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Stephen L. Buchwald. Perry, Ian B. (Ian Brooks) Massachusetts Institute of Technology. Department of Chemistry. Massachusetts Institute of Technology. Department of Chemistry 2017-12-05T19:13:19Z 2017-12-05T19:13:19Z 2017 http://hdl.handle.net/1721.1/112449 1008968222 Thesis: S.B., Massachusetts Institute of Technology, Department of Chemistry, 2017. Cataloged from PDF version of thesis. "June 2017." Includes bibliographical references. Chapter 1. Copper-Catalyzed Asymmetric Addition of Olefin-Derived Nucleophiles to Ketones A copper (I) catalyzed coupling olefins and ketones has been developed for the diastereo- and enantioselective generation of homopropargyl alcohols bearing vicinal stereocenters. This method allows for the generation of enantioenriched tertiary alcohols with a high degree of functional group compatibility. The utility of the process is further illustrated by a large scale synthesis with extremely low catalyst loading as well as the late stage modification of several pharmaceuticals. Chapter 2. Copper-Catalyzed Enantioselective Addition of Styrene-Derived Nucleophiles to Imines We describe the catalytic generation of amines bearing vicinal stereocenters with a moderate degree of diastereoselectivity. The stereoselective hydrocupration of an unactivated olefinic component is followed by nucleophilic addition of the organocuprate to an N-phosphinoyl protected imine. The mild and general process tolerates a broad-range of functionality, and the process was shown to be successful at a gram-scale synthesis. Chapter 3. Palladium-facilitated Regioselective Nucleophilic Fluorination of Aryl and Heteroaryl Halides. The preliminary findings regarding an aryl and heteroaryl halide fluorination process facilitated by palladium as a reagent is described. Stoichiometric studies illustrate the utility of the method in producing aryl fluorides with unprecedented regioselectivity, and preliminary studies into the fluorination of five- and six-membered heteroaryl bromides are described. Halogen atom substitution as a route to irreversible oxidative addition of aryl and heteroaryl halides is discussed. This strategy may serve to facilitate the fluorination of particularly problematic heteroaryl bromide and chloride substrates. by Ian B. Perry. S.B. 58 pages eng Massachusetts Institute of Technology MIT theses are protected by copyright. They may be viewed, downloaded, or printed from this source but further reproduction or distribution in any format is prohibited without written permission. http://dspace.mit.edu/handle/1721.1/7582 Chemistry. Transition metal-facilitated C-C and C-F bond forming Thesis application/pdf false Publication unknown unknown <Publication xmlns="https://www.openaire.eu/cerif-profile/1.1/" id="11dbfb64-2a74-4d90-a129-ec1242f9be14"> <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>Transition metal-facilitated C-C and C-F bond forming</Title> <PublishedIn> <Publication> </Publication> </PublishedIn> <PublicationDate>2017</PublicationDate> <Authors> <Author> <DisplayName>Perry, Ian B. (Ian Brooks)</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. Copper-Catalyzed Asymmetric Addition of Olefin-Derived Nucleophiles to Ketones A copper (I) catalyzed coupling olefins and ketones has been developed for the diastereo- and enantioselective generation of homopropargyl alcohols bearing vicinal stereocenters. This method allows for the generation of enantioenriched tertiary alcohols with a high degree of functional group compatibility. The utility of the process is further illustrated by a large scale synthesis with extremely low catalyst loading as well as the late stage modification of several pharmaceuticals. Chapter 2. Copper-Catalyzed Enantioselective Addition of Styrene-Derived Nucleophiles to Imines We describe the catalytic generation of amines bearing vicinal stereocenters with a moderate degree of diastereoselectivity. The stereoselective hydrocupration of an unactivated olefinic component is followed by nucleophilic addition of the organocuprate to an N-phosphinoyl protected imine. The mild and general process tolerates a broad-range of functionality, and the process was shown to be successful at a gram-scale synthesis. Chapter 3. Palladium-facilitated Regioselective Nucleophilic Fluorination of Aryl and Heteroaryl Halides. The preliminary findings regarding an aryl and heteroaryl halide fluorination process facilitated by palladium as a reagent is described. Stoichiometric studies illustrate the utility of the method in producing aryl fluorides with unprecedented regioselectivity, and preliminary studies into the fluorination of five- and six-membered heteroaryl bromides are described. Halogen atom substitution as a route to irreversible oxidative addition of aryl and heteroaryl halides is discussed. This strategy may serve to facilitate the fluorination of particularly problematic heteroaryl bromide and chloride substrates.</Abstract> <Access xmlns="http://purl.org/coar/access_right" > </Access> </Publication>