{"id":{"repo_id":"wvu","oai_identifier":"oai:researchrepository.wvu.edu:etd-2053"},"canonical_url":"https://search.dev.ndltd.org/etd/wvu/oai:researchrepository.wvu.edu:etd-2053","repository":{"repo_id":"wvu","name":"West Virginia University","base_url":"https://researchrepository.wvu.edu/do/oai/"},"display":{"title":"Synthesis of o-isotoluenes, o-quinodimethanes, and benzoenynyl carbodiimides and their cyclizations to polycyclic and heterocyclic compounds","abstract":"Treatment of alkenyldicyclohexylboranes with 1-lithio-5-butyl-3,4-nonadien-1-yne, derived from 5-butyl-3,4-nonadien-1-yne, followed by trimethyltin chloride and acetic acid furnished the corresponding o-isotoluenes in a single operation. The reaction proceeded through an initial formation of (Z)-diene-allenes, which underwent facile eletrocyclizations to produce o-isotoluenes.;Treatment of allenyldicyclohexylborane with 1-lithio-5,5-pentamethylene-3,4-pentadien-1-yne produced the organoborate complex, which on further treatment with trimethyltin chloride furnished a (Z)-1,2,4,6,7-octapentaene (enediallene) derivative in situ. The subsequent electrocyclic reaction then generated the corresponding o-quinodimethane attached with a dicyclohexylboryl group and a trimethyltin group. The resulting o-quinodimethane then underwent a [1,5]-sigmatropic hydrogen shift, and on subsequent oxidative workup and protonation gave the 4-(1-cyclohexenyl)-3-methylphenol (51%). The presence of a boron group and a tin group in the benzene ring of a reaction intermediate also provides handles to allow their transformations to an allyl substituent and an iodo substituent to produce a tetrasubstituted benzene ring (30%) in a single operation. Attempts to capture the o-quinodimethane intermediate with a carbon--carbon double bond intramolecularly afforded a tricyclic phenol in low yield (6%). A number of other o-quinodimethanes were also generated by using different combinations of organoboranes and 1-lithio-1-alkynes.;6H-Indolo[2,3-b]quinolines were synthesized from N-[2-(1-alkynyl)- phenyl]-N'-phenylcarbodiimides via a thermally-induced biradical-forming reaction. The Pd-catalyzed cross-coupling reaction between methyl 2-iodobenzoate and 1-alkynes furnished methyl 2-(1-alkynyl)benzoates, which were hydrolyzed to afford the corresponding benzoic acids. Treatment of the benzoic acids with diphenyl phosphorazidate produced the 2-(1-alkynyl)phenyl isocyanates. The subsequent aza-Wittig reactions with the iminophosphorane, derived from aniline and Ph3P·Br2 then gave the benzoenynyl carbodiimides. Thermolysis of the benzoenynyl carbodiimides in refluxing p-xylene at 138°C produced the corresponding 6H-indolo[2,3-b]quinolines. Similarly, thermolysis of the carbodiimides having two benzoenynyl carbodiimide moieties produced compounds having two indoloquinoline units connected at the 11 and the 11' positions with either a three-carbon or a five-carbon tether. By using 1,4-phenylene diisocyanate for the aza-Wittig reaction with two equiv of the iminophosphorane followed by thermolysis furnished a compound (66%) having two indoloquinoline units incorporated in the seven fused rings.;The synthetic pathway to the 6H-indolo[2,3- b]quinolines was successfully adopted for preparation of the 5-aza anologues of ellipticine, a naturally occuring alkaloid having potent anti-cancer properties. This approach, which constructs the B and the C rings in one step, is an efficient route in producing the aza analogues of the ellipticine family of antitumor alkaloids.","abstract_html":"Treatment of alkenyldicyclohexylboranes with 1-lithio-5-butyl-3,4-nonadien-1-yne, derived from 5-butyl-3,4-nonadien-1-yne, followed by trimethyltin chloride and acetic acid furnished the corresponding o-isotoluenes in a single operation. The reaction proceeded through an initial formation of (Z)-diene-allenes, which underwent facile eletrocyclizations to produce o-isotoluenes.;Treatment of allenyldicyclohexylborane with 1-lithio-5,5-pentamethylene-3,4-pentadien-1-yne produced the organoborate complex, which on further treatment with trimethyltin chloride furnished a (Z)-1,2,4,6,7-octapentaene (enediallene) derivative in situ. The subsequent electrocyclic reaction then generated the corresponding o-quinodimethane attached with a dicyclohexylboryl group and a trimethyltin group. The resulting o-quinodimethane then underwent a [1,5]-sigmatropic hydrogen shift, and on subsequent oxidative workup and protonation gave the 4-(1-cyclohexenyl)-3-methylphenol (51%). The presence of a boron group and a tin group in the benzene ring of a reaction intermediate also provides handles to allow their transformations to an allyl substituent and an iodo substituent to produce a tetrasubstituted benzene ring (30%) in a single operation. Attempts to capture the o-quinodimethane intermediate with a carbon--carbon double bond intramolecularly afforded a tricyclic phenol in low yield (6%). A number of other