{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/70254"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/70254","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Studies of the Synthesis of Polycyclic Homocyclopropylcarbinols","abstract":"A new synthetic route to polycyclic homocyclopropylcarbinols has been realized by lithiation of bromocyclopropyl epoxides with n-butyllithium and subsequent intramolecular attack of the metallated cyclopropane ring onto the epoxide. A series of bromocyclopropyl epoxides was prepared from diene precursors in three or four steps by dibromocyclopropanation, epoxidation, and stereoselective reduction of one bromine atom. As an example, endo-7-bromobicyclo{4.1.0}hept-3-ene anti-oxide prepared from 1,4-cyclohexadiene underwent cyclization to endo-tricyclo{3.2.0.0('2,7)}-heptan-4-ol in 69% yield. Lithiation of a stereoisomeric mixture of the bromocyclopropyl epoxides from 1,5-hexadiene afforded the endo and exo isomers of both bicyclo{4.1.0}heptan-3-ol and bicyclo{3.1.0}hexane-2-methanol.","abstract_html":"A new synthetic route to polycyclic homocyclopropylcarbinols has been realized by lithiation of bromocyclopropyl epoxides with n-butyllithium and subsequent intramolecular attack of the metallated cyclopropane ring onto the epoxide. A series of bromocyclopropyl epoxides was prepared from diene precursors in three or four steps by dibromocyclopropanation, epoxidation, and stereoselective reduction of one bromine atom. As an example, endo-7-bromobicyclo{4.1.0}hept-3-ene anti-oxide prepared from 1,4-cyclohexadiene underwent cyclization to endo-tricyclo{3.2.0.0('2,7)}-heptan-4-ol in 69% yield. Lithiation of a stereoisomeric mixture of the bromocyclopropyl epoxides from 1,5-hexadiene afforded the endo and exo isomers of both bicyclo{4.1.0}heptan-3-ol and bicyclo{3.1.0}hexane-2-methanol.","abstract_has_math":false,"creators":["Last, Larry Alan"],"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":"2014-12-15T23:18:10Z","date_published":"2014-12-15T23:18:10Z","updated_at":"2026-07-22T22:26:02Z","subjects":["Chemistry, Organic"],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["(UMI)AAI8422113"],"render_values":[{"text":"(UMI)AAI8422113","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/70254","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["Last, Larry Alan"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2014-12-15T23:18:10Z","10000-01-01","1984"]},{"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/2142/70254","(UMI)AAI8422113"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["A new synthetic route to polycyclic homocyclopropylcarbinols has been realized by lithiation of bromocyclopropyl epoxides with n-butyllithium and subsequent intramolecular attack of the metallated cyclopropane ring onto the epoxide. A series of bromocyclopropyl epoxides was prepared from diene precursors in three or four steps by dibromocyclopropanation, epoxidation, and stereoselective reduction of one bromine atom. As an example, endo-7-bromobicyclo{4.1.0}hept-3-ene anti-oxide prepared from 1,4-cyclohexadiene underwent cyclization to endo-tricyclo{3.2.0.0('2,7)}-heptan-4-ol in 69% yield. Lithiation of a stereoisomeric mixture of the bromocyclopropyl epoxides from 1,5-hexadiene afforded the endo and exo isomers of both bicyclo{4.1.0}heptan-3-ol and bicyclo{3.1.0}hexane-2-methanol.","Novel concerted electrocyclic ring openings of two (beta)-lithio cyclopropyl oxiranes are described. Metalation of exo-7-bromobicyclo{4.1.0}hept-2-ene anti-oxide with n-butyllithium at 0(DEGREES)C afforded exo-bicyclo{3.2.0}hept-6-en-2-ol. A mechanism involving conrotatory ring opening to (Z,E)-cyclohepta-2,4-dienoxide, followed by conrotatory ring closure is proposed. Evidence for the intermediacy of this (Z,E)-diene was obtained by trapping with 1,3-diphenylisobenzofuran. When the metalation was carried out at -70(DEGREES)C, the major products were 2,5-di-n-butylcyclohept-3-en-1-ol and 4,5-di-n-butylcyclohept-2-en-1-ol. These compounds were evidently formed by addition of n-butyllithium to the trans double bond of the dienyl intermediate giving an allylic carbanion, which undergoes alkylation with n-butyl bromide at the termini of the allyl anion. Metalation of 8-bromobicyclo{5.1.0}oct-2-ene anti-oxide led to a similar mechanism involving the intermediacy of (Z,E)-cycloocta-2,4-dienoxide.","Made available in DSpace on 2014-12-15T23:18:10Z (GMT). No. of bitstreams: 1 8422113.pdf: 4112877 bytes, checksum: fef3e081f40098291fd812820bb70289 (MD5) Previous issue date: 1984","Embargo set by: Seth Robbins for item 70420 Lift date: Forever Reason: Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs","Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs","U of I Only","120 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1984."]},{"key":"dc:title","label":"Title","values":["Studies of the Synthesis of Polycyclic Homocyclopropylcarbinols"]}]}],"canonical_facts":{"dc:creator":["Last, Larry Alan"],"dc:date":["2014-12-15T23:18:10Z","10000-01-01","1984"],"dc:description":["A new synthetic route to polycyclic homocyclopropylcarbinols has been realized by lithiation of bromocyclopropyl epoxides with n-butyllithium and subsequent intramolecular attack of the metallated cyclopropane ring onto the epoxide. A series of bromocyclopropyl epoxides was prepared from diene precursors in three or four steps by dibromocyclopropanation, epoxidation, and stereoselective reduction of one bromine atom. As an example, endo-7-bromobicyclo{4.1.0}hept-3-ene anti-oxide prepared from 1,4-cyclohexadiene underwent cyclization to endo-tricyclo{3.2.0.0('2,7)}-heptan-4-ol in 69% yield. Lithiation of a stereoisomeric mixture of the bromocyclopropyl epoxides from 1,5-hexadiene afforded the endo and exo isomers of both bicyclo{4.1.0}heptan-3-ol and bicyclo{3.1.0}hexane-2-methanol.","Novel concerted electrocyclic ring openings of two (beta)-lithio cyclopropyl oxiranes are described. Metalation of exo-7-bromobicyclo{4.1.0}hept-2-ene anti-oxide with n-butyllithium at 0(DEGREES)C afforded exo-bicyclo{3.2.0}hept-6-en-2-ol. A mechanism involving conrotatory ring opening to (Z,E)-cyclohepta-2,4-dienoxide, followed by conrotatory ring closure is proposed. Evidence for the intermediacy of this (Z,E)-diene was obtained by trapping with 1,3-diphenylisobenzofuran. When the metalation was carried out at -70(DEGREES)C, the major products were 2,5-di-n-butylcyclohept-3-en-1-ol and 4,5-di-n-butylcyclohept-2-en-1-ol. These compounds were evidently formed by addition of n-butyllithium to the trans double bond of the dienyl intermediate giving an allylic carbanion, which undergoes alkylation with n-butyl bromide at the termini of the allyl anion. Metalation of 8-bromobicyclo{5.1.0}oct-2-ene anti-oxide led to a similar mechanism involving the intermediacy of (Z,E)-cycloocta-2,4-dienoxide.","Made available in DSpace on 2014-12-15T23:18:10Z (GMT). No. of bitstreams: 1 8422113.pdf: 4112877 bytes, checksum: fef3e081f40098291fd812820bb70289 (MD5) Previous issue date: 1984","Embargo set by: Seth Robbins for item 70420 Lift date: Forever Reason: Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs","Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs","U of I Only","120 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1984."],"dc:identifier":["http://hdl.handle.net/2142/70254","(UMI)AAI8422113"],"dc:subject":["Chemistry, Organic"],"dc:title":["Studies of the Synthesis of Polycyclic Homocyclopropylcarbinols"],"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":"2026-07-22T22:26:02Z"}