{"id":{"repo_id":"glasgow","oai_identifier":"oai:theses.gla.ac.uk:123"},"canonical_url":"https://search.dev.ndltd.org/etd/glasgow/oai:theses.gla.ac.uk:123","repository":{"repo_id":"glasgow","name":"University of Glasgow","base_url":"https://theses.gla.ac.uk/cgi/oai2"},"display":{"title":"Organocatalysts for the asymmetric reduction of aromatic ketimines with trichlorosilane","abstract":"Asymmetric reduction of N-aryl ketimines 189a j, 212, and 213 with trichlorosilane can be catalyzed by new N-methyl L-amino acid-derived Lewis-basic organocatalysts, such as bisamide 197c (10 mol%), in toluene at room temperature with high enantioselectivity (≤92% ee). The structure-reactivity investigation shows that the product configuration is controlled by the nature of the side chain of the catalyst scaffold (e.g., i Pr vs Me, as in 197c and 208c), so that catalysts of the same absolute configuration may induce the formation of the opposite enantiomers of the product. Arene-arene interactions between the catalyst and the incoming imine appear to be the prerequisite for asymmetric induction. This metal-free, organocatalytic protocol is competitive with the traditional, metal-catalyzed methodology.","abstract_html":"Asymmetric reduction of N-aryl ketimines 189a j, 212, and 213 with trichlorosilane can be catalyzed by new N-methyl L-amino acid-derived Lewis-basic organocatalysts, such as bisamide 197c (10 mol%), in toluene at room temperature with high enantioselectivity (≤92% ee). The structure-reactivity investigation shows that the product configuration is controlled by the nature of the side chain of the catalyst scaffold (e.g., i Pr vs Me, as in 197c and 208c), so that catalysts of the same absolute configuration may induce the formation of the opposite enantiomers of the product. Arene-arene interactions between the catalyst and the incoming imine appear to be the prerequisite for asymmetric induction. This metal-free, organocatalytic protocol is competitive with the traditional, metal-catalyzed methodology.","abstract_has_math":false,"creators":["MacDougall, Kenneth N."],"institution":"University of Glasgow","degree_name":null,"degree_level":"PhD","degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2008,"date_issued":"2008","date_published":"2008","updated_at":"2026-07-24T02:23:14Z","subjects":["QD Chemistry"],"languages":["en"],"rights":[],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":null,"outbound_label":null,"outbound_source":null},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["MacDougall, Kenneth N."]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2008"]},{"key":"dc:date.issued","label":"Date","values":["2008"]},{"key":"dc:publisher.institution","label":"Dc Publisher Institution","values":["University of Glasgow"]},{"key":"dc:relation.isreferencedby","label":"Dc Relation Isreferencedby","values":["https://theses.gla.ac.uk/123/"]},{"key":"dc:relation.isreferencedby.uri","label":"Dc Relation Isreferencedby URI","values":["https://gla.on.worldcat.org/oclc/1547496589"]},{"key":"dc:type","label":"Dc Type","values":["Thesis"]},{"key":"dc:type.qualificationlevel","label":"Dc Type Qualificationlevel","values":["PhD"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["QD Chemistry"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["en"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["https://theses.gla.ac.uk/123/1/2007MacDougall1PhD.pdf"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["Asymmetric reduction of N-aryl ketimines 189a j, 212, and 213 with trichlorosilane can be catalyzed by new N-methyl L-amino acid-derived Lewis-basic organocatalysts, such as bisamide 197c (10 mol%), in toluene at room temperature with high enantioselectivity (≤92% ee). The structure-reactivity investigation shows that the product configuration is controlled by the nature of the side chain of the catalyst scaffold (e.g., i Pr vs Me, as in 197c and 208c), so that catalysts of the same absolute configuration may induce the formation of the opposite enantiomers of the product. Arene-arene interactions between the catalyst and the incoming imine appear to be the prerequisite for asymmetric induction. This metal-free, organocatalytic protocol is competitive with the traditional, metal-catalyzed methodology."]},{"key":"dc:format","label":"Dc Format","values":["pdf"]},{"key":"dc:title","label":"Title","values":["Organocatalysts for the asymmetric reduction of aromatic ketimines with trichlorosilane"]}]}],"canonical_facts":{"dc:creator":["MacDougall, Kenneth N."],"dc:date":["2008"],"dc:date.issued":["2008"],"dc:description.abstract":["Asymmetric reduction of N-aryl ketimines 189a j, 212, and 213 with trichlorosilane can be catalyzed by new N-methyl L-amino acid-derived Lewis-basic organocatalysts, such as bisamide 197c (10 mol%), in toluene at room temperature with high enantioselectivity (≤92% ee). The structure-reactivity investigation shows that the product configuration is controlled by the nature of the side chain of the catalyst scaffold (e.g., i Pr vs Me, as in 197c and 208c), so that catalysts of the same absolute configuration may induce the formation of the opposite enantiomers of the product. Arene-arene interactions between the catalyst and the incoming imine appear to be the prerequisite for asymmetric induction. This metal-free, organocatalytic protocol is competitive with the traditional, metal-catalyzed methodology."],"dc:format":["pdf"],"dc:identifier.uri":["https://theses.gla.ac.uk/123/1/2007MacDougall1PhD.pdf"],"dc:language":["en"],"dc:publisher.institution":["University of Glasgow"],"dc:relation.isreferencedby":["https://theses.gla.ac.uk/123/"],"dc:relation.isreferencedby.uri":["https://gla.on.worldcat.org/oclc/1547496589"],"dc:subject":["QD Chemistry"],"dc:title":["Organocatalysts for the asymmetric reduction of aromatic ketimines with trichlorosilane"],"dc:type":["Thesis"],"dc:type.qualificationlevel":["PhD"]},"updated_at":"2026-07-24T02:23:14Z"}