Atroposelective desymmetrization of 2-arylresorcinols via Tsuji-Trost allylation.

Palladium-catalyzed asymmetric allylic alkylation has proven to be a powerful method for the preparation of a wide variety of chiral molecules. However, the catalytic and atroposelective allylic alkylation is still rare and challenging, especially for biaryl substrates. Herein, we report the palladium-catalyzed desymmetric and atroposelective allylation, in which the palladium complex with a chiral phosphoramidite ligand enables desymmetrization of nucleophilic 2-arylresorcinols in a highly enantioselective manner. With the aid of the secondary kinetic resolution effect, a wide variety of substrates containing a hydroxymethyl group at the bottom aromatic ring are able to provide O-allylated products up to 98:2 er. Computational studies show an accessible quadrant of the allylpalladium complex and provide three plausible transition states with intra- or intermolecular hydrogen bonding. The energetically favorable transition state is in good agreement with the observed enantioselectivity and suggests that the catalytic reaction would proceed with an intramolecular hydrogen bond.

Organocatalytic Atroposelective Synthesis of Isoquinolines via Dynamic Kinetic Resolution.

Herein, a highly enantioselective Pictet-Spengler reaction for the synthesis of axially chiral tetrahydroisoquinolines via dynamic kinetic resolution is described. Chiral phosphoric acids catalyze cyclization to yield single regioisomeric isoquinolines with excellent enantioselectivities around the C-C bond up to 99% ee. The current protocol is effective for a wide range of substrates, and the observed enantiodivergence depends on the substituents on the catalysts.

Janus Graphene Oxide Sheets with Fe3O4 Nanoparticles and Polydopamine as Anodes for Lithium-Ion Batteries.

In this study, a one-step process to fabricate "Janus"-structured nanocomposites with iron oxide (Fe3O4) nanoparticles (Fe3O4 NPs) and polydopamine (PDA) on each side of a graphene oxide (GO) nanosheet using the Langmuir-Schaefer technique has been proposed. The Fe3O4 NPs-GO hybrid is used as a high-capacity active material, while PDA is added as a binder due to its unique wet-resistant adhesive property. The transmission electron microscopy image shows a superlattice-like out-of-plane section of the multilayered nanocomposite, which maximizes the density of the composite materials. Grazing-incidence small-angle X-ray scattering results combined with scanning electron microscopy images confirm that the multilayered Janus composite exhibits an in-plane hexagonal array structure of closely packed Fe3O4 NPs. This Janus multilayered structure is expected to maximize the amount of active material in a specific volume and reduce volume changes caused by the conversion reaction of Fe3O4 NPs. According to the electrochemical results, the Janus multilayer electrode delivers an excellent capacity of ∼903 mAh g-1 at a current density of 200 mA g-1 and a reversible capacity of ∼639 mAh g-1 at 1 A g-1 up to the 1800th cycle, indicating that this Janus composite can be a promising anode for Li-ion batteries.

Bottlebrush Copolymer as Surface Neutralizer for Vertical Alignment of Block Copolymer Nanodomains in Thin Films.

Herein we designed bottlebrush copolymers for use as a neutral additive to block copolymer (BCP) thin films in which they are segregated to the interfaces via architectural effects and produce nonpreferential interfaces to induce perpendicular orientation of BCP microdomains. Two BCP systems were employed, a conventional poly(styrene-b-methyl methacrylate) (PS-b-PMMA) with relatively low χ and similar surface energies between blocks, and a high χ poly(styrene-b-methacrylic acid) (PS-b-PMAA) with distinct surface energies. The bottlebrushes, with either short side-chains of PS-r-PMMA or PS-r-PMAA random copolymers, were synthesized via ring-opening metathesis polymerization (ROMP). Remarkably, it was observed that the top and bottom interfaces of both BCP films were enriched with bottlebrush copolymers, regardless of the surface energy difference between blocks, hence, vertically oriented microdomains were achieved for both BCP systems. This can be attributed to the screening of polymer interactions by a good solvent during the spin-casting process, allowing architectural effects to play a role in surface segregation of bottlebrush copolymers, as confirmed by contact angle measurements and time-of-flight secondary ion mass spectroscopy (TOF-SIMS). We believe that this concept can be further extended to various applications that require polymer films with functional surfaces.