Direct Phenolysis Reactions of Unactivated Amides into Phenolic Esters Promoted by a Heterogeneous CeO Catalyst.

The direct catalytic esterification of amides that leads to the construction of C-O bonds through the cleavage of amide C-N bonds is a highly attractive strategy in organic synthesis. While aliphatic and aromatic alcohols can be readily used for the alcoholysis of activated and unactivated amides, the introduction of phenols is more challenging due to their lower nucleophilicity in the phenolysis of unactivated amides. Herein, we demonstrate that phenols can be used for the phenolysis of unactivated amides into the corresponding phenolic esters using a simple heterogenous catalytic system based on CeO under additive-free reaction conditions.

Selective Transformations of Triglycerides into Fatty Amines, Amides, and Nitriles by using Heterogeneous Catalysis.

The use of triglycerides as an important class of biomass is an effective strategy to realize a more sustainable society. Herein, three heterogeneous catalytic methods are reported for the selective one-pot transformation of triglycerides into value-added chemicals: i) the reductive amination of triglycerides into fatty amines with aqueous NH under H promoted by ZrO -supported Pt clusters; ii) the amidation of triglycerides under gaseous NH catalyzed by high-silica H-beta (Hβ) zeolite at 180 °C; iii) the Hβ-promoted synthesis of nitriles from triglycerides and gaseous NH at 220 °C. These methods are widely applicable to the transformation of various triglycerides (C -C skeletons) into the corresponding amines, amides, and nitriles.

Direct Olefination of Alcohols with Sulfones by Using Heterogeneous Platinum Catalysts.

Carbon-supported Pt nanoparticles (Pt/C) were found to be effective heterogeneous catalysts for the direct Julia olefination of alcohols in the presence of sulfones and KOtBu under oxidant-free conditions. Primary alcohols, including aryl, aliphatic, allyl, and heterocyclic alcohols, underwent olefination with dimethyl sulfone and aryl alkyl sulfones to give terminal and internal olefins, respectively. Secondary alcohols underwent methylenation with dimethyl sulfone.

Triarylamine-substituted imidazole- and quinoxaline-fused push-pull porphyrins for dye-sensitized solar cells.

We have prepared a push-pull porphyrin with an electron-donating triarylamino group at the β,β'-edge through a fused imidazole group and an electron-withdrawing carboxyquinoxalino anchoring group at the opposite β,β'-edge (ZnPQI) and evaluated the effects of the push-pull structure of ZnPQI on optical, electrochemical, and photovoltaic properties. ZnPQI showed red-shifted Soret and Q bands relative to a reference porphyrin with only an electron-withdrawing group (ZnPQ), thus demonstrating the improved light-harvesting property of ZnPQI. The optical HOMO-LUMO gap was consistent with that estimated by DFT calculations.