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Part I. Asymmetric hydrosilylation of acetophenone using titanium catalysts. Part II. Synthesis of water-soluble palladacycles and their applications to the Suzuki reaction. Part III. Rhodium-catalyzed addition of aryl and alkenylboronic acids to aldehyd

Posted on:2006-03-12Degree:Ph.DType:Thesis
University:The University of AlabamaCandidate:Huang, RongcaiFull Text:PDF
GTID:2451390008959022Subject:Organic Chemistry
Abstract/Summary:
This dissertation consists of three parts. The first part deals with the asymmetric hydrosilylation of acetophenone using titanium catalysts. Titanium complexes were formed in situ by treating bisoxazolines with n-BuLi followed by the addition of titanium salts. The catalytically active titanium (III) hydride species were generated by treating the titanium complexes formed in situ with two equivalents of n-BuLi (relative to titanium). Acetophenone was reduced to phenethyl alcohol with enriched ee at room temperature in twelve to twenty-four hours in the presence of triethoxysilane.;Part two deals with synthesis of water-soluble palladacycles and their applications to the Suzuki reaction. Application of green chemistry to organic synthesis has been achieved through aqueous-phase, homogenous catalysis. Water is the most attractive alternative among the commonly explored solvents due to its nontoxicity, low flammability, low cost, wide availability, and environmentally benign features. Palladacycles are efficient catalyst precursors for homogenous catalysis. Four water-soluble palladacycles were successfully synthesized. The combination of water-soluble palladacycles with a sterically demanding, water-soluble ligand t-Bu-Amphos provided highly active catalysts for the Suzuki reaction in water. Efficient recyclable catalytic systems in water were developed.;Part three deals with rhodium-catalyzed addition of aryl and alkenylboronic acids to aldehydes. The combination of RhCl3•3H2O with t-Bu-Amphos provided a facile method for the addition of aryl- or alkenylboronic acids to aldehydes in aqueous media. The addition reaction of benzaldehyde occurred in neat water, providing an environmentally benign route to the synthesis of benzhydrol. Catalyst recycling was accomplished for nine cycles under the applied conditions.
Keywords/Search Tags:Titanium, Part, Water-soluble palladacycles, Synthesis, Suzuki reaction, Alkenylboronic acids, Catalysts, Acetophenone
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