Modifications to the literature-reported procedure for the synthesis of cross-bridged cyclam and homocyclen tetraamines are presented. The synthesis involves the use of a cis-tricyclic bisaminal intermediate for the preparation of tetracyclic bisaminals and the microwave-assisted reductive ring opening of N,N'-dibenzyl bisaminal salts. The cis-tricyclic bisaminal was also used in the preparation of a C-functionalized cross-bridged cyclam. The resolution of racemic cross-bridged cyclam by selective crystallization of its diastereomeric salt of L-(+)-tartaric acid is described. Additionally, the kinetics of racemization of enantiopure cross-bridged cyclam is presented.
","abstract_html":"<p>Modifications to the literature-reported procedure for the synthesis of cross-bridged cyclam and homocyclen tetraamines are presented. The synthesis involves the use of a cis-tricyclic bisaminal intermediate for the preparation of tetracyclic bisaminals and the microwave-assisted reductive ring opening of N,N'-dibenzyl bisaminal salts. The cis-tricyclic bisaminal was also used in the preparation of a C-functionalized cross-bridged cyclam. The resolution of racemic cross-bridged cyclam by selective crystallization of its diastereomeric salt of L-(+)-tartaric acid is described. Additionally, the kinetics of racemization of enantiopure cross-bridged cyclam is presented.</p>","abstract_has_math":false,"creators":["Odendaal, Antoinette Yolanda"],"institution":null,"degree_name":"Doctor of Philosophy","degree_level":"Dissertation","degree_discipline":null,"degree_department":null,"school":null,"contributors":["Gary Weisman"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2009,"date_issued":"2009-01-01T08:00:00Z","date_published":"2009-01-01T08:00:00Z","updated_at":"2026-07-24T05:22:25Z","subjects":["Chemistry","Organic"],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"https://scholars.unh.edu/dissertation/481","outbound_label":"Repository record","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Gary Weisman"]},{"key":"dc:creator","label":"Author","values":["Odendaal, Antoinette Yolanda"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"thesis:degree_level","label":"Degree Level","values":["Dissertation"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Doctor of Philosophy"]}]},{"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":["https://scholars.unh.edu/dissertation/481"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["Modifications to the literature-reported procedure for the synthesis of cross-bridged cyclam and homocyclen tetraamines are presented. The synthesis involves the use of a cis-tricyclic bisaminal intermediate for the preparation of tetracyclic bisaminals and the microwave-assisted reductive ring opening of N,N'-dibenzyl bisaminal salts. The cis-tricyclic bisaminal was also used in the preparation of a C-functionalized cross-bridged cyclam. The resolution of racemic cross-bridged cyclam by selective crystallization of its diastereomeric salt of L-(+)-tartaric acid is described. Additionally, the kinetics of racemization of enantiopure cross-bridged cyclam is presented.
"]},{"key":"dc:title","label":"Title","values":["A modified synthesis, C-functionalization, resolution and racemization kinetics of cross -bridged tetraazamacrocycles"]}]}],"canonical_facts":{"dc:contributor":["Gary Weisman"],"dc:creator":["Odendaal, Antoinette Yolanda"],"dc:description.abstract":["Modifications to the literature-reported procedure for the synthesis of cross-bridged cyclam and homocyclen tetraamines are presented. The synthesis involves the use of a cis-tricyclic bisaminal intermediate for the preparation of tetracyclic bisaminals and the microwave-assisted reductive ring opening of N,N'-dibenzyl bisaminal salts. The cis-tricyclic bisaminal was also used in the preparation of a C-functionalized cross-bridged cyclam. The resolution of racemic cross-bridged cyclam by selective crystallization of its diastereomeric salt of L-(+)-tartaric acid is described. Additionally, the kinetics of racemization of enantiopure cross-bridged cyclam is presented.
"],"dc:identifier":["https://scholars.unh.edu/dissertation/481"],"dc:subject":["Chemistry","Organic"],"dc:title":["A modified synthesis, C-functionalization, resolution and racemization kinetics of cross -bridged tetraazamacrocycles"],"thesis:degree_level":["Dissertation"],"thesis:degree_name":["Doctor of Philosophy"]},"updated_at":"2026-07-24T05:22:25Z"}