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Stephen L. Buchwald. Rainka, Matthew P. (Matthew Paul) Massachusetts Institute of Technology. Dept. of Chemistry. Massachusetts Institute of Technology. Department of Chemistry 2006-03-29T18:49:42Z 2006-03-29T18:49:42Z 2005 2005 http://hdl.handle.net/1721.1/32494 61858488 Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2005. Vita. Includes bibliographical references. Chapter 1. A general catalyst system for the synthesis of tetra-ortho-substituted biaryls via the Suzuki-Miyaura cross-coupling reaction is described. It was found that the most efficient catalyst system is based on a phenanthrene-substituted biaryl phosphine ligand. Utilizing this ligand, a number of tetra-ortho-substituted biaryls were synthesized in good to excellent yields. Chapter 2. A procedure for the arylation of methyl and cyclic ketone enolates with o-halonitroarenes was developed. An unusual additive effect of phenols on the outcome of the reaction was observed and explored. This process has provided for the regioselective synthesis of a wide variety of substituted indoles from commercially available materials. Chapter 3. The first method for the asymmetric copper-catalyzed conjugate reduction of [alpha] ,[beta] unsaturated esters containing [beta]-heteroatoms was developed. We found that this system tolerated the presence of both lactams as well as azaheterocycles in the [beta]-position of various enoates. This has led to the asymmetric synthesis of a number of interesting [5- amino acid derivatives. Chapter 4. A copper-catalyzed conjugate reduction reaction that allows for a variety of [gamma]-aryl containing [alpha], [beta]-unsaturated butenolides to be reduced in both high enantiomeric and diastereomeric excess was developed. While a number of catalysts based on chiral bisphosphines were found to successfully perform this transformation, optimal enantioselectivity was obtained when employing the commercially SYNPHOS ligand. by Matthew P. Rainka. Ph.D. 130 leaves 5428815 bytes 5435258 bytes application/pdf application/pdf eng Massachusetts Institute of Technology M.I.T. theses are protected by copyright. They may be viewed from this source for any purpose, but reproduction or distribution in any format is prohibited without written permission. See provided URL for inquiries about permission. http://dspace.mit.edu/handle/1721.1/7582 Chemistry. Development of transitional metal-catalyzed reactions for organic synthesis Thesis application/pdf Publication unknown unknown <Publication xmlns="https://www.openaire.eu/cerif-profile/1.1/" id="973dc014-6f51-455f-8ad4-9a658d5a0ef6"> <Type xmlns="https://www.openaire.eu/cerif-profile/vocab/COAR_Publication_Types">http://purl.org/coar/resource_type/c_1843</Type> <Language>eng</Language> <Title>Development of transitional metal-catalyzed reactions for organic synthesis</Title> <PublishedIn> <Publication> </Publication> </PublishedIn> <PublicationDate>2005</PublicationDate> <Authors> <Author> <DisplayName>Rainka, Matthew P. (Matthew Paul)</DisplayName> <Affiliation> <OrgUnit> </OrgUnit> </Affiliation> </Author> </Authors> <Editors> </Editors> <Publishers> <Publisher> <DisplayName>Massachusetts Institute of Technology</DisplayName> <OrgUnit /> </Publisher> </Publishers> <License>http://dspace.mit.edu/handle/1721.1/7582</License> <Keyword>Chemistry.</Keyword> <Abstract>Chapter 1. A general catalyst system for the synthesis of tetra-ortho-substituted biaryls via the Suzuki-Miyaura cross-coupling reaction is described. It was found that the most efficient catalyst system is based on a phenanthrene-substituted biaryl phosphine ligand. Utilizing this ligand, a number of tetra-ortho-substituted biaryls were synthesized in good to excellent yields. Chapter 2. A procedure for the arylation of methyl and cyclic ketone enolates with o-halonitroarenes was developed. An unusual additive effect of phenols on the outcome of the reaction was observed and explored. This process has provided for the regioselective synthesis of a wide variety of substituted indoles from commercially available materials. Chapter 3. The first method for the asymmetric copper-catalyzed conjugate reduction of [alpha] ,[beta] unsaturated esters containing [beta]-heteroatoms was developed. We found that this system tolerated the presence of both lactams as well as azaheterocycles in the [beta]-position of various enoates. This has led to the asymmetric synthesis of a number of interesting [5- amino acid derivatives. Chapter 4. A copper-catalyzed conjugate reduction reaction that allows for a variety of [gamma]-aryl containing [alpha], [beta]-unsaturated butenolides to be reduced in both high enantiomeric and diastereomeric excess was developed. While a number of catalysts based on chiral bisphosphines were found to successfully perform this transformation, optimal enantioselectivity was obtained when employing the commercially SYNPHOS ligand.</Abstract> <Access xmlns="http://purl.org/coar/access_right" > </Access> </Publication>