Using an internally oxidizing directing group (DG) strategy, we report a RhIII-catalyzed synthesis of isoquinolones via C–H activation/annulation of benzoylhydrazines and alkynes. Tunable double cascade cyclization of benzoylhydrazines with two equivalents of alkynes led to tetracyclic amides. These N-heterocycles demonstrated adjustable AIE properties.

We report a palladium-catalyzed intermolecular [4 + 1] annulation pathway for N-phenoxyacetamides with aldehydes to form 1,2-benzisoxazoles. By activating the C–H bonds ortho to phenol-derived O–N bonds, the method enables the simultaneous construction of C–C and CN bonds in 1,2-benzisoxazoles with the O–N bonds intact. The method has been successfully applied to the synthesis of active pharmaceutical intermediates, such as risperidone.

An efficient Rh(III)-catalyzed coupling reaction of N-phenoxyacetamides with α,β-unsaturated aldehydes to give 1,2-oxazepines via C–H activation/[4+3] annulation has been developed. This transformation does not require oxidants and features C–C/C–N bond formation to yield seven-membered oxazepine rings at room temperature. Further derivation of 1,2-oxazepines leads to important chroman derivatives.

Monodisperse porous zirconia (ZrO2) microspheres with nanocrystallized framework were fabricated by impregnation of porous polymer microspheres as a novel hard template with zirconia precursors followed by calcination to remove the template. Porous phosphorylated zirconia (PhZr) microspheres were prepared by further treating porous zirconia microspheres with phosphoric acid. The morphology, structure, and properties of these microspheres were studied by scanning electron microscopy (SEM), transmission electron microscopy (TEM), N2 adsorption/desorption measurement, FT-IR, and X-ray powder diffraction. The as-prepared zirconia and phosphorylated zirconia microspheres showed uniform particle size and well-defined morphology. The phosphorylated zirconia microspheres served as highly active solid acid catalysts for Friedel–Crafts alkylation of indoles with chalcones and could be reused for 22 cycles with negligible loss of activity. In situ pyridine-adsorbed FT-IR analysis of the best performing PhZr microspheres suggested the presence of both Lewis and Brønsted acid sites, and the total acidity as measured by temperature-programmed desorption of ammonia (NH3-TPD) was 328 μmol·g-1.Keywords: Friedel−Crafts alkylation; indoles; monodisperse; phosphorylation; porous zirconia microspheres;

A monodisperse Pt/ceria hybrid with controlled nanoporous structure was fabricated with the aid of poly(glycidyl methacrylate-co-ethylene glycol dimethacrylate) microspheres as a hard template. Functional groups on the polymer microspheres interacted with Pt species and then cerium precursors were impregnated into the microsphere pores through a sol–gel method. Porous ceria microspheres embedded with uniform and fine Pt nanoparticles formed after removal of the polymer templates by calcination. The hierarchical Pt/ceria hybrid possesses catalytic activity, excellent stability and ease of recyclability. For example, a highly efficient catalytic reduction of 4-nitrophenol (4-NP) with sodium borohydride was accomplished. This facile and general synthetic method could be extended to other novel metal/oxide hybrid combinations.

We developed a photoactivatable firefly luciferase (pfLuc) whose activation can be controlled by light. A photocaged Lys analogue was site-specifically incorporated into fLuc to replace its key catalytic Lys residue, Lys529, rendering fLuc inactive until light-triggered removal of the caging group. This photoinduced gain of luminescence provides a facile approach for assessing the photolysis efficiency of this valuable photosensitive Lys analogue within the context of its carrier protein in vitro and in living cells. We further took advantage of the spatial and temporal activation feature of pfLuc for intracellular measurement of labile ATP levels without impairment of cellular physiology.

Sialic acid analogues containing a unique chemical functionality or chemical reporter have been metabolically incorporated into sialylated glycans. This process, termed metabolic glycan labeling, has emerged as a powerful tool for studying sialylation as well as other types of glycosylation. Currently, this technique can install only a single functionality. Here we describe a strategy for dual labeling of sialylated glycans using a new class of bifunctional sialic acid analogues containing two distinct chemical reporters at the N-acyl and C9 positions. These bifunctional unnatural sialic acids were metabolically incorporated into cellular glycans, where the two chemical reporters exerted their distinct functions. This approach expands the capability of metabolic glycan labeling to probe sialylation and glycan–protein interactions.

An efficient Rh(III)-catalyzed coupling reaction of N-phenoxyacetamides with α,β-unsaturated aldehydes to give 1,2-oxazepines via C–H activation/[4+3] annulation has been developed. This transformation does not require oxidants and features C–C/C–N bond formation to yield seven-membered oxazepine rings at room temperature. Further derivation of 1,2-oxazepines leads to important chroman derivatives.

Using an internally oxidizing directing group (DG) strategy, we report a RhIII-catalyzed synthesis of isoquinolones via C–H activation/annulation of benzoylhydrazines and alkynes. Tunable double cascade cyclization of benzoylhydrazines with two equivalents of alkynes led to tetracyclic amides. These N-heterocycles demonstrated adjustable AIE properties.

We report a palladium-catalyzed intermolecular [4 + 1] annulation pathway for N-phenoxyacetamides with aldehydes to form 1,2-benzisoxazoles. By activating the C–H bonds ortho to phenol-derived O–N bonds, the method enables the simultaneous construction of C–C and CN bonds in 1,2-benzisoxazoles with the O–N bonds intact. The method has been successfully applied to the synthesis of active pharmaceutical intermediates, such as risperidone.