o-quinodimethanes were also generated by using different combinations of organoboranes and 1-lithio-1-alkynes.;6H-Indolo[2,3-b]quinolines were synthesized from N-[2-(1-alkynyl)- phenyl]-N'-phenylcarbodiimides via a thermally-induced biradical-forming reaction. The Pd-catalyzed cross-coupling reaction between methyl 2-iodobenzoate and 1-alkynes furnished methyl 2-(1-alkynyl)benzoates, which were hydrolyzed to afford the corresponding benzoic acids. Treatment of the benzoic acids with diphenyl phosphorazidate produced the 2-(1-alkynyl)phenyl isocyanates. The subsequent aza-Wittig reactions with the iminophosphorane, derived from aniline and Ph3P·Br2 then gave the benzoenynyl carbodiimides. Thermolysis of the benzoenynyl carbodiimides in refluxing p-xylene at 138°C produced the corresponding 6H-indolo[2,3-b]quinolines. Similarly, thermolysis of the carbodiimides having two benzoenynyl carbodiimide moieties produced compounds having two indoloquinoline units connected at the 11 and the 11' positions with either a three-carbon or a five-carbon tether. By using 1,4-phenylene diisocyanate for the aza-Wittig reaction with two equiv of the iminophosphorane followed by thermolysis furnished a compound (66%) having two indoloquinoline units incorporated in the seven fused rings.;The synthetic pathway to the 6H-indolo[2,3- b]quinolines was successfully adopted for preparation of the 5-aza anologues of ellipticine, a naturally occuring alkaloid having potent anti-cancer properties. This approach, which constructs the B and the C rings in one step, is an efficient route in producing the aza analogues of the ellipticine family of antitumor alkaloids.","abstract_has_math":false,"creators":["Zhang, Quan"],"institution":null,"degree_name":"PhD","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Kung K. Wang."],"advisors":[],"committee_chairs":[],"committee_members":[],"year":1999,"date_issued":"1999-05-01T07:00:00Z","date_published":"1999-05-01T07:00:00Z","updated_at":"2026-07-24T06:15:16Z","subjects":["Organic chemistry","Pharmacy sciences"],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["https://researchrepository.wvu.edu/etd/1050"],"render_values":[{"text":"https://researchrepository.wvu.edu/etd/1050","href":"https://researchrepository.wvu.edu/etd/1050","code":true}]}]},"links":{"outbound_url":"https://doi.org/10.33915/etd.1050","outbound_label":"DOI","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Kung K. Wang."]},{"key":"dc:creator","label":"Author","values":["Zhang, Quan"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.available","label":"Dc Date Available","values":["2019-01-17T08:00:00Z"]},{"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":["PhD"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Organic chemistry","Pharmacy sciences"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["https://doi.org/10.33915/etd.1050","https://researchrepository.wvu.edu/etd/1050"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["Treatment of alkenyldicyclohexylboranes with 1-lithio-5-butyl-3,4-nonadien-1-yne, derived from 5-butyl-3,4-nonadien-1-yne, followed by trimethyltin chloride and acetic acid furnished the corresponding o-isotoluenes in a single operation. The reaction proceeded through an initial formation of (Z)-diene-allenes, which underwent facile eletrocyclizations to produce o-isotoluenes.;Treatment of allenyldicyclohexylborane with 1-lithio-5,5-pentamethylene-3,4-pentadien-1-yne produced the organoborate complex, which on further treatment with trimethyltin chloride furnished a (Z)-1,2,4,6,7-octapentaene (enediallene) derivative in situ. The subsequent electrocyclic reaction then generated the corresponding o-quinodimethane attached with a dicyclohexylboryl group and a trimethyltin group. The resulting o-quinodimethane then underwent a [1,5]-sigmatropic hydrogen shift, and on subsequent oxidative workup and protonation gave the 4-(1-cyclohexenyl)-3-methylphenol (51%). The presence of a boron group and a tin group in the benzene ring of a reaction intermediate also provides handles to allow their transformations to an allyl substituent and an iodo substituent to produce a tetrasubstituted benzene ring (30%) in a single operation. Attempts to capture the o-quinodimethane intermediate with a carbon--carbon double bond intramolecularly afforded a tricyclic phenol in low yield (6%). A number of other o-quinodimethanes were also generated by using different combinations of organoboranes and 1-lithio-1-alkynes.;6H-Indolo[2,3-b]quinolines were synthesized from N-[2-(1-alkynyl)- phenyl]-N'-phenylcarbodiimides via a thermally-induced biradical-forming reaction. The Pd-catalyzed cross-coupling reaction between methyl 2-iodobenzoate and 1-alkynes furnished methyl 2-(1-alkynyl)benzoates, which were hydrolyzed to afford the corresponding benzoic acids. Treatment of the benzoic acids with diphenyl phosphorazidate produced the 2-(1-alkynyl)phenyl isocyanates. The