. report the net heterolysis of symmetric and homopolar σ-bonds (that is, those with similar electronegativity and equal leaving group ability) by means of stimulated doublet–doublet electron transfer (SDET). As exemplified by Se–Se and C–Se σ-bonds, symmetric and homopolar bonds initially undergo thermal homolysis, followed by photochemically SDET, eventually leading to net heterolysis. Two key factors make this process feasible and synthetically valuable: (1) photoexcitation probably occurs in only one of the incipient radical pair members, thus leading to coincidental symmetry breaking and consequently net heterolysis even of symmetric σ-bonds. (2) If non-identical radicals are formed, each radical may be excited at different wavelengths, thus rendering the net heterolysis highly chemospecific and orthogonal to conventional heterolyses. This feature is demonstrated in a series of atypical SN1 reactions, in which selenides show SDET-induced nucleofugalities rivalling those of more electronegative halides or diazoniums.

The stereoselective activation of alkanes constitutes a long-standing and grand challenge for chemistry. Although metal-containing enzymes oxidize alkanes with remarkable ease and selectivity, chemical approaches have largely been limited to transition metal–based catalytic carbon–hydrogen functionalizations. Alkanes can be protonated to form pentacoordinated carbonium ions and fragmented into smaller hydrocarbons in the presence of strong Brønsted acids. However, catalytic stereocontrol over such reactions has not previously been accomplished. List et al. show here that strong and confined acids catalyze highly enantioselective fragmentations of a variety of cyclopropanes into the corresponding alkenes, expanding the boundaries of catalytic selective alkane activation. Computational studies suggest the involvement of the long-debated cycloproponium ions.

Samarium diiodide (SmI2) is a privileged, single-electron reductant deployed in diverse synthetic settings. However, generalizable methods for catalytic turnover remain elusive because of the well-known challenge associated with cleaving strong SmIII–O bonds. Prior efforts have focused on the use of highly reactive oxophiles to enable catalyst turnover. However, such approaches give rise to complex catalyst speciation and intrinsically limit the synthetic scope. Herein, Peters et al. leveraged a mild and selective protonolysis strategy to achieve samarium-catalyzed, intermolecular reductive cross-coupling of ketones and acrylates with broad scope. The modularity of our approach allows rational control of selectivity based on solvent, pKa (where Ka is the acid dissociation constant), and the samarium coordination sphere and provides a basis for future developments in catalytic and electrocatalytic lanthanide chemistry.

Transition metal–catalyzed cross-couplings have great potential to furnish complex ethers; however, challenges in the C(sp3)–O functionalization step have precluded general methods. Here, White et al. describe computationally guided transition metal–ligand design that positions a hydrogen-bond acceptor anion at the reactive site to promote functionalization. A general cross-coupling of primary, secondary, and tertiary aliphatic alcohols with terminal olefins to furnish >130 ethers is achieved. The mild conditions tolerate functionality that is prone to substitution, elimination, and epimerization and achieve site selectivity in polyol settings. Mechanistic studies support the hypothesis that the ligand’s geometry and electronics direct positioning of the phosphate anion at the π-allyl-palladium terminus, facilitating the phosphate’s hydrogen-bond acceptor role toward the alcohol. Ligand-directed counteranion positioning in cationic transition metal catalysis has the potential to be a general strategy for promoting challenging bimolecular reactivity.