{"id":{"repo_id":"aachen","oai_identifier":"oai:publications.rwth-aachen.de:62259"},"canonical_url":"https://search.dev.ndltd.org/etd/aachen/oai:publications.rwth-aachen.de:62259","repository":{"repo_id":"aachen","name":"RWTH Aachen University","base_url":"https://publications.rwth-aachen.de/oai2d"},"display":{"title":"Iron catalyzed C-H activation and synthesis of novel ligands","abstract":"Iron-catalyzed benzylic oxidations, nitrogen transfer reactions such as iminations of sulfides and sulfoxides, aziridinations of olefins and a-aminations of silyl enol ethers were developed. Also, the synthesis of novel nitrogen containing ligands such as 1,4,7-triazacyclononane (TACN) derivatives and dipyridylamine derivatives was undertaken.Iron-catalyzed benzylic oxidation was successfully performed by using a combination of iron(III) chloride (2 mol%) as a catalyst and tert-butyl hydroperoxide (TBHP) as an oxidant. Diarylmethane derivatives gave the corresponding ketones in excellent yields (up to >99%). Also, less reactive substrates bearing one annulated aryl group in a cyclic system, noncyclic compounds bearing one (hetero)aryl group and p-methoxytoluene led to the corresponding ketones or carboxylic acid in good yield. Even diphenylcarbinol was oxidized to afford benzophenone in 86% yield. Interestingly, the oxidation of triphenylmethane afforded tert-butyl triphenylmethyl peroxide in 91% yield instead of triphenylmethanol. Additionally, 1,4-dihydroxynaphthaline underwent oxidation in actonitrile at ambient temperature to afford 1,4-naphthoquinone in high yield (82%). Iron-catalyzed aziridination was achieved by using iron(II) triflate (2.5 mol%), MS 4A (20 mg), 20 equivs. of styrene and 1 equiv. of [N-(p-nitrobenzenesulfonyl)imino]phenyliodinane (PhINNs) affording phenylaziridine in 88% yield. Poorly reactive olefins such as a- or b-methyl styrene were aziridinated. A cyclic olefin such as cis-cyclooctene can be aziridinated efficiently by increasing the catalyst loading up to 20 mol%. These conditions were applied for the asymmetric aziridination of styrene. After ligand screening, an (S,S)-i-Pr-pybox ligand was discovered to be an efficient ligand, affording (R)-phenylaziridine in 83% yield with 40% ee. Also, aziridinations using in situ generated iminophenyliodinanes using 10-20 mol% of iron(II) triflate and a combination of the corresponding sulfonamide and iodobenzene diacetate (2 equivs.) with magnesium oxide (5 equivs.) as a base or iodosylbenzene (PhI=O) led to the corresponding phenylaziridines in high yields (up to 76%). Further investigation of the iron(II) triflate catalyzed aziridination of styrene, has led to the discovery that attempted iron(II) triflate catalyzed aziridinations of silyl enol ethers using the same conditions gave a-amino ketones, or esters. In the synthesis of novel ligands, aryl-TACN derivatives were synthesized by using palladium catalysis. Triple N-arylation of TACN was achieved by use of a catalyst comprised of tris(dibenzyllideneacetone)dipalladium(0) and 2-dicyclohexylphosphino-2’-(N,N-dimethylamino)biphenyl as a phosphine ligand in the presence of 4.2 equivs. of sodium tert-butoxide in toluene at 100 °C. Also, double N-phenylation of mono-tosyl TACN proceeded under the same conditions affording di-phenyl TACN in 70% yield. Furthermore, mono-N-phenylation of di-(Boc), (Cbz) or (Ts) protected TACN was successful by using a mixture of palladium(II) acetate and rac-BINAP affording mono-phenylated TACNs in good yields. Also, a synthesis of dipyridylamine ligands has been developed using palladium catalysis. As a representative example, N-arylation of 2-picolylamine with 2-bromopyridine was achieved by using tris(dibenzyllideneacetone)dipalladium(0) (2 mol%) and rac-BINAP (2 mol%) in the presence of sodium tert-butoxide (2.2 equivs.) in toluene at 100 °C affording 2,2’-N,N-dipyridyl-picolylamine in 80% yield.","abstract_html":"Iron-catalyzed benzylic oxidations, nitrogen transfer reactions such as iminations of sulfides and sulfoxides, aziridinations of olefins and a-aminations of silyl enol ethers were developed. Also, the synthesis of novel nitrogen containing ligands such as 1,4,7-triazacyclononane (TACN) derivatives and dipyridylamine derivatives was undertaken.Iron-catalyzed benzylic oxidation was successfully performed by using a combination of iron(III) chloride (2 mol%) as a catalyst and tert-butyl hydroperoxide (TBHP) as an oxidant. Diarylmethane derivatives gave the