Nickel‐Catalyzed α‐Arylation of Ketones with Phenol Derivatives

The nickel‐catalyzed α‐arylation of ketones with readily available phenol derivatives (esters and carbamates) provides access to useful α‐arylketones. For this transformation, 3,4‐bis(dicyclohexylphosphino)thiophene (dcypt) was identified as a new, enabling, air‐stable ligand for this transformation. The intermediate of an assumed C? O oxidative addition was isolated and characterized by X‐ray crystal‐structure analysis.     

Selective Aerobic Oxidation of Primary Alcohols to Aldehydes over Nb2O5 Photocatalyst with Visible Light

Primary alcohols are selectively converted into aldehydes by using a Nb₂O₅ photocatalyst under visible‐light irradiation. A strong interaction between the alcohol and Nb₂O₅ generates a donor level within the forbidden band of Nb₂O₅, which provides a visible‐light‐harvesting ability. Over oxidation of aldehydes into carboxylic acids does not proceed under visible‐light irradiation.     

Spiroborate-Based Host Materials with High Triplet Energies and Ambipolar Charge-Transport Properties

Organic light-emitting diodes (OLEDs) receive considerable attention because of their commercial use in flat panel displays. Herein, highly efficient spiroborate-based host materials are reported for use in blue OLEDs. Our designed spiroborates ( SBOX ) were simple to synthesize and exhibited high triplet excitation energies, narrow S-T gaps, and balanced charge carrier mobilities. A blue OLED containing one of the designed spiroborates, SBON , as a host exhibited a high external quantum efficiency (27.6 %) and low turn-on voltage (3.7 V) compared to those observed using 3,3′-di(9H-carbazol-9-yl)-1,1′-biphenyl (17.6 % and 4.5 V, respectively), indicating their potential as host materials in OLEDs.     

Asymmetric Total Synthesis of Heronamides A–C: Stereochemical Confirmation and Impact of Long‐Range Stereochemical Communication on the Biological Activity

Heronamides are biosynthetically related metabolites isolated from marine‐derived actinomycetes. Heronamide C shows potent antifungal activity by targeting membrane phospholipids possessing saturated hydrocarbon chains with as‐yet‐unrevealed modes of action. In spite of their curious hypothesized biosynthesis and fascinating biological activities, there have been conflicts in regard to the reported stereochemistries of heronamides. Here, we describe the asymmetric total synthesis of the originally proposed and revised structures of heronamide C, which unambiguously confirmed the chemical structure of this molecule. We also demonstrated nonenzymatic synthesis of heronamides A and B from heronamide C, which not only proved the postulated biosynthesis, but also confirmed the correct structures of heronamides A and B. Investigation of the structure–activity relationship of synthetic and natural heronamides revealed the importance of both long‐range stereochemical communication and the 20‐membered macrolactam ring for the biological activity of these compounds.     

Intermolecular [2+2+1] Carbonylative Cycloaddition of Aldehydes with Alkynes,and Subsequent Oxidation to γ‐Hydroxybutenolides by a Supported Ruthenium Catalyst

Intermolecular [2+2+1] carbonylative cycloaddition of aldehydes with alkynes and subsequent oxidation to γ‐hydroxybutenolides is achieved using a supported ruthenium catalyst. A ceria‐supported ruthenium catalyst promotes the reaction efficiently, even with an ambient pressure of CO or without external CO, thus giving the corresponding γ‐hydroxybutenolide derivatives in good to high yields. Moreover this catalyst can be reused with no loss of activity.     

Enzymatic polymerization to artificial hyaluronic acid using a transition state analogue monomer

Artificial hyaluronic acid has been synthesized in vitro via enzymatic polymerization catalyzed by testicular hyaluronidases, which is the first successful example of the hyaluronic acid synthesis via non-biosynthetic pathways. The novel GlcAβ(1→3)GlcNAc oxazoline derivative was designed and synthesized as a transition state analogue monomer for the hyaluronidase catalysis. The oxazoline monomer was efficiently recognized by the enzymes at pH 7.1 to 9.0 and the polymerization reaction proceeded in a regio- and stereo-selective manner to give rise to artificial hyaluronic acid with molecular weight higher than 15000. These results strongly suggest that the transition state of these testicular hyaluronidases catalysis corresponds to a sugar oxazolinium ion.