Rhodium-Catalyzed Regioselective Hydroformylation of Alkynes to α,ß-Unsaturated Aldehydes Using Formic Acid.

A rhodium-catalyzed hydroformylation of alkynes with formic acid was developed. The method provides α,ß-unsaturated aldehydes in high yield and E-selectivity without the need to handle toxic CO gas.

Hydrogen bonding-induced aromatic oligoamide foldamers as spherand analogues to accelerate the hydrolysis of nitro-substituted anisole in aqueous media.

Four intramolecular hydrogen bonding-driven aromatic amide foldamers 2-5 have been designed and synthesized in which a 2-methoxy-3-nitrobenzamide unit was incorporated at the end of the backbone. Kinetic studies in dioxane-water (4:1, v/v) at 60-90 degrees C have revealed that the folded backbone of the oligomers was, like the rigidified spherand, able to complex Li+, Na+, and K+ and, consequently, accelerated the hydrolysis of the nitro-appended anisole unit of the foldamers. Generally, longer foldamers displayed an increased accelerating effect, and LiOH displayed the highest reactivity probably due to the most efficient complexation by the folded oligomers. Addition of excessive potassium chloride substantially reduced the complexing interaction, and the hydrolysis of the longer oligomers became slower than that of the shorter ones due to an increased steric effect. The results indicate that, even in a hot aqueous medium of high polarity, intramolecular hydrogen bonding is still able to induce structurally matched oligomers to generate a preorganized rigidified conformation.