{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/108577"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/108577","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Prediction of higher selectivity catalysts by a computer driven workflow and machine learning and computational investigation of boronate esters in the Suzuki-Miyaura cross coupling","abstract":"Chapter one of this work provides a comprehensive overview of chemoinformatics in enantioselective catalysis. Chapter two is comprised of completely unpublished work detailing the synthesis of a diverse set of bisoxazoline ligands in the planned optimization of an enantioselective aziridination reaction. Although this work was unsuccessful in the optimization of the target reaction, it revealed deficiencies in our computationally-guided workflow. In Chapter three, we address the limitations revealed in chapter two using an algorithmically selected set of BINOLphosphoric acids to simulate an optimization of an enantioselective reaction. In this chapter, we demonstrate the ability to use suboptimal reaction results to predict reaction outcomes for optimal catalysts. In Chapter 4, we transition from chemoinformatics-guided optimization to applied quantum chemistry to elucidate the influence of boronic ester structure on the rate of transmetalation. Here we find that the activation barrier for transmetalation is dependent on the interplay between ground state destabilization of a Pd-O dative interaction and hyperconjugative activation of the Cipso-B σ bond.","abstract_html":"Chapter one of this work provides a comprehensive overview of chemoinformatics in enantioselective catalysis. Chapter two is comprised of completely unpublished work detailing the synthesis of a diverse set of bisoxazoline ligands in the planned optimization of an enantioselective aziridination reaction. Although this work was unsuccessful in the optimization of the target reaction, it revealed deficiencies in our computationally-guided workflow. In Chapter three, we address the limitations revealed in chapter two using an algorithmically selected set of BINOLphosphoric acids to simulate an optimization of an enantioselective reaction. In this chapter, we demonstrate the ability to use suboptimal reaction results to predict reaction outcomes for optimal catalysts. In Chapter 4, we transition from chemoinformatics-guided optimization to applied quantum chemistry to elucidate the influence of boronic ester structure on the rate of transmetalation. Here we find that the activation barrier for transmetalation is dependent on the interplay between ground state destabilization of a Pd-O dative interaction and hyperconjugative activation of the Cipso-B σ bond.","abstract_has_math":false,"creators":["Zahrt, Andrew F"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Denmark, Scott E","Burke, Martin D.","Peng, Jian","Pogorelov, Taras V."],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2020,"date_issued":"2020-10-07T22:44:23Z","date_published":"2020-10-07T22:44:23Z","updated_at":"2026-07-22T22:24:48Z","subjects":["Machine learning","Computational Chemistry","Chemoinformatics"],"languages":["en"],"rights":["Copyright 2020 Andrew Zahrt"],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"http://hdl.handle.net/2142/108577","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Denmark, Scott E","Burke, Martin D.","Peng, Jian","Pogorelov, Taras V."]},{"key":"dc:creator","label":"Author","values":["Zahrt, Andrew F"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2020-10-07T22:44:23Z","2022-10-07T22:44:53Z","2020-07-09","2020-08"]},{"key":"dc:type","label":"Dc Type","values":["text","Thesis"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry"]},{"key":"thesis:degree_level","label":"Degree Level","values":["Dissertation"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Ph.D."]},{"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":["Machine learning","Computational Chemistry","Chemoinformatics"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["en"]},{"key":"dc:rights","label":"Dc Rights","values":["Copyright 2020 Andrew Zahrt"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["http://hdl.handle.net/2142/108577"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Chapter one of this work provides a comprehensive overview of chemoinformatics in enantioselective catalysis. Chapter two is comprised of completely unpublished work detailing the synthesis of a diverse set of bisoxazoline ligands in the planned optimization of an enantioselective aziridination reaction. Although this work was unsuccessful in the optimization of the target reaction, it revealed deficiencies in our computationally-guided workflow. In Chapter three, we address the limitations revealed in chapter two using an algorithmically selected set of BINOLphosphoric acids to simulate an optimization of an enantioselective reaction. In this chapter, we demonstrate the ability to use suboptimal reaction results to predict reaction outcomes for optimal catalysts. In Chapter 4, we transition from chemoinformatics-guided optimization to applied quantum chemistry to elucidate the influence of boronic ester structure on the rate of transmetalation. Here we find that the activation barrier for transmetalation is dependent on the interplay between ground state destabilization of a Pd-O dative interaction and hyperconjugative activation of the Cipso-B σ bond.","Submission published under a 24 month embargo labeled 'U of I Access', the embargo will last until 2022-08-01","The student, Andrew Zahrt, accepted the attached license on 2020-07-02 at 21:21.","The student, Andrew Zahrt, submitted this Dissertation for approval on 2020-07-02 at 21:30.","This Dissertation was approved for publication on 2020-07-09 at 16:56.","DSpace SAF Submission Ingestion Package generated from Vireo submission #15490 on 2020-10-02 at 15:31:13","Made available in DSpace on 2020-10-07T22:44:23Z (GMT). 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Here we find that the activation barrier for transmetalation is dependent on the interplay between ground state destabilization of a Pd-O dative interaction and hyperconjugative activation of the Cipso-B σ bond.","Submission published under a 24 month embargo labeled 'U of I Access', the embargo will last until 2022-08-01","The student, Andrew Zahrt, accepted the attached license on 2020-07-02 at 21:21.","The student, Andrew Zahrt, submitted this Dissertation for approval on 2020-07-02 at 21:30.","This Dissertation was approved for publication on 2020-07-09 at 16:56.","DSpace SAF Submission Ingestion Package generated from Vireo submission #15490 on 2020-10-02 at 15:31:13","Made available in DSpace on 2020-10-07T22:44:23Z (GMT). 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