Aseries of Mn I complexes containing lutidine-based chiral pincer ligands with modular and tunable structures has been developed. The complex shows unprecedentedly high activities (up to 9800 TON; TON = turnover number), broad substrate scope (81 examples), good functional-group tolerance,a nd excellent enantioselectivities (85-98 %e e) in the hydrogenation of various ketones.T hese aspects are rare in earth-abundant metal catalyzedhydrogenations.T he utility of the protocol have been demonstrated in the asymmetric synthesis of av ariety of key intermediates for chiral drugs. Preliminary mechanistic investigations indicate that an outersphere mode of substrate-catalyst interactions probably dominates the catalysis.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.
Sweat pH monitoring is a routine indicator in wearable biotechnology. The state-of-the-art wearable pH sensors mostly rely on organic materials but face the risk of biological toxicity. WO 3 is a typical H + -sensitive inorganic material with chemical stability, biocompatibility, and low cost but low sensitivity and slow response. Lattice H + intercalation is herein proposed as an efficient approach that can greatly improve the sensitivity and selectivity of WO 3based pH sensors. Specifically, lattice H + intercalation can promote WO 3 from the monoclinic phase to cubic phase, which enhances the ion exchange capacity between WO 3 and H + . The resistance decreases more than two orders of magnitudes, which improves the interfacial charge transport. The occupancy of lattice H + leads to ion exchange only with H + , thus increasing the H + recognition. The intercalated H x WO 3 exhibits much improved sensitivity, reversibility, and response time. Additionally, the H x WO 3 is integrated with a solid reference electrode on a miniaturized chip for wearable sweat pH monitoring. The pH sensor exhibits good potential response even at curving over 270°. On-body sweat pH measurments show high accuracy compared with ex situ analyses. This work emphasizes the concept of lattice proton intercalation to regulate the H + recognition of solid contacts.
Aseries of Mn I complexes containing lutidine-based chiral pincer ligands with modular and tunable structures has been developed. The complex shows unprecedentedly high activities (up to 9800 TON; TON = turnover number), broad substrate scope (81 examples), good functional-group tolerance,a nd excellent enantioselectivities (85-98 %e e) in the hydrogenation of various ketones.T hese aspects are rare in earth-abundant metal catalyzedhydrogenations.T he utility of the protocol have been demonstrated in the asymmetric synthesis of av ariety of key intermediates for chiral drugs. Preliminary mechanistic investigations indicate that an outersphere mode of substrate-catalyst interactions probably dominates the catalysis.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.
A practical route from oxetane or thietane to γ-(thio)butyrolactone via solvated-proton-assisted cobalt-catalyzed carbonylative ring expansion under syngas atmosphere has been established. A wide variety of γ-(thio)butyrolactones can be afforded in good to excellent yields. The versatility of this method has been well demonstrated in the synthesis of intermediates towards the natural product Arctigenin as well as the pharmaceuticals Baclofen and Montelukast. The observed promoting effect of glycol ether solvent has been rationally interpreted.
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