ABSTRACT
Isosorbide and its functionalized derivatives have numerous applications as bio-sourced building blocks. In this context, the synthesis of diols from isosorbide diallyl ether by hydrohydroxymethylation reaction is of extreme interest. This hydrohydroxymethylation, which consists of carbon-carbon double bonds converting into primary alcohol functions, can be obtained by a hydroformylation reaction followed by a hydrogenation reaction. In this study, reductive hydroformylation was achieved using isosorbide diallyl ether as a substrate in a rhodium/amine catalytic system. The highest yield in bis-primary alcohols obtained was equal to 79%.
ABSTRACT
Linear α-olefins (LAO) are one of the main targets in the field of surfactants, lubricants, and polymers. With the depletion of petroleum resources, the production of LAO from renewable feedstocks has gained increasing interest in recent years. In the present study, we demonstrated that Ir catalysts were suitable to decarbonylate a wide range of biosourced substrates under rather mild conditions (160 °C, 5â h reaction time) in the presence of potassium iodide and acetic anhydride. The resulting LAO were obtained with good conversion and selectivity provided that the purity of the substrate, the nature of the ligand, and the amounts of the additives were controlled accurately. The catalytic system could be recovered efficiently by using a Kugelrohr distillation apparatus and recycled.
Subject(s)
Alkenes/chemistry , Fatty Acids, Unsaturated/chemistry , Catalysis , Iridium/chemistry , Kinetics , TemperatureABSTRACT
New compound Zn[(S,S)-iPr-pybox](Et)(2) (1) was fully characterized, including by X-ray diffraction structural studies. Its grafting onto partially dehydroxylated silica affords material 2, which bears well-defined chiral ([triple bond]SiO)Zn[(S,S)-iPr-pybox](Et) sites. Hybrid material 2 displays significantly better catalytic performances than 1 in enantioselective silylcyanation, thus demonstrating a beneficial grafting effect.