subsequent aza-Wittig reactions with the iminophosphorane, derived from aniline and Ph3P·Br2 then gave the benzoenynyl carbodiimides. Thermolysis of the benzoenynyl carbodiimides in refluxing p-xylene at 138°C produced the corresponding 6H-indolo[2,3-b]quinolines. Similarly, thermolysis of the carbodiimides having two benzoenynyl carbodiimide moieties produced compounds having two indoloquinoline units connected at the 11 and the 11' positions with either a three-carbon or a five-carbon tether. By using 1,4-phenylene diisocyanate for the aza-Wittig reaction with two equiv of the iminophosphorane followed by thermolysis furnished a compound (66%) having two indoloquinoline units incorporated in the seven fused rings.;The synthetic pathway to the 6H-indolo[2,3- b]quinolines was successfully adopted for preparation of the 5-aza anologues of ellipticine, a naturally occuring alkaloid having potent anti-cancer properties. This approach, which constructs the B and the C rings in one step, is an efficient route in producing the aza analogues of the ellipticine family of antitumor alkaloids."]},{"key":"dc:title","label":"Title","values":["Synthesis of o-isotoluenes, o-quinodimethanes, and benzoenynyl carbodiimides and their cyclizations to polycyclic and heterocyclic compounds"]}]}],"canonical_facts":{"dc:contributor":["Kung K. Wang."],"dc:creator":["Zhang, Quan"],"dc:date.available":["2019-01-17T08:00:00Z"],"dc:description.abstract":["Treatment of alkenyldicyclohexylboranes with 1-lithio-5-butyl-3,4-nonadien-1-yne, derived from 5-butyl-3,4-nonadien-1-yne, followed by trimethyltin chloride and acetic acid furnished the corresponding o-isotoluenes in a single operation. The reaction proceeded through an initial formation of (Z)-diene-allenes, which underwent facile eletrocyclizations to produce o-isotoluenes.;Treatment of allenyldicyclohexylborane with 1-lithio-5,5-pentamethylene-3,4-pentadien-1-yne produced the organoborate complex, which on further treatment with trimethyltin chloride furnished a (Z)-1,2,4,6,7-octapentaene (enediallene) derivative in situ. The subsequent electrocyclic reaction then generated the corresponding o-quinodimethane attached with a dicyclohexylboryl group and a trimethyltin group. The resulting o-quinodimethane then underwent a [1,5]-sigmatropic hydrogen shift, and on subsequent oxidative workup and protonation gave the 4-(1-cyclohexenyl)-3-methylphenol (51%). The presence of a boron group and a tin group in the benzene ring of a reaction intermediate also provides handles to allow their transformations to an allyl substituent and an iodo substituent to produce a tetrasubstituted benzene ring (30%) in a single operation. Attempts to capture the o-quinodimethane intermediate with a carbon--carbon double bond intramolecularly afforded a tricyclic phenol in low yield (6%). A number of other o-quinodimethanes were also generated by using different combinations of organoboranes and 1-lithio-1-alkynes.;6H-Indolo[2,3-b]quinolines were synthesized from N-[2-(1-alkynyl)- phenyl]-N'-phenylcarbodiimides via a thermally-induced biradical-forming reaction. The Pd-catalyzed cross-coupling reaction between methyl 2-iodobenzoate and 1-alkynes furnished methyl 2-(1-alkynyl)benzoates, which were hydrolyzed to afford the corresponding benzoic acids. Treatment of the benzoic acids with diphenyl phosphorazidate produced the 2-(1-alkynyl)phenyl isocyanates. The subsequent aza-Wittig reactions with the iminophosphorane, derived from aniline and Ph3P·Br2 then gave the benzoenynyl carbodiimides. Thermolysis of the benzoenynyl carbodiimides in refluxing p-xylene at 138°C produced the corresponding 6H-indolo[2,3-b]quinolines. Similarly, thermolysis of the carbodiimides having two benzoenynyl carbodiimide moieties produced compounds having two indoloquinoline units connected at the 11 and the 11' positions with either a three-carbon or a five-carbon tether. By using 1,4-phenylene diisocyanate for the aza-Wittig reaction with two equiv of the iminophosphorane followed by thermolysis furnished a compound (66%) having two indoloquinoline units incorporated in the seven fused rings.;The synthetic pathway to the 6H-indolo[2,3- b]quinolines was successfully adopted for preparation of the 5-aza anologues of ellipticine, a naturally occuring alkaloid having potent anti-cancer properties. This approach, which constructs the B and the C rings in one step, is an efficient route in producing the aza analogues of the ellipticine family of antitumor alkaloids."],"dc:identifier":["https://doi.org/10.33915/etd.1050","https://researchrepository.wvu.edu/etd/1050"],"dc:subject":["Organic chemistry","Pharmacy sciences"],"dc:title":["Synthesis of o-isotoluenes, o-quinodimethanes, and benzoenynyl carbodiimides and their cyclizations to polycyclic and heterocyclic compounds"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["Dissertation"],"thesis:degree_name":["PhD"]},"updated_at":"2026-07-24T06:15:16Z"}