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Abstract Recent years have witnessed marked progress in the efficient synthesis of various enantioenriched 1,2,3,4-tetrahydroquinoxalines. However, enantio- and diastereoselective access to trans-2,3-disubstituted 1,2,3,4-tetrahydroquinoxalines remains much less explored. Herein we report that a frustrated Lewis pair-based catalyst generated via in situ hydroboration of 2-vinylnaphthalene with HB(C6F5)2 allows for the one-pot tandem cyclization/hydrosilylation of 1,2-diaminobenzenes and 1,2-diketones with commercially available PhSiH3 to exclusively afford trans-2,3-disubstituted 1,2,3,4-tetrahydroquinoxalines in high yields with excellent diastereoselectivities (>20 : 1 dr). Furthermore, this reaction can be rendered asymmetric by using an enantioenriched borane-based catalyst derived from HB(C6F5)2 and a binaphthyl-based chiral diene to give rise to enantioenriched trans-2,3-disubstituted 1,2,3,4-tetrahydroquinoxalines in high yields with almost complete diastereo- and enantiocontrol (>20 : 1 dr, up to >99 % ee). A wide substrate scope, good tolerance of diverse functionality and up to 20-gram scale production are demonstrated. The enantio- and diastereocontrol are achieved by the judicious choice of borane catalyst and hydrosilane. The catalytic pathway and the origin of the excellent stereoselectivity are elucidated by mechanistic experiments and DFT calculations. 

Li₂MnO₃has been contemplated as a high‐capacity cathode candidate for Li‐ion batteries; however, it evolves oxygen during battery charging under ambient conditions, which hinders a reversible reaction. However, it is unclear if this irreversible process still holds under subambient conditions. Here, the low‐temperature electrochemical properties of Li₂MnO₃in an aqueous LiCl electrolyte are evaluated and a reversible discharge capacity of 302 mAh g⁻¹at a potential of 1.0 V versus Ag/AgCl at −78 °C with good rate capability and stable cycling performance, in sharp contrast to the findings in a typical Li₂MnO₃cell cycled at room temperature, is observed. However, the results reveal that the capacity does not originate from the reversible oxygen oxidation in Li₂MnO₃but the reversible Cl₂(l)/Cl⁻(aq.) redox from the electrolyte. The results demonstrate the good catalytic properties of Li₂MnO₃to promote the Cl₂/Cl⁻redox at low temperatures.