corresponding ketones in excellent yields (up to >99%). Also, less reactive substrates bearing one annulated aryl group in a cyclic system, noncyclic compounds bearing one (hetero)aryl group and p-methoxytoluene led to the corresponding ketones or carboxylic acid in good yield. Even diphenylcarbinol was oxidized to afford benzophenone in 86% yield. Interestingly, the oxidation of triphenylmethane afforded tert-butyl triphenylmethyl peroxide in 91% yield instead of triphenylmethanol. Additionally, 1,4-dihydroxynaphthaline underwent oxidation in actonitrile at ambient temperature to afford 1,4-naphthoquinone in high yield (82%). Iron-catalyzed aziridination was achieved by using iron(II) triflate (2.5 mol%), MS 4A (20 mg), 20 equivs. of styrene and 1 equiv. of [N-(p-nitrobenzenesulfonyl)imino]phenyliodinane (PhINNs) affording phenylaziridine in 88% yield. Poorly reactive olefins such as a- or b-methyl styrene were aziridinated. A cyclic olefin such as cis-cyclooctene can be aziridinated efficiently by increasing the catalyst loading up to 20 mol%. These conditions were applied for the asymmetric aziridination of styrene. After ligand screening, an (S,S)-i-Pr-pybox ligand was discovered to be an efficient ligand, affording (R)-phenylaziridine in 83% yield with 40% ee. Also, aziridinations using in situ generated iminophenyliodinanes using 10-20 mol% of iron(II) triflate and a combination of the corresponding sulfonamide and iodobenzene diacetate (2 equivs.) with magnesium oxide (5 equivs.) as a base or iodosylbenzene (PhI=O) led to the corresponding phenylaziridines in high yields (up to 76%). Further investigation of the iron(II) triflate catalyzed aziridination of styrene, has led to the discovery that attempted iron(II) triflate catalyzed aziridinations of silyl enol ethers using the same conditions gave a-amino ketones, or esters. In the synthesis of novel ligands, aryl-TACN derivatives were synthesized by using palladium catalysis. Triple N-arylation of TACN was achieved by use of a catalyst comprised of tris(dibenzyllideneacetone)dipalladium(0) and 2-dicyclohexylphosphino-2’-(N,N-dimethylamino)biphenyl as a phosphine ligand in the presence of 4.2 equivs. of sodium tert-butoxide in toluene at 100 °C. Also, double N-phenylation of mono-tosyl TACN proceeded under the same conditions affording di-phenyl TACN in 70% yield. Furthermore, mono-N-phenylation of di-(Boc), (Cbz) or (Ts) protected TACN was successful by using a mixture of palladium(II) acetate and rac-BINAP affording mono-phenylated TACNs in good yields. Also, a synthesis of dipyridylamine ligands has been developed using palladium catalysis. As a representative example, N-arylation of 2-picolylamine with 2-bromopyridine was achieved by using tris(dibenzyllideneacetone)dipalladium(0) (2 mol%) and rac-BINAP (2 mol%) in the presence of sodium tert-butoxide (2.2 equivs.) in toluene at 100 °C affording 2,2’-N,N-dipyridyl-picolylamine in 80% yield.","abstract_has_math":false,"creators":["Nakanishi, Masafumi"],"institution":"Publikationsserver der RWTH Aachen University","degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":null,"school":null,"contributors":["Bolm, Carsten"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2007,"date_issued":"2007","date_published":"2007","updated_at":"2026-07-30T19:43:19Z","subjects":["info:eu-repo/classification/ddc/540","Eisen","Chemie","Iron","C-H Activation","Novel Ligands","Aziridination","Oxidation"],"languages":["eng"],"rights":["info:eu-repo/semantics/openAccess"],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["https://publications.rwth-aachen.de/search?p=id:%22RWTH-CONV-123837%22"],"render_values":[{"text":"https://publications.rwth-aachen.de/search?p=id:%22RWTH-CONV-123837%22","href":"https://publications.rwth-aachen.de/search?p=id:%22RWTH-CONV-123837%22","code":true}]}]},"links":{"outbound_url":"https://publications.rwth-aachen.de/record/62259","outbound_label":"Repository record","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Bolm, Carsten"]},{"key":"dc:creator","label":"Author","values":["Nakanishi, Masafumi"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:coverage","label":"Dc Coverage","values":["DE"]},{"key":"dc:date","label":"Dc Date","values":["2007"]},{"key":"dc:publisher","label":"Institution","values":["Publikationsserver der RWTH Aachen University"]},{"key":"dc:relation","label":"Dc Relation","values":["info:eu-repo/semantics/altIdentifier/urn/urn:nbn:de:hbz:82-opus-20627"]},{"key":"dc:type","label":"Dc