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https://www.selleckchem.com/products/Semagacestat(LY450139).html The preparation of compounds with novel atomic oxidation states and emergent properties is of fundamental interest in chemistry. As s-block elements, alkali-earth metals invariably show a +2 formal oxidation state at normal conditions, and among them, barium (Ba) presents the strongest chemical reactivity. Herein, we propose that novel valence states of Ba can be achieved in pressure-induced chalcogenides, where it also shows a feature of 5d-elements. First-principles swarm-intelligence structural search calculations identify three novel stoichiometric compounds BaCh4 (Ch = O, S) containing Ba2+, Ba3Ch2 (Ch = S, Se, Te) with Ba+ and Ba2+, and Ba2Ch (Ch = Se, Te) with Ba+ cations. The pressure-induced drop of the Ba 5d level relative to Ba 6s is responsible for this unusual oxidation state. These compounds display captivating structural characters, such as Ba-centered polyhedra and chain-shaped Ch units. More interestingly still, the interaction between two Ba+ ions ensures their structural stability.A catalytic intermolecular amination of nonactivated tertiary C(sp3)-H bonds (BDE of 96 kcal·mol-1) is reported for substrates displaying an activated benzylic site (BDE of 85 kcal·mol-1). The tertiary C(sp3)-H bond is selectively functionalized to afford α,α,α-trisubstituted amides in high yields. This unusual site-selectivity results from the synergistic combination of Rh2(S-tfpttl)4, a rhodium(II) complex with a well-defined catalytic pocket, with tert-butylphenol sulfamate (TBPhsNH2), which leads to a discriminating rhodium-bound nitrene species under mild oxidative conditions. This catalytic system is very robust, and the reaction was performed on a 50 mmol scale with only 0.01 mol % of catalyst. The TBPhs group can be removed under mild conditions to afford the corresponding NH-free amines.MAT2a is a methionine adenosyltransferase that synthesizes the essential metabolite S-adenosylmethionine (SAM) fr

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