Amines are prominent in natural products, pharmaceutical agents, and agrochemicals. Moreover, they are synthetically valuable building blocks for the construction of complex organic molecules and functional materials. However, amines, especially aliphatic and aromatic amines with free N-H, are prone to coordinate with transition-metal and deactivating the catalyst, posing a tremendous challenge to the application of Lewis basic amines in the amination of ole ns. Herein we present the rst case of oxidative amination of simple ole ns with various Lewis basic amines. The combination of a palladium catalyst, 2,6-dimethyl-1,4-benzoquinone (2,6-DMBQ), and a phosphorous ligand leads to the e cient synthesis of alkyl and aryl allylamines. A series of allylamines are obtained with good yields and excellent regio-and stereoselectivities. Intramolecular amination to synthesize tetrahydropyrrole and piperidine derivatives was also realized. Mechanistic investigations reveal that the reaction undergoes allylic C(sp 3 )-H activation and subsequent functionalization.

Two nanosize lanthanide clusters Na3[Eu48O6(OH)84(tca)34(gly)12(H2O)22]·2Htca·6Cl·6H2O·NO3 (Eu 48 ) and Na­[Tb48O6(OH)84(fca)26(dmp)14(H2O)24]·4Hfca·NO3·8Cl (Tb 48 ) have been isolated in the presence of the monodentate carboxylic acid and tridentate chelate ligands under solvothermal condition. Single-crystal X-ray diffraction analyses indicate that Eu 48 and Tb 48 feature a nanopillar structure constructed by [Ln3(μ3-OH)4] and [Ln5(μ4-O)­(μ3-OH)8] building blocks. In the cavity of the nanopillar, two kinds of anion templates, i.e., NO3 – and Cl–, exist, which connect with the nanopillar by hydrogen bond interactions. As the hitherto highest-nuclearity Eu and Tb clusters, the solid-state photoluminescence properties of Eu 48 (λEx = 365 nm) and Tb 48 (λEx = 370 nm) display dual emission from the characteristic emissions of Eu3+ and Tb3+ ions and weak ligand emissions. Nevertheless, the Eu3+-centered emission was shown under 395 nm excitation with no discernible ligand emission. Moreover, the luminescence properties of Eu 48 and Tb 48 display a response to temperature. With the temperature lowering, the emission peak intensities gradually increase, and good linker relations exist in the range of 118–298 K. This work provides a reference for choosing suitable ligands to synthesize the high-nuclearity luminescent lanthanide nanoclusters.

A binary hybrid system comprising a hypervalent iodine(III) reagent and BF 3 •OEt 2 Lewis acid was found to be effective for the diastereoselective α-acetoxylation of cyclic ketones. In this hybrid system, BF 3 •OEt 2 Lewis acid allowed the activation of the hypervalent iodine(III) reagent and cyclic ketones for smooth α-acetoxylation reaction, achieving high diastereoselectivity. This hypervalent iodine-mediated α-acetoxylation of the cyclic ketone reaction plausibly undergoes an S N 2 substitution mechanism via an α-C-bound hypervalent iodine intermediate. The diastereoselectivity of the reaction mainly originates from thermodynamic control.

No abstract