Palladium-Catalyzed Intramolecular Insertion of Alkenes into the Carbon–Nitrogen Bond of β‑Lactams

The carbon–nitrogen bond of β-lactams is cleaved by palladium(0), and an alkene is intramolecularly inserted therein. The following reductive elimination produces nitrogen-containing benzo-fused tricycles in good to high yields

Metal–Organic Frameworks with Precisely Designed Interior for Carbon Dioxide Capture in the Presence of Water

The selective capture of carbon dioxide in the presence of water is an outstanding challenge. Here, we show that the interior of IRMOF-74-III can be covalently functionalized with primary amine (IRMOF-74-III-CH₂NH₂) and used for the selective capture of CO₂ in 65% relative humidity. This study encompasses the synthesis, structural characterization, gas adsorption, and CO₂ capture properties of variously functionalized IRMOF-74-III compounds (IRMOF-74-III-CH₃, -NH₂, -CH₂NHBoc, -CH₂NMeBoc, -CH₂NH₂, and -CH₂NHMe). Cross-polarization magic angle spinning ¹³C NMR spectra showed that CO₂ binds chemically to IRMOF-74-III-CH₂NH₂ and -CH₂NHMe to make carbamic species. Carbon dioxide isotherms and breakthrough experiments show that IRMOF-74-III-CH₂NH₂ is especially efficient at taking up CO₂ (3.2 mmol of CO₂ per gram at 800 Torr) and, more significantly, removing CO₂ from wet nitrogen gas streams with breakthrough time of 610 ± 10 s g^–1 and full preservation of the IRMOF structure

Introduction of Functionality, Selection of Topology, and Enhancement of Gas Adsorption in Multivariate Metal–Organic Framework-177

Metal–organic framework-177 (MOF-177) is one of the most porous materials whose structure is composed of octahedral Zn₄O­(−COO)₆ and triangular 1,3,5-benzenetribenzoate (BTB) units to make a three-dimensional extended network based on the <b>qom</b> topology. This topology violates a long-standing thesis where highly symmetric building units are expected to yield highly symmetric networks. In the case of octahedron and triangle combinations, MOFs based on pyrite (<b>pyr</b>) and rutile (<b>rtl</b>) nets were expected instead of <b>qom</b>. In this study, we have made 24 MOF-177 structures with different functional groups on the triangular BTB linker, having one or more functionalities. We find that the position of the functional groups on the BTB unit allows the selection for a specific net (<b>qom</b>, <b>pyr</b>, and <b>rtl</b>), and that mixing of functionalities (-H, -NH₂, and -C₄H₄) is an important strategy for the incorporation of a specific functionality (-NO₂) into MOF-177 where otherwise incorporation of such functionality would be difficult. Such mixing of functionalities to make multivariate MOF-177 structures leads to enhancement of hydrogen uptake by 25%

Introduction of Functionality, Selection of Topology, and Enhancement of Gas Adsorption in Multivariate Metal–Organic Framework-177

Metal–organic framework-177 (MOF-177) is one of the most porous materials whose structure is composed of octahedral Zn₄O­(−COO)₆ and triangular 1,3,5-benzenetribenzoate (BTB) units to make a three-dimensional extended network based on the <b>qom</b> topology. This topology violates a long-standing thesis where highly symmetric building units are expected to yield highly symmetric networks. In the case of octahedron and triangle combinations, MOFs based on pyrite (<b>pyr</b>) and rutile (<b>rtl</b>) nets were expected instead of <b>qom</b>. In this study, we have made 24 MOF-177 structures with different functional groups on the triangular BTB linker, having one or more functionalities. We find that the position of the functional groups on the BTB unit allows the selection for a specific net (<b>qom</b>, <b>pyr</b>, and <b>rtl</b>), and that mixing of functionalities (-H, -NH₂, and -C₄H₄) is an important strategy for the incorporation of a specific functionality (-NO₂) into MOF-177 where otherwise incorporation of such functionality would be difficult. Such mixing of functionalities to make multivariate MOF-177 structures leads to enhancement of hydrogen uptake by 25%