{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/70245"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/70245","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"The Electrophilic Amination of Organolithium Compounds With Methyllithium-Methoxylamines","abstract":"Strongly basic aliphatic and benzenoid aromatic organolithium compounds can be stoichiometrically converted to primary amines, upon treatment with two equivalents of a methoxylamine-methyllithium complex, in 14-97% yields, or to secondary amines, either inter- or intramolecularly, upon treatment with one equivalent of a N-alkylmethoxylamine-methyllithium complex, in 30-73% yields. N-Methyl- and N-1-phenylethylmethoxylamines were used to illustrate the intermolecular applications of this methodology, and indoline, isolated as its N-acetyl derivative, was prepared from methyllithium-N-2-(2'-bromophenyl)ethylmethoxylamine in 42% yield, as an illustration of an intramolecular application. A double labelling reaction was done to distinguish between a stepwise or concerted mechanism in these amination reactions using N-methyl-O-(2-bromo)benzylhydroxylamine and N-methyl-d(,1)-O-(2-bromo-(alpha),(alpha)-dideutero)benzylhydroxylamine to provide N-methyl-2-aminobenzyl alcohol, isolated as its N,O-diacetyl derivative, in 13% yield. The deuterium distribution of the latter suggests that amination occurred intermolecularly and is, therefore, sensitive to geometric restraints in this case. This result suggests that electrophilic amination of carbanions with methoxylamine appears to occur via a concerted displacement mechanism, and sets a precedent for the use of a double labelling experiment in mechanistic studies of other systems where traditional probes cannot be used. The amination of methyllithium with either methoxylamine or N,N-dideuteromethoxylamine provides methylamine, isolated as its benzamide derivative, in 33% yield. The possible role of methyllithium, as well as the nature of the active aminating species in aminations with methyllithium-methoxylamines is discussed.","abstract_html":"Strongly basic aliphatic and benzenoid aromatic organolithium compounds can be stoichiometrically converted to primary amines, upon treatment with two equivalents of a methoxylamine-methyllithium complex, in 14-97% yields, or to secondary amines, either inter- or intramolecularly, upon treatment with one equivalent of a N-alkylmethoxylamine-methyllithium complex, in 30-73% yields. N-Methyl- and N-1-phenylethylmethoxylamines were used to illustrate the intermolecular applications of this methodology, and indoline, isolated as its N-acetyl derivative, was prepared from methyllithium-N-2-(2'-bromophenyl)ethylmethoxylamine in 42% yield, as an illustration of an intramolecular application. A double labelling reaction was done to distinguish between a stepwise or concerted mechanism in these amination reactions using N-methyl-O-(2-bromo)benzylhydroxylamine and N-methyl-d(,1)-O-(2-bromo-(alpha),(alpha)-dideutero)benzylhydroxylamine to provide N-methyl-2-aminobenzyl alcohol, isolated as its N,O-diacetyl derivative, in 13% yield. The deuterium distribution of the latter suggests that amination occurred intermolecularly and is, therefore, sensitive to geometric restraints in this case. This result suggests that electrophilic amination of carbanions with methoxylamine appears to occur via a concerted displacement mechanism, and sets a precedent for the use of a double labelling experiment in mechanistic studies of other systems where traditional probes cannot be used. The amination of methyllithium with either methoxylamine or N,N-dideuteromethoxylamine provides methylamine, isolated as its benzamide derivative, in 33% yield. The possible role of methyllithium, as well as the nature of the active aminating species in aminations with methyllithium-methoxylamines is discussed.","abstract_has_math":false,"creators":["Kokko, Bruce Jerome"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":[],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2014,"date_issued":"2014-12-15T23:18:07Z","date_published":"2014-12-15T23:18:07Z","updated_at":"2026-07-22T22:26:02Z","subjects":["Chemistry, Organic"],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["(UMI)AAI8409973"],"render_values":[{"text":"(UMI)AAI8409973","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/70245","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["Kokko, Bruce Jerome"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2014-12-15T23:18:07Z","10000-01-01","1983"]},{"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":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["http://hdl.handle.net/2142/70245","(UMI)AAI8409973"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Strongly basic aliphatic and benzenoid aromatic organolithium compounds can be stoichiometrically converted to primary amines, upon treatment with two equivalents of a methoxylamine-methyllithium complex, in 14-97% yields, or to secondary amines, either inter- or intramolecularly, upon treatment with one equivalent of a N-alkylmethoxylamine-methyllithium complex, in 30-73% yields. N-Methyl- and N-1-phenylethylmethoxylamines were used to illustrate the intermolecular applications of this methodology, and indoline, isolated as its N-acetyl derivative, was prepared from methyllithium-N-2-(2'-bromophenyl)ethylmethoxylamine in 42% yield, as an illustration of an intramolecular application. A double labelling reaction was done to distinguish between a stepwise or concerted mechanism in these amination reactions using N-methyl-O-(2-bromo)benzylhydroxylamine and N-methyl-d(,1)-O-(2-bromo-(alpha),(alpha)-dideutero)benzylhydroxylamine to provide N-methyl-2-aminobenzyl alcohol, isolated as its N,O-diacetyl derivative, in 13% yield. The deuterium distribution of the latter suggests that amination occurred intermolecularly and is, therefore, sensitive to geometric restraints in this case. This result suggests that electrophilic amination of carbanions with methoxylamine appears to occur via a concerted displacement mechanism, and sets a precedent for the use of a double labelling experiment in mechanistic studies of other systems where traditional probes cannot be used. The amination of methyllithium with either methoxylamine or N,N-dideuteromethoxylamine provides methylamine, isolated as its benzamide derivative, in 33% yield. The possible role of methyllithium, as well as the nature of the active aminating species in aminations with methyllithium-methoxylamines is discussed.","Made available in DSpace on 2014-12-15T23:18:07Z (GMT). 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N-Methyl- and N-1-phenylethylmethoxylamines were used to illustrate the intermolecular applications of this methodology, and indoline, isolated as its N-acetyl derivative, was prepared from methyllithium-N-2-(2'-bromophenyl)ethylmethoxylamine in 42% yield, as an illustration of an intramolecular application. A double labelling reaction was done to distinguish between a stepwise or concerted mechanism in these amination reactions using N-methyl-O-(2-bromo)benzylhydroxylamine and N-methyl-d(,1)-O-(2-bromo-(alpha),(alpha)-dideutero)benzylhydroxylamine to provide N-methyl-2-aminobenzyl alcohol, isolated as its N,O-diacetyl derivative, in 13% yield. The deuterium distribution of the latter suggests that amination occurred intermolecularly and is, therefore, sensitive to geometric restraints in this case. This result suggests that electrophilic amination of carbanions with methoxylamine appears to occur via a concerted displacement mechanism, and sets a precedent for the use of a double labelling experiment in mechanistic studies of other systems where traditional probes cannot be used. The amination of methyllithium with either methoxylamine or N,N-dideuteromethoxylamine provides methylamine, isolated as its benzamide derivative, in 33% yield. The possible role of methyllithium, as well as the nature of the active aminating species in aminations with methyllithium-methoxylamines is discussed.","Made available in DSpace on 2014-12-15T23:18:07Z (GMT). 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