Biomimetic Total Synthesis of Clavicipitic Acid: A DDQ-Mediated Intramolecular Cross-Dehydrogenative Coupling Approach.

Clavicipitic acid, a communesin alkaloid precursor, has attracted significant attention due to its unique azepino[5,4,3-cd]indole framework. Herein, we report a novel biomimetic synthesis of clavicipitic acid diastereomers by utilizing a DDQ-mediated cross-dehydrogenative coupling (CDC) reaction. The synthesis involves Suzuki coupling for the prenylation of a 4-bromotryptophan derivative, followed by an intramolecular CDC reaction to construct the azepinoindole core. The trans isomer was obtained as the major product, and the two diastereomers were separable. The CDC reaction conditions, including temperature, solvent, and protecting groups, were investigated, and a plausible mechanism for the observed diastereoselectivity was proposed.

High Entropy Oxide (CrMnFeNiMg)3 O4 with Large Compositional Space Shows Long-Term Stability as Cathode in Lithium-Sulfur Batteries.

The repeated formation and irreversible diffusion of liquid-state lithium polysulfides (LiPSs) are the primary challenges in the development of high-energy-density lithium-sulfur battery (LSB). An effective strategy to alleviate the resulting polysulfide loss is critical for the stability of LSBs. In this regard, high entropy oxides (HEOs) appear as a promising additive for the adsorption and conversion of LiPSs owing to the diverse active sites, offering unparalleled synergistic effects. Herein, we have developed a (CrMnFeNiMg)3 O4 HEO as a functional polysulfide trapper in LSB cathode. The adsorption of LiPSs by the metal species (i. e., Cr, Mn, Fe, Ni, and Mg) in the HEO takes place through two different paths and leads to enhanced electrochemical stability. We demonstrate that the optimal sulfur cathode with the (CrMnFeNiMg)3 O4 HEO attains a high peak and reversible discharge capacities of 857 mAh g-1 and 552 mAh g-1 , respectively, at a cycling rate of C/10, a long cycle life of 300 cycles, and a high rate performance at the cycling rates from C/10 to C/2.

Organoselenium-Catalyzed Asymmetric Cyclopropanations of (E)-Chalcones.

We report a new class of chiral tetrahydroselenophene based on (S)-diphenyl(tetrahydroselenophen-2-yl)methanol, which was prepared from (R)-3-(3-bromopropyl)-2,2-diphenyloxirane and sodium selenide. These chiral tetrahydroselenophene-based compounds were used to catalyze asymmetric cyclopropanation reactions; the selenonium ylide intermediates formed from these selenium-containing catalysts and benzyl bromide efficiently react with (E)-chalcones to give various cyclopropanes (27 examples) with excellent enantioselectivities of ≤99% ee and are the first examples of organoselenium-catalyzed asymmetric cyclopropanations.

Module-Designed Carbon-Coated Separators for High-Loading, High-Sulfur-Utilization Cathodes in Lithium-Sulfur Batteries.

Lithium-sulfur batteries have great potential as next-generation energy-storage devices because of their high theoretical charge-storage capacity and the low cost of the sulfur cathode. To accelerate the development of lithium-sulfur technology, it is necessary to address the intrinsic material and extrinsic technological challenges brought about by the insulating active solid-state materials and the soluble active liquid-state materials. Herein, we report a systematic investigation of module-designed carbon-coated separators, where the carbon coating layer on the polypropylene membrane decreases the irreversible loss of dissolved polysulfides and increases the reaction kinetics of the high-loading sulfur cathode. Eight different conductive carbon coatings were considered to investigate how the materials' characteristics contribute to the lithium-sulfur cell's cathode performance. The cell with a nonporous-carbon-coated separator delivered an optimized peak capacity of 1112 mA∙h g-1 at a cycling rate of C/10 and retained a high reversible capacity of 710 mA∙h g-1 after 200 cycles under lean-electrolyte conditions. Moreover, we demonstrate the practical high specific capacity of the cathode and its commercial potential, achieving high sulfur loading and content of 4.0 mg cm-2 and 70 wt%, respectively, and attaining high areal and gravimetric capacities of 4.45 mA∙h cm-2 and 778 mA∙h g-1, respectively.