{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/21980"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/21980","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Studies of alpha-lithioamine synthetic equivalents: I. Elaboration of primary amines. II. Detection of an intermediate in the lithiation of a benzylic urea","abstract":"Reagents for the $\\alpha$-substitution of N-Boc-benzylamine and N-Boc-allylamine have been developed via dilithiation and electrophilic substitution. Discussion of the specific conditions employed to accomplish these transformations is presented, as well as mechanistic speculation. Dilithiation and substitution of O-benzyl-N-methyl carbamate has been achieved, and use of sec-BuLi/(-)sparteine as the base provided the corresponding products with up to 57% enantiomeric excess. Lithiation of N-tert-butyl-N-benzyl carbamates resulted in rearrangement to phenylglycine derivatives. These related investigations are also discussed.","abstract_html":"Reagents for the <span class=\"etd-inline-math\">&alpha;</span>-substitution of N-Boc-benzylamine and N-Boc-allylamine have been developed via dilithiation and electrophilic substitution. Discussion of the specific conditions employed to accomplish these transformations is presented, as well as mechanistic speculation. Dilithiation and substitution of O-benzyl-N-methyl carbamate has been achieved, and use of sec-BuLi/(-)sparteine as the base provided the corresponding products with up to 57% enantiomeric excess. Lithiation of N-tert-butyl-N-benzyl carbamates resulted in rearrangement to phenylglycine derivatives. These related investigations are also discussed.","abstract_has_math":true,"creators":["Resek, James Edward"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Beak, Peter"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2011,"date_issued":"2011-05-07T13:25:08Z","date_published":"2011-05-07T13:25:08Z","updated_at":"2026-07-22T22:25:19Z","subjects":["Chemistry, Organic"],"languages":["eng"],"rights":["Copyright 1994 Resek, James Edward"],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI9416430","(UMI)AAI9416430"],"render_values":[{"text":"AAI9416430","href":null,"code":true},{"text":"(UMI)AAI9416430","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/21980","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Beak, Peter"]},{"key":"dc:creator","label":"Author","values":["Resek, James Edward"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2011-05-07T13:25:08Z","10000-01-01","1994"]},{"key":"dc:type","label":"Dc Type","values":["text"]},{"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":["Chemistry, Organic"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["eng"]},{"key":"dc:rights","label":"Dc Rights","values":["Copyright 1994 Resek, James Edward"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI9416430","(UMI)AAI9416430","http://hdl.handle.net/2142/21980"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Reagents for the $\\alpha$-substitution of N-Boc-benzylamine and N-Boc-allylamine have been developed via dilithiation and electrophilic substitution. Discussion of the specific conditions employed to accomplish these transformations is presented, as well as mechanistic speculation. Dilithiation and substitution of O-benzyl-N-methyl carbamate has been achieved, and use of sec-BuLi/(-)sparteine as the base provided the corresponding products with up to 57% enantiomeric excess. Lithiation of N-tert-butyl-N-benzyl carbamates resulted in rearrangement to phenylglycine derivatives. These related investigations are also discussed.","The intramolecular and intermolecular primary hydrogen-deuterium kinetic isotope effects for the benzylic deprotonation of N-benzyl-N,N$\\sp\\prime$-dimethyl urea with sec-BuLi/TMEDA have been measured to be 13 $\\pm$ 3 and 2.0 $\\pm$ 0.7, respectively, at $-$78$\\sp\\circ$C. These substantially different values exclude a one-step deprotonation mechanism and are taken as evidence for the formation of a pre-lithiation complex between the substrate and sec-BuLi which has a rate of decomplexation that is competitive with proton transfer. Detailed kinetic analysis and discussion of the implications of these results are presented.","Made available in DSpace on 2011-05-07T13:25:08Z (GMT). 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Detection of an intermediate in the lithiation of a benzylic urea"]}]}],"canonical_facts":{"dc:contributor":["Beak, Peter"],"dc:creator":["Resek, James Edward"],"dc:date":["2011-05-07T13:25:08Z","10000-01-01","1994"],"dc:description":["Reagents for the $\\alpha$-substitution of N-Boc-benzylamine and N-Boc-allylamine have been developed via dilithiation and electrophilic substitution. Discussion of the specific conditions employed to accomplish these transformations is presented, as well as mechanistic speculation. Dilithiation and substitution of O-benzyl-N-methyl carbamate has been achieved, and use of sec-BuLi/(-)sparteine as the base provided the corresponding products with up to 57% enantiomeric excess. Lithiation of N-tert-butyl-N-benzyl carbamates resulted in rearrangement to phenylglycine derivatives. These related investigations are also discussed.","The intramolecular and intermolecular primary hydrogen-deuterium kinetic isotope effects for the benzylic deprotonation of N-benzyl-N,N$\\sp\\prime$-dimethyl urea with sec-BuLi/TMEDA have been measured to be 13 $\\pm$ 3 and 2.0 $\\pm$ 0.7, respectively, at $-$78$\\sp\\circ$C. These substantially different values exclude a one-step deprotonation mechanism and are taken as evidence for the formation of a pre-lithiation complex between the substrate and sec-BuLi which has a rate of decomplexation that is competitive with proton transfer. Detailed kinetic analysis and discussion of the implications of these results are presented.","Made available in DSpace on 2011-05-07T13:25:08Z (GMT). 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Detection of an intermediate in the lithiation of a benzylic urea"],"dc:type":["text"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["Dissertation"],"thesis:degree_name":["Ph.D."],"thesis:institution_name":["University of Illinois at Urbana-Champaign"]},"updated_at":"2026-07-22T22:25:19Z"}