A ruthenium/C-TunePhos catalytic system has been identified for highly efficient direct reductive amination of simple ketones. The strategy makes use of ammonium acetate as the amine source and H as the reductant and is a user-friendly and operatively simple access to industrially relevant primary amines. Excellent enantiocontrol (>90% ee for most cases) was achieved with a wide range of alkyl aryl ketones. The practicability of this methodology has been highlighted by scalable synthesis of key intermediates of three drug molecules. Moreover, an improved synthetic route to the optimal diphosphine ligand C-TunePhos is also presented.

We report a quite flexible naphthol-based cage (so-called “naphthocage”) which adopts a self-inclusion conformation in its free state and is able to bind singly charged organic cations extremely strongly (K a > 107 M–1). Ion-selective electrodes prepared with this naphthocage show a super-Nernstian response to acetylcholine. In addition, the highly stable complex (1010 M–1) between ferrocenium and the naphthocage can be switched electrochemically, which lays a basis for its application in stimuli-responsive materials.

A diversity-oriented synthetic strategy was developed for the total synthesis of kainoid amino acids, which led to the enantioselective synthesis of (-)-kainic acid and the first total synthesis of (+)-acromelic acid C. Rh(i)-catalyzed asymmetric enyne cycloisomerization served as the key reaction in this strategy for the rapid construction of highly functionalized lactam, and the resulting vinyl acetate moiety was further utilized as a versatile building block for the installation of both isopropylidene and 2-pyridone units existing in natural kainoids.

Radialenes and expanded radialenes are cross‐conjugated macrocycles displaying poor aromatic character. In this work, three 9‐fluorenylidene substituted expanded [n]radialenes (ER‐n, n=3–5) with a diacetylene spacer were synthesized and their structures were confirmed by X‐ray crystallographic analysis and NMR spectroscopy. They all can be easily reduced into relatively stable dianions. Detailed experimental measurements and theoretical calculations suggest that their dianions (ER‐n2−, n=3–5) are stabilized by both the aromatic fluorenyl anion substituents and the central aromatic rings with formally [4n+2] delocalized π electrons. In addition, the dianions of the extended radialenes (ER‐42− and ER‐52−) show unique open‐shell diradical character with a small singlet‐triplet energy gap. For comparison, their linear counterparts (L‐3 and L‐4) were also synthesized; their dianions exhibit very different redox and optical properties from their respective macrocycles.