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Relevant academic research and scientific papers

Cationic carboxylato complexes of dirhodium(II) with oxo thioethers: Catalysts for silane alcoholysis under homogeneous and liquid-liquid biphasic conditions

A set of cationic dirhodium(II) complexes with oxo thioethers was prepared and employed as catalysts for the silane alcoholysis reaction. The complexes were found to be highly active under homogeneous conditions, both in the absence and in the presence of a solvent, including coordinating solvents such as N,N-dimethylformamide ; the catalysts could be conveniently employed in concentrations as low as 0.01 mol%, and a maximum TON of 30000 was recorded after 24 h. The same catalysts were also employed under liquid-liquid biphasic conditions with an ionic liquid as the catalyst-containing phase: comparable catalytic activity was observed under these conditions, and the catalyst-containing phase could be recovered and recycled. A chiral cationic dirhodium(II) complex was also prepared in the frame of this work; kinetic resolution of a racemic alcohol was attempted with this catalyst, unfortunately without success.

MYOGLOBIN-BASED CATALYSTS FOR CARBENE TRANSFER REACTIONS

Methods are provided for carrying out carbene transfer transformations such as olefin cyclopropanation reactions, carbene heteroatom-H insertion reactions (heteroatom = N, S, Si), sigmatropic rearrangement reactions, and aldehyde olefination reactions with high efficiency and selectivity by using a novel class of myoglobin-based biocatalysts. These methods are useful for the synthesis of a variety of organic compounds which contain one or more new carbon-carbon or carbon-heteroatom (N, S, or Si) bond. The methods can be applied for conducting these transformations in vitro (i.e., using the biocatalyst in isolated form) and in vivo (i.e., using the biocatalyst in a whole cell system).