Tunable Low-Relative Humidity and High-Capacity Water Adsorption in a Bibenzotriazole Metal-Organic Framework.

Materials capable of selectively adsorbing or releasing water can enable valuable applications ranging from efficient humidity and temperature control to the direct atmospheric capture of potable water. Despite recent progress in employing metal-organic frameworks (MOFs) as privileged water sorbents, developing a readily accessible, water-stable MOF platform that can be systematically modified for high water uptake at low relative humidity remains a significant challenge. We herein report the development of a tunable MOF that efficiently captures atmospheric water (up to 0.

Photoredox Catalysis-Enabled Sulfination of Alcohols and Bromides.

Sulfinates are important lynchpin intermediates in pharmaceutical production; however, their synthesis via photoredox catalysis is challenging because of their facile oxidation. We herein disclose a photocatalytic strategy for the direct conversion of alcohols and alkyl bromides into alkyl sulfinates. These transformations are enabled by the utilization of easily oxidized radical precursors─namely, alcohol -heterocyclic carbene adducts and -adamantyl aminosupersilane─that facilitate efficient synthesis of the oxidatively labile sulfinate products.

Decatungstate-Catalyzed C()-H Sulfinylation: Rapid Access to Diverse Organosulfur Functionality.

Here we report the direct conversion of strong, aliphatic C()-H bonds into the corresponding alkyl sulfinic acids via decatungstate photocatalysis. This transformation has been applied to a diverse range of C()-rich scaffolds, including natural products and approved pharmaceuticals, providing efficient access to complex sulfur-containing products. To demonstrate the broad potential of this methodology for the divergent synthesis of pharmaceutically relevant molecules, procedures for the diversification of the sulfinic acid products into a range of medicinally relevant functional groups have been developed.

The merger of decatungstate and copper catalysis to enable aliphatic C(sp)-H trifluoromethylation.

The introduction of a trifluoromethyl (CF) group can dramatically improve a compound's biological properties. Despite the well-established importance of trifluoromethylated compounds, general methods for the trifluoromethylation of alkyl C-H bonds remain elusive. Here we report the development of a dual-catalytic C(sp)-H trifluoromethylation through the merger of light-driven, decatungstate-catalysed hydrogen atom transfer and copper catalysis.

Direct arylation of strong aliphatic C-H bonds.

Despite the widespread success of transition-metal-catalysed cross-coupling methodologies, considerable limitations still exist in reactions at sp-hybridized carbon atoms, with most approaches relying on prefunctionalized alkylmetal or bromide coupling partners. Although the use of native functional groups (for example, carboxylic acids, alkenes and alcohols) has improved the overall efficiency of such transformations by expanding the range of potential feedstocks, the direct functionalization of carbon-hydrogen (C-H) bonds-the most abundant moiety in organic molecules-represents a more ideal approach to molecular construction. In recent years, an impressive range of reactions that form C(sp)-heteroatom bonds from strong C-H bonds has been reported.