{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/95599"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/95599","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Design of a second generation MIDA boronate: iterating c(sp3) based Suzuki cross couplings","abstract":"Small molecules have had a tremendous positive impact on human health and society in general. Despite this, small molecule synthesis is still a time and cost intensive process practiced primarily by highly trained specialists. Inspired by the impact of general, automated synthesis platforms for peptides and other biomolecules, we have pioneered iterative cross coupling (ICC) as an analogous platform for small molecules. Enabled by both a building block based synthesis strategy and a general purification protocol, our group has designed and built a small molecule synthesizer. We have demonstrated the ability of this synthesizer to access a wide variety of small molecules, including natural products, pharmaceuticals, and materials components. Further, the synthesizer is able to access complex, polycyclic, C(sp3) rich natural products through the use of the “linear-to-cyclized” strategy wherein linear precursors are prepared on the machine in an automated fashion and then manually cyclized. Given the ubiquity of stereogenic C(sp3) carbons in natural products, the ability to stereospecifically couple secondary alkyl fragments iteratively would be highly enabling. However, all currently known methods for such transformations require conditions which hydrolyze MIDA boronates (aqueous base, high heat, strong base, etc.). In this thesis I describe the development of a second generation iminodiacetic acid ligand for boronic acids which is refractory to hydrolysis and has enabled the first examples of coupling unactivated, secondary alkyl boronic acids in the context of an iterative cross coupling cycle.","abstract_html":"Small molecules have had a tremendous positive impact on human health and society in general. Despite this, small molecule synthesis is still a time and cost intensive process practiced primarily by highly trained specialists. Inspired by the impact of general, automated synthesis platforms for peptides and other biomolecules, we have pioneered iterative cross coupling (ICC) as an analogous platform for small molecules. Enabled by both a building block based synthesis strategy and a general purification protocol, our group has designed and built a small molecule synthesizer. We have demonstrated the ability of this synthesizer to access a wide variety of small molecules, including natural products, pharmaceuticals, and materials components. Further, the synthesizer is able to access complex, polycyclic, C(sp3) rich natural products through the use of the “linear-to-cyclized” strategy wherein linear precursors are prepared on the machine in an automated fashion and then manually cyclized. Given the ubiquity of stereogenic C(sp3) carbons in natural products, the ability to stereospecifically couple secondary alkyl fragments iteratively would be highly enabling. However, all currently known methods for such transformations require conditions which hydrolyze MIDA boronates (aqueous base, high heat, strong base, etc.). In this thesis I describe the development of a second generation iminodiacetic acid ligand for boronic acids which is refractory to hydrolysis and has enabled the first examples of coupling unactivated, secondary alkyl boronic acids in the context of an iterative cross coupling cycle.","abstract_has_math":false,"creators":["Schmidt, Michael Joseph"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"M.S.","degree_level":"Thesis","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Burke, Martin D."],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2017,"date_issued":"2017-03-01T17:01:49Z","date_published":"2017-03-01T17:01:49Z","updated_at":"2026-07-22T22:26:37Z","subjects":["Suzuki","coupling","cross coupling","MIDA boronate","iteration","automation"],"languages":["en"],"rights":["Copyright 2016 Michael Schmidt"],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"http://hdl.handle.net/2142/95599","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Burke, Martin D."]},{"key":"dc:creator","label":"Author","values":["Schmidt, Michael Joseph"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2017-03-01T17:01:49Z","2019-03-02T10:15:07Z","2016-12-02","2016-12"]},{"key":"dc:type","label":"Dc Type","values":["text"]},{"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":["Suzuki","coupling","cross coupling","MIDA boronate","iteration","automation"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["en"]},{"key":"dc:rights","label":"Dc Rights","values":["Copyright 2016 Michael Schmidt"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["http://hdl.handle.net/2142/95599"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Small molecules have had a tremendous positive impact on human health and society in general. Despite this, small molecule synthesis is still a time and cost intensive process practiced primarily by highly trained specialists. Inspired by the impact of general, automated synthesis platforms for peptides and other biomolecules, we have pioneered iterative cross coupling (ICC) as an analogous platform for small molecules. Enabled by both a building block based synthesis strategy and a general purification protocol, our group has designed and built a small molecule synthesizer. We have demonstrated the ability of this synthesizer to access a wide variety of small molecules, including natural products, pharmaceuticals, and materials components. Further, the synthesizer is able to access complex, polycyclic, C(sp3) rich natural products through the use of the “linear-to-cyclized” strategy wherein linear precursors are prepared on the machine in an automated fashion and then manually cyclized. Given the ubiquity of stereogenic C(sp3) carbons in natural products, the ability to stereospecifically couple secondary alkyl fragments iteratively would be highly enabling. However, all currently known methods for such transformations require conditions which hydrolyze MIDA boronates (aqueous base, high heat, strong base, etc.). In this thesis I describe the development of a second generation iminodiacetic acid ligand for boronic acids which is refractory to hydrolysis and has enabled the first examples of coupling unactivated, secondary alkyl boronic acids in the context of an iterative cross coupling cycle.","Submission published under a 24 month embargo labeled 'Closed Access', the embargo will last until 2018-12-01","The student, Michael Schmidt, accepted the attached license on 2016-11-30 at 20:06.","The student, Michael Schmidt, submitted this Thesis for approval on 2016-11-30 at 20:20.","This Thesis was approved for publication on 2016-12-02 at 09:11.","DSpace SAF Submission Ingestion Package generated from Vireo submission #10386 on 2017-02-28 at 14:42:36","Made available in DSpace on 2017-03-01T17:01:49Z (GMT). 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Despite this, small molecule synthesis is still a time and cost intensive process practiced primarily by highly trained specialists. Inspired by the impact of general, automated synthesis platforms for peptides and other biomolecules, we have pioneered iterative cross coupling (ICC) as an analogous platform for small molecules. Enabled by both a building block based synthesis strategy and a general purification protocol, our group has designed and built a small molecule synthesizer. We have demonstrated the ability of this synthesizer to access a wide variety of small molecules, including natural products, pharmaceuticals, and materials components. Further, the synthesizer is able to access complex, polycyclic, C(sp3) rich natural products through the use of the “linear-to-cyclized” strategy wherein linear precursors are prepared on the machine in an automated fashion and then manually cyclized. Given the ubiquity of stereogenic C(sp3) carbons in natural products, the ability to stereospecifically couple secondary alkyl fragments iteratively would be highly enabling. However, all currently known methods for such transformations require conditions which hydrolyze MIDA boronates (aqueous base, high heat, strong base, etc.). In this thesis I describe the development of a second generation iminodiacetic acid ligand for boronic acids which is refractory to hydrolysis and has enabled the first examples of coupling unactivated, secondary alkyl boronic acids in the context of an iterative cross coupling cycle.","Submission published under a 24 month embargo labeled 'Closed Access', the embargo will last until 2018-12-01","The student, Michael Schmidt, accepted the attached license on 2016-11-30 at 20:06.","The student, Michael Schmidt, submitted this Thesis for approval on 2016-11-30 at 20:20.","This Thesis was approved for publication on 2016-12-02 at 09:11.","DSpace SAF Submission Ingestion Package generated from Vireo submission #10386 on 2017-02-28 at 14:42:36","Made available in DSpace on 2017-03-01T17:01:49Z (GMT). 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