Type","values":["info:eu-repo/semantics/doctoralThesis","info:eu-repo/semantics/publishedVersion"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["info:eu-repo/classification/ddc/540","Eisen","Chemie","Iron","C-H Activation","Novel Ligands","Aziridination","Oxidation"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["eng"]},{"key":"dc:rights","label":"Dc Rights","values":["info:eu-repo/semantics/openAccess"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["https://publications.rwth-aachen.de/record/62259","https://publications.rwth-aachen.de/search?p=id:%22RWTH-CONV-123837%22"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Iron-catalyzed benzylic oxidations, nitrogen transfer reactions such as iminations of sulfides and sulfoxides, aziridinations of olefins and a-aminations of silyl enol ethers were developed. Also, the synthesis of novel nitrogen containing ligands such as 1,4,7-triazacyclononane (TACN) derivatives and dipyridylamine derivatives was undertaken.Iron-catalyzed benzylic oxidation was successfully performed by using a combination of iron(III) chloride (2 mol%) as a catalyst and tert-butyl hydroperoxide (TBHP) as an oxidant. Diarylmethane derivatives gave the corresponding ketones in excellent yields (up to >99%). Also, less reactive substrates bearing one annulated aryl group in a cyclic system, noncyclic compounds bearing one (hetero)aryl group and p-methoxytoluene led to the corresponding ketones or carboxylic acid in good yield. Even diphenylcarbinol was oxidized to afford benzophenone in 86% yield. Interestingly, the oxidation of triphenylmethane afforded tert-butyl triphenylmethyl peroxide in 91% yield instead of triphenylmethanol. Additionally, 1,4-dihydroxynaphthaline underwent oxidation in actonitrile at ambient temperature to afford 1,4-naphthoquinone in high yield (82%). Iron-catalyzed aziridination was achieved by using iron(II) triflate (2.5 mol%), MS 4A (20 mg), 20 equivs. of styrene and 1 equiv. of [N-(p-nitrobenzenesulfonyl)imino]phenyliodinane (PhINNs) affording phenylaziridine in 88% yield. Poorly reactive olefins such as a- or b-methyl styrene were aziridinated. A cyclic olefin such as cis-cyclooctene can be aziridinated efficiently by increasing the catalyst loading up to 20 mol%. These conditions were applied for the asymmetric aziridination of styrene. After ligand screening, an (S,S)-i-Pr-pybox ligand was discovered to be an efficient ligand, affording (R)-phenylaziridine in 83% yield with 40% ee. Also, aziridinations using in situ generated iminophenyliodinanes using 10-20 mol% of iron(II) triflate and a combination of the corresponding sulfonamide and iodobenzene diacetate (2 equivs.) with magnesium oxide (5 equivs.) as a base or iodosylbenzene (PhI=O) led to the corresponding phenylaziridines in high yields (up to 76%). Further investigation of the iron(II) triflate catalyzed aziridination of styrene, has led to the discovery that attempted iron(II) triflate catalyzed aziridinations of silyl enol ethers using the same conditions gave a-amino ketones, or esters. In the synthesis of novel ligands, aryl-TACN derivatives were synthesized by using palladium catalysis. Triple N-arylation of TACN was achieved by use of a catalyst comprised of tris(dibenzyllideneacetone)dipalladium(0) and 2-dicyclohexylphosphino-2’-(N,N-dimethylamino)biphenyl as a phosphine ligand in the presence of 4.2 equivs. of sodium tert-butoxide in toluene at 100 °C. Also, double N-phenylation of mono-tosyl TACN proceeded under the same conditions affording di-phenyl TACN in 70% yield. Furthermore, mono-N-phenylation of di-(Boc), (Cbz) or (Ts) protected TACN was successful by using a mixture of palladium(II) acetate and rac-BINAP affording mono-phenylated TACNs in good yields. Also, a synthesis of dipyridylamine ligands has been developed using palladium catalysis. As a representative example, N-arylation of 2-picolylamine with 2-bromopyridine was achieved by using tris(dibenzyllideneacetone)dipalladium(0) (2 mol%) and rac-BINAP (2 mol%) in the presence of sodium tert-butoxide (2.2 equivs.) in toluene at 100 °C affording 2,2’-N,N-dipyridyl-picolylamine in 80% yield."]