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1.
Angew Chem Int Ed Engl ; : e202405620, 2024 May 06.
Artículo en Inglés | MEDLINE | ID: mdl-38709194

RESUMEN

Manganese-based layered oxides are currently of significant interest as cathode materials for sodium-ion batteries due to their low toxicity and high specific capacity. However, the practical applications are impeded by sluggish intrinsic Na+ migration and poor structure stability as a result of Jahn-Teller distortion and complicated phase transition. In this study, a high-entropy strategy is proposed to enhance the high-voltage capacity and cycling stability. The designed P2-Na0.67Mn0.6Cu0.08Ni0.09Fe0.18Ti0.05O2 achieves a deeply desodiation and delivers charging capacity of 158.1 mA h g-1 corresponding to 0.61 Na with a high initial Coulombic efficiency of 98.2%. The charge compensation is attributed to the cationic and anionic redox reactions conjunctively. Moreover, the crystal structure is effectively stabilized, leading to a slight variation of lattice parameters. This research carries implications for the expedited development of low-cost, high-energy-density cathode materials for sodium-ion batteries.

2.
Angew Chem Int Ed Engl ; : e202401181, 2024 May 09.
Artículo en Inglés | MEDLINE | ID: mdl-38725281

RESUMEN

Developing novel catalysts with potent activity is of great importance in organocatalysis. In this study, we designed and prepared a new class of benzotetramisole Lewis base catalysts (AxBTM) that have both central and axial chirality. This unique feature of these catalysts results in a three-dimensional microenvironment with multi-layers of chirality. The performance of the developed catalysts was tested in a series of cycloaddition reactions. These included the AxBTM-catalyzed (2 + 2) cycloaddition between α-fluoro-α-aryl anhydride with imines or oxindoles, and the sequential gold/AxBTM-catalyzed (4 + 2) cycloaddition of enynamides with pentafluorophenyl esters. The interplay between axial and central chirality had a collaborative effect in regulating the stereochemistry in these cycloadditions, leading to high levels of stereoselectivity that would otherwise be challenging to achieve using conventional BTM catalysts. However, the (2 + 2) and (4 + 2) cycloadditions have different predilections for axial and central chirality combinations.

3.
Angew Chem Int Ed Engl ; 62(2): e202215714, 2023 01 09.
Artículo en Inglés | MEDLINE | ID: mdl-36380525

RESUMEN

Synergistic catalysis has emerged as one of the most powerful tools for stereodivergent formation of Csp3 -Csp3 bonds bearing vicinal stereocenters. Despite the many successes that have been achieved in this field, stereodivergent Csp3 -Csp3 coupling reactions involving stabilized nucleophiles remain challenging because of the competing single-catalysis pathway. Herein, we report a synergistic palladium/phase-transfer catalyst system that enables diastereodivergent Csp3 -Csp3 coupling reactions of 1,3-dienes with stabilized nucleophile oxindoles. Both the syn and anti coupling products, bearing quaternary and tertiary vicinal stereocenters, could be selectively produced in good yields with high enantio- and diastereoselectivities. Non-covalent activation of the stabilized nucleophile via chiral ion pair in a biphasic system is a crucial success factor in achieving diastereodivergence.


Asunto(s)
Paladio , Paladio/química , Estereoisomerismo , Oxindoles , Catálisis
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