ingest cdrApp 2018-08-23T19:46:29.969Z d39a25df-af15-48e9-aec2-c9af81a997a2 modifyDatastreamByValue RELS-EXT fedoraAdmin 2018-08-23T19:47:15.588Z Setting exclusive relation addDatastream MD_TECHNICAL fedoraAdmin 2018-08-23T19:47:26.858Z Adding technical metadata derived by FITS addDatastream MD_FULL_TEXT fedoraAdmin 2018-08-23T19:47:41.960Z Adding full text metadata extracted by Apache Tika modifyDatastreamByValue RELS-EXT fedoraAdmin 2018-08-23T19:48:03.980Z Setting exclusive relation modifyDatastreamByValue MD_DESCRIPTIVE cdrApp 2018-09-26T19:41:29.581Z modifyDatastreamByValue MD_DESCRIPTIVE cdrApp 2019-03-20T13:32:29.483Z Stephanie Murray Author Department of Chemistry College of Arts and Sciences New Methods for Stereoselective Incorporation of Boron into Molecules Utilizing 1,1-Organodiboronate Esters I. Enantio- and Diastereoselective 1,2-Additions of 1,1-Diborylalkanes to alpha-Ketoesters An enantio- and diastereoselective addition of 1,1-diborylalkanes to alpha-ketoesters is reported. The reaction is catalyzed by a copper-phosphoramidite catalyst system and yields products in up to 70% yield, 99:1 er and >20:1 dr after oxidation to the corresponding diol. The utility of the products is illustrated through functionalizations including homologation, cross-metathesis, and tetrahydropyran synthesis. II. Stereoselective 3-Component Bis-Electrophile Couplings of 1,1-Diborylalkanes A stereoselective tandem epoxide ring-opening/allylation reaction facilitated by a copper catalyst is reported. The reaction is tolerant of alkyl and aryl epoxides in good yield (up to 99%) and diastereoselectivity (up to >20:1). The application of this technique to the synthesis of polyol motifs is explored. Cross coupling, amination, and alkene functionalization reactions illustrate the versatility of the products. III. Synthesis of Stereodefined Alkenyl Boronates from Epoxides and Diborylmethane through Pd-Catalyzed Dehydroboration The palladium catalyzed synthesis of alkenyl boronate esters from epoxides and diborylmethane via a dehydroboration process is reported. Products are obtained in up to 75% yield as single olefin isomer. The substrate scope includes alkyl, aryl, and complex steroid derived molecules. The products are further functionalized through cross coupling and cycloproponation procedures. Summer 2018 2018 Organic chemistry boron, catalysis, copper, methodology, stereoselective eng Doctor of Philosophy Dissertation University of North Carolina at Chapel Hill Graduate School Degree granting institution Chemistry Simon Meek Thesis advisor Marcey Waters Thesis advisor Jeffrey Johnson Thesis advisor Jillian Dempsey Thesis advisor Alexander Miller Thesis advisor text Stephanie Murray Creator Department of Chemistry College of Arts and Sciences New Methods for Stereoselective Incorporation of Boron into Molecules Utilizing 1,1-Organodiboronate Esters I. Enantio- and Diastereoselective 1,2-Additions of 1,1-Diborylalkanes to alpha-Ketoesters An enantio- and diastereoselective addition of 1,1-diborylalkanes to alpha-ketoesters is reported. The reaction is catalyzed by a copper-phosphoramidite catalyst system and yields products in up to 70% yield, 99:1 er and >20:1 dr after oxidation to the corresponding diol. The utility of the products is illustrated through functionalizations including homologation, cross-metathesis, and tetrahydropyran synthesis. II. Stereoselective 3-Component Bis-Electrophile Couplings of 1,1-Diborylalkanes A stereoselective tandem epoxide ring-opening/allylation reaction facilitated by a copper catalyst is reported. The reaction is tolerant of alkyl and aryl epoxides in good yield (up to 99%) and diastereoselectivity (up to >20:1). The application of this technique to the synthesis of polyol motifs is explored. Cross coupling, amination, and alkene functionalization reactions illustrate the versatility of the products. III. Synthesis of Stereodefined Alkenyl Boronates from Epoxides and Diborylmethane through Pd-Catalyzed Dehydroboration The palladium catalyzed synthesis of alkenyl boronate esters from epoxides and diborylmethane via a dehydroboration process is reported. Products are obtained in up to 75% yield as single olefin isomer. The substrate scope includes alkyl, aryl, and complex steroid derived molecules. The products are further functionalized through cross coupling and cycloproponation procedures. Organic chemistry boron; catalysis; copper; methodology; stereoselective Doctor of Philosophy Dissertation University of North Carolina at Chapel Hill Graduate School Degree granting institution Chemistry Simon Meek Thesis advisor Marcey Waters Thesis advisor Jeffrey Johnson Thesis advisor Jillian Dempsey Thesis advisor Alexander Miller Thesis advisor 2018 2018-08 eng text Stephanie Murray Creator Department of Chemistry College of Arts and Sciences I. Enantio- and Diastereoselective 1,2-Additions of 1,1-Diborylalkanes to alpha-Ketoesters An enantio- and diastereoselective addition of 1,1-diborylalkanes to alpha-ketoesters is reported. The reaction is catalyzed by a copper-phosphoramidite catalyst system and yields products in up to 70% yield, 99:1 er and >20:1 dr after oxidation to the corresponding diol. The utility of the products is illustrated through functionalizations including homologation, cross-metathesis, and tetrahydropyran synthesis. II. Stereoselective 3-Component Bis-Electrophile Couplings of 1,1-Diborylalkanes A stereoselective tandem epoxide ring-opening/allylation reaction facilitated by a copper catalyst is reported. The reaction is tolerant of alkyl and aryl epoxides in good yield (up to 99%) and diastereoselectivity (up to >20:1). The application of this technique to the synthesis of polyol motifs is explored. Cross coupling, amination, and alkene functionalization reactions illustrate the versatility of the products. III. Synthesis of Stereodefined Alkenyl Boronates from Epoxides and Diborylmethane through Pd-Catalyzed Dehydroboration The palladium catalyzed synthesis of alkenyl boronate esters from epoxides and diborylmethane via a dehydroboration process is reported. Products are obtained in up to 75% yield as single olefin isomer. The substrate scope includes alkyl, aryl, and complex steroid derived molecules. The products are further functionalized through cross coupling and cycloproponation procedures. Organic chemistry boron; catalysis; copper; methodology; stereoselective Doctor of Philosophy Dissertation University of North Carolina at Chapel Hill Graduate School Degree granting institution Simon Meek Thesis advisor Marcey Waters Thesis advisor Jeffrey Johnson Thesis advisor Jillian Dempsey Thesis advisor Alexander Miller Thesis advisor 2018 2018-08 eng text Murray_unc_0153D_18012.pdf uuid:c7333a1e-183a-404a-a0c4-9c386e3f2300 2020-08-23T00:00:00 2018-07-11T16:41:28Z proquest application/pdf 28275235