{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/16816"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/16816","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Part I. Large scale procedure for the α-arylation of esters catalyzed by the pd(i) dimer [p(tbu)3]pd(μ-br)]2. Part II. Palladium-catalyzed γ-arylation of α,β-unsaturated esters","abstract":"We report the development of a procedure for the α-arylation of esters on 42 mmol scale which did not require use of a glovebox. The coupling of 3-bromoanisole and methyl isobutyrate catalyzed by 0.075 % [(P(tBu)3Pd(μ-Br)]2 occurred in 72% yield. The reaction was performed with commercially available reagents at a lab bench utilizing Schlenk technique. We report the γ-arylation of α,β-unsaturated esters in high yield with broad scope by coupling aryl, heteroaryl and vinyl halides with the corresponding silicon dienolates. These reactions occur in high yield with a variety of esters and with aromatic and vinylic electrophiles bearing potentially reactive functional groups. The coupling also proceeds in moderate to good yield for the coupling with silyl ketene acetals containing substitution at the α,β,γ- or δ-position. Moreover, these reactions occur without typical fluoride activators.","abstract_html":"We report the development of a procedure for the α-arylation of esters on 42 mmol scale which did not require use of a glovebox. The coupling of 3-bromoanisole and methyl isobutyrate catalyzed by 0.075 % [(P(tBu)3Pd(μ-Br)]2 occurred in 72% yield. The reaction was performed with commercially available reagents at a lab bench utilizing Schlenk technique. We report the γ-arylation of α,β-unsaturated esters in high yield with broad scope by coupling aryl, heteroaryl and vinyl halides with the corresponding silicon dienolates. These reactions occur in high yield with a variety of esters and with aromatic and vinylic electrophiles bearing potentially reactive functional groups. The coupling also proceeds in moderate to good yield for the coupling with silyl ketene acetals containing substitution at the α,β,γ- or δ-position. Moreover, these reactions occur without typical fluoride activators.","abstract_has_math":false,"creators":["Huang, David S."],"institution":"University of Illinois at Urbana-Champaign","degree_name":"M.S.","degree_level":"Thesis","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Hartwig, John F."],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2010,"date_issued":"2010-08-20T17:58:44Z","date_published":"2010-08-20T17:58:44Z","updated_at":"2026-07-22T22:25:09Z","subjects":["cross-coupling","enolates","homogeneous catalysis","palladium"],"languages":["en"],"rights":["Copyright 2010 David S. Huang"],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"http://hdl.handle.net/2142/16816","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Hartwig, John F."]},{"key":"dc:creator","label":"Author","values":["Huang, David S."]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2010-08-20T17:58:44Z","2010-08"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry"]},{"key":"thesis:degree_level","label":"Degree Level","values":["Thesis"]},{"key":"thesis:degree_name","label":"Degree Name","values":["M.S."]},{"key":"thesis:institution_name","label":"Thesis Institution Name","values":["University of Illinois at Urbana-Champaign"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["cross-coupling","enolates","homogeneous catalysis","palladium"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["en"]},{"key":"dc:rights","label":"Dc Rights","values":["Copyright 2010 David S. Huang"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["http://hdl.handle.net/2142/16816"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["We report the development of a procedure for the α-arylation of esters on 42 mmol scale which did not require use of a glovebox. The coupling of 3-bromoanisole and methyl isobutyrate catalyzed by 0.075 % [(P(tBu)3Pd(μ-Br)]2 occurred in 72% yield. The reaction was performed with commercially available reagents at a lab bench utilizing Schlenk technique. We report the γ-arylation of α,β-unsaturated esters in high yield with broad scope by coupling aryl, heteroaryl and vinyl halides with the corresponding silicon dienolates. These reactions occur in high yield with a variety of esters and with aromatic and vinylic electrophiles bearing potentially reactive functional groups. The coupling also proceeds in moderate to good yield for the coupling with silyl ketene acetals containing substitution at the α,β,γ- or δ-position. Moreover, these reactions occur without typical fluoride activators.","Item withdrawn by Mark Zulauf (zulauf@illinois.edu) on 2010-07-21T15:51:08Z Item was in collections: University of Illinois Theses & Dissertations (ID: 1) No. of bitstreams: 1 Huang_David.pdf: 708478 bytes, checksum: f697cc2e41c5e7e27954e8962d494355 (MD5)","Made available in DSpace on 2010-08-20T17:58:44Z (GMT). No. of bitstreams: 3 Huang_David.pdf: 708478 bytes, checksum: f697cc2e41c5e7e27954e8962d494355 (MD5) 1_Huang_David.pdf: 699640 bytes, checksum: 3c23e2a98521ba5348f1e9424cd26668 (MD5) license.txt: 4061 bytes, checksum: 38cd6fe8788b3b6fd74eca9c8bdb6c98 (MD5)"]},{"key":"dc:title","label":"Title","values":["Part I. Large scale procedure for the α-arylation of esters catalyzed by the pd(i) dimer [p(tbu)3]pd(μ-br)]2. Part II. Palladium-catalyzed γ-arylation of α,β-unsaturated esters"]}]}],"canonical_facts":{"dc:contributor":["Hartwig, John F."],"dc:creator":["Huang, David S."],"dc:date":["2010-08-20T17:58:44Z","2010-08"],"dc:description":["We report the development of a procedure for the α-arylation of esters on 42 mmol scale which did not require use of a glovebox. The coupling of 3-bromoanisole and methyl isobutyrate catalyzed by 0.075 % [(P(tBu)3Pd(μ-Br)]2 occurred in 72% yield. The reaction was performed with commercially available reagents at a lab bench utilizing Schlenk technique. We report the γ-arylation of α,β-unsaturated esters in high yield with broad scope by coupling aryl, heteroaryl and vinyl halides with the corresponding silicon dienolates. These reactions occur in high yield with a variety of esters and with aromatic and vinylic electrophiles bearing potentially reactive functional groups. The coupling also proceeds in moderate to good yield for the coupling with silyl ketene acetals containing substitution at the α,β,γ- or δ-position. Moreover, these reactions occur without typical fluoride activators.","Item withdrawn by Mark Zulauf (zulauf@illinois.edu) on 2010-07-21T15:51:08Z Item was in collections: University of Illinois Theses & Dissertations (ID: 1) No. of bitstreams: 1 Huang_David.pdf: 708478 bytes, checksum: f697cc2e41c5e7e27954e8962d494355 (MD5)","Made available in DSpace on 2010-08-20T17:58:44Z (GMT). No. of bitstreams: 3 Huang_David.pdf: 708478 bytes, checksum: f697cc2e41c5e7e27954e8962d494355 (MD5) 1_Huang_David.pdf: 699640 bytes, checksum: 3c23e2a98521ba5348f1e9424cd26668 (MD5) license.txt: 4061 bytes, checksum: 38cd6fe8788b3b6fd74eca9c8bdb6c98 (MD5)"],"dc:identifier":["http://hdl.handle.net/2142/16816"],"dc:language":["en"],"dc:rights":["Copyright 2010 David S. Huang"],"dc:subject":["cross-coupling","enolates","homogeneous catalysis","palladium"],"dc:title":["Part I. Large scale procedure for the α-arylation of esters catalyzed by the pd(i) dimer [p(tbu)3]pd(μ-br)]2. Part II. Palladium-catalyzed γ-arylation of α,β-unsaturated esters"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["Thesis"],"thesis:degree_name":["M.S."],"thesis:institution_name":["University of Illinois at Urbana-Champaign"]},"updated_at":"2026-07-22T22:25:09Z"}