Comprehensive Summary

One dihydride-bridged dimeric Dy(III) guanidinate complex, formulated as [{(Me₃Si)₂NC(NⁱPr)₂}₂Dy(μ-H)]₂ (1Dy), was successfully isolated and the introduction of hydride bridges significantly reduces the intramolecular Dy(III)···Dy(III) distance to only 3.688(1) Å. To investigate the effect of such a short Dy(III)···Dy(III) distance for magnetism, we also prepared its dibromide-bridged analogue [{(Me₃Si)₂NC(NⁱPr)₂}₂Dy(μ-Br)]₂ (2Dy), which has a much longer Dy(III)···Dy(III) distance of 4.605(4) Å. Surprisingly, 2Dy demonstrates much larger effective energy barrier for magnetization reversal (U _eff) and higher blocking temperature (T _B). The worse performance of 1Dy is attributed to the concerted effect of strong antiferromagnetic interactions between Dy(III) ions (J _total = -2.683 cm^-1) and the unparallel arrangement of magnetic principle axes of the Dy(III) ions for 1Dy.

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Comprehensive Summary

Herein we report a condition-controlled divergent synthesis of spiro indene-2,1'-isoindolinones and spiro isochroman-3,1'-isoindolinones through cobalt-catalyzed formal [4 + 1] and [4 + 1 + 1] spirocyclization of aromatic amides with 2-diazo-1H-indene-1,3(2H)-dione. When the reaction is carried out under air in ethyl acetate, spiro indene-2,1'-isoindolinones are formed through Co(II)-catalyzed C−H/N−H [4 + 1] spirocyclization. When the reaction is run under O₂ in CH₃CN, on the other hand, spiro isochroman-3,1'-isoindolinones are generated through Baeyer-Villiger oxidation of the in situ formed spiro indene-2,1'-isoindolinones with O₂ as a cheaper and environmental-friendly oxygen source. In general, these protocols have advantages such as using non-precious and earth-abundant metal catalyst, no extra additive, high efficiency and regioselectivity. A gram-scale synthesis and the removal of the directing group further highlight its utility.

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4-(2-Aminophenyl)-3-yn-1-ols are selectively transformed into high value added 3,5-dihydrofuro[3,2-c]quinolin-4(2H)-ones by a PdI₂-catalyzed sequential 5-endo-dig O-cyclization – N-cyclocarbonylation process under oxidative conditions.

Comprehensive Summary

The PdI₂/KI-catalyzed oxidative carbonylation of 4-(2-aminophenyl)-3-yn-1-ols, bearing two potential nucleophilic groups in suitable position selectively leads to dihydrofuroquinolinone derivatives in fair to high yields (60%—89%) and excellent turnover numbers (180—267 mol of product per mol of Pd) over 19 examples, through a mechanistic pathway involving initial O-cyclization followed by N-cyclocarbonylation. In such process, the selective catalytic construction of two rings and three new bonds is achieved in one synthetic step to afford high value added fused heterocyclic structures starting from readily available materials.

This cover picture shows that the continuously changing surfaces of Dynamic Surface Antifouling (DSAF) materials can effectively prevent microorganisms from landing and adhering. Due to the degradation of the main chain and the hydrolysis of the side chain, the surface renewing is not driven by external force, so the DSAF materials have good antifouling ability even under static conditions. They are also eco-friendly since such degradation yields low molecular weight molecules instead of microplastics. DSAF provides a general strategy to defeat marine biofouling. More details are discussed in the article by Zhang et al. on page 2881—2888.

This cover picture shows that the continuously changing surfaces of Dynamic Surface Antifouling (DSAF) materials can effectively prevent microorganisms from landing and adhering. Due to the degradation of the main chain and the hydrolysis of the side chain, the surface renewing is not driven by external force, so the DSAF materials have good antifouling ability even under static conditions. They are also eco-friendly since such degradation yields low molecular weight molecules instead of microplastics. DSAF provides a general strategy to defeat marine biofouling. More details are discussed in the article by Zhang et al. on page 2881—2888.

Synthesis of C—N axial chirality N-arylindoles via Pd(II)/SPA-catalyzed free amine-directed atroposelective C—H olefination was achieved. A series of C—N axially chiral N-aromatic amine indoles were obtained in high yields with good enantioselectivities (35 examples, up to 91% yield and 96% ee).

Comprehensive Summary

Axially chiral N-arylindoles bearing a stereogenic C—N axis are unique important scaffolds in natural products, advance materials, pharmaceuticals and privileged chiral ligands or catalysts. Herein, we report the direct synthesis of C—N axially chiral N-arylindoles through a Pd-catalyzed free amine-directed atroposelective C—H olefination enabled by a spiro phosphoric acid (SPA) ligand. A wide range of enantioenriched N-aromatic amine indoles were obtained in high yields with good enantioselectivities (35 examples, up to 91% yield and up to 96% ee). The chiral products with free amine group offer an effective functional handle for down-stream diversity-oriented synthesis.