},{"key":"dc:source","label":"Dc Source","values":["Aachen : Publikationsserver der RWTH Aachen University 216 S. (2007). = Aachen, Techn. Hochsch., Diss., 2007"]},{"key":"dc:title","label":"Title","values":["Iron catalyzed C-H activation and synthesis of novel ligands"]}]}],"canonical_facts":{"dc:contributor":["Bolm, Carsten"],"dc:coverage":["DE"],"dc:creator":["Nakanishi, Masafumi"],"dc:date":["2007"],"dc:description":["Iron-catalyzed benzylic oxidations, nitrogen transfer reactions such as iminations of sulfides and sulfoxides, aziridinations of olefins and a-aminations of silyl enol ethers were developed. Also, the synthesis of novel nitrogen containing ligands such as 1,4,7-triazacyclononane (TACN) derivatives and dipyridylamine derivatives was undertaken.Iron-catalyzed benzylic oxidation was successfully performed by using a combination of iron(III) chloride (2 mol%) as a catalyst and tert-butyl hydroperoxide (TBHP) as an oxidant. Diarylmethane derivatives gave the corresponding ketones in excellent yields (up to >99%). Also, less reactive substrates bearing one annulated aryl group in a cyclic system, noncyclic compounds bearing one (hetero)aryl group and p-methoxytoluene led to the corresponding ketones or carboxylic acid in good yield. Even diphenylcarbinol was oxidized to afford benzophenone in 86% yield. Interestingly, the oxidation of triphenylmethane afforded tert-butyl triphenylmethyl peroxide in 91% yield instead of triphenylmethanol. Additionally, 1,4-dihydroxynaphthaline underwent oxidation in actonitrile at ambient temperature to afford 1,4-naphthoquinone in high yield (82%). Iron-catalyzed aziridination was achieved by using iron(II) triflate (2.5 mol%), MS 4A (20 mg), 20 equivs. of styrene and 1 equiv. of [N-(p-nitrobenzenesulfonyl)imino]phenyliodinane (PhINNs) affording phenylaziridine in 88% yield. Poorly reactive olefins such as a- or b-methyl styrene were aziridinated. A cyclic olefin such as cis-cyclooctene can be aziridinated efficiently by increasing the catalyst loading up to 20 mol%. These conditions were applied for the asymmetric aziridination of styrene. After ligand screening, an (S,S)-i-Pr-pybox ligand was discovered to be an efficient ligand, affording (R)-phenylaziridine in 83% yield with 40% ee. Also, aziridinations using in situ generated iminophenyliodinanes using 10-20 mol% of iron(II) triflate and a combination of the corresponding sulfonamide and iodobenzene diacetate (2 equivs.) with magnesium oxide (5 equivs.) as a base or iodosylbenzene (PhI=O) led to the corresponding phenylaziridines in high yields (up to 76%). Further investigation of the iron(II) triflate catalyzed aziridination of styrene, has led to the discovery that attempted iron(II) triflate catalyzed aziridinations of silyl enol ethers using the same conditions gave a-amino ketones, or esters. In the synthesis of novel ligands, aryl-TACN derivatives were synthesized by using palladium catalysis. Triple N-arylation of TACN was achieved by use of a catalyst comprised of tris(dibenzyllideneacetone)dipalladium(0) and 2-dicyclohexylphosphino-2’-(N,N-dimethylamino)biphenyl as a phosphine ligand in the presence of 4.2 equivs. of sodium tert-butoxide in toluene at 100 °C. Also, double N-phenylation of mono-tosyl TACN proceeded under the same conditions affording di-phenyl TACN in 70% yield. Furthermore, mono-N-phenylation of di-(Boc), (Cbz) or (Ts) protected TACN was successful by using a mixture of palladium(II) acetate and rac-BINAP affording mono-phenylated TACNs in good yields. Also, a synthesis of dipyridylamine ligands has been developed using palladium catalysis. As a representative example, N-arylation of 2-picolylamine with 2-bromopyridine was achieved by using tris(dibenzyllideneacetone)dipalladium(0) (2 mol%) and rac-BINAP (2 mol%) in the presence of sodium tert-butoxide (2.2 equivs.) in toluene at 100 °C affording 2,2’-N,N-dipyridyl-picolylamine in 80% yield."],"dc:identifier":["https://publications.rwth-aachen.de/record/62259","https://publications.rwth-aachen.de/search?p=id:%22RWTH-CONV-123837%22"],"dc:language":["eng"],"dc:publisher":["Publikationsserver der RWTH Aachen University"],"dc:relation":["info:eu-repo/semantics/altIdentifier/urn/urn:nbn:de:hbz:82-opus-20627"],"dc:rights":["info:eu-repo/semantics/openAccess"],"dc:source":["Aachen : Publikationsserver der RWTH Aachen University 216 S. (2007). = Aachen, Techn. Hochsch., Diss., 2007"],"dc:subject":["info:eu-repo/classification/ddc/540","Eisen","Chemie","Iron","C-H Activation","Novel Ligands","Aziridination","Oxidation"],"dc:title":["Iron catalyzed C-H activation and synthesis of novel ligands"],"dc:type":["info:eu-repo/semantics/doctoralThesis","info:eu-repo/semantics/publishedVersion"]},"updated_at":"2026-07-30T19:43:19Z"}