Iron complexes of tetramine ligands catalyse allylic hydroxyamination via a nitroso–ene mechanism
Iron(II) complexes of the tetradentate amines tris(2-pyridylmethyl)amine (TPA) and N,N′-bis(2-pyridylmethyl)-N,N′-dimethylethane-1,2-diamine (BPMEN) are established catalysts of C–O bond formation, oxidising hydrocarbon substrates via hydroxylation, epoxidation and dihydroxylation pathways. Herein w...
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| Format: | Article |
| Language: | English |
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Beilstein-Institut
2015-12-01
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| Series: | Beilstein Journal of Organic Chemistry |
| Subjects: | |
| Online Access: | https://doi.org/10.3762/bjoc.11.275 |
| _version_ | 1819275151054733312 |
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| author | David Porter Belinda M.-L. Poon Peter J. Rutledge |
| author_facet | David Porter Belinda M.-L. Poon Peter J. Rutledge |
| author_sort | David Porter |
| collection | DOAJ |
| description | Iron(II) complexes of the tetradentate amines tris(2-pyridylmethyl)amine (TPA) and N,N′-bis(2-pyridylmethyl)-N,N′-dimethylethane-1,2-diamine (BPMEN) are established catalysts of C–O bond formation, oxidising hydrocarbon substrates via hydroxylation, epoxidation and dihydroxylation pathways. Herein we report the capacity of these catalysts to promote C–N bond formation, via allylic amination of alkenes. The combination of N-Boc-hydroxylamine with either FeTPA (1 mol %) or FeBPMEN (10 mol %) converts cyclohexene to the allylic hydroxylamine (tert-butyl cyclohex-2-en-1-yl(hydroxy)carbamate) in moderate yields. Spectroscopic studies and trapping experiments suggest the reaction proceeds via a nitroso–ene mechanism, with involvement of a free N-Boc-nitroso intermediate. Asymmetric induction is not observed using the chiral tetramine ligand (+)-(2R,2′R)-1,1′-bis(2-pyridylmethyl)-2,2′-bipyrrolidine ((R,R′)-PDP). |
| first_indexed | 2024-12-23T23:19:46Z |
| format | Article |
| id | doaj.art-1a0cc420687447a9ae2b24def4dc4f8d |
| institution | Directory Open Access Journal |
| issn | 1860-5397 |
| language | English |
| last_indexed | 2024-12-23T23:19:46Z |
| publishDate | 2015-12-01 |
| publisher | Beilstein-Institut |
| record_format | Article |
| series | Beilstein Journal of Organic Chemistry |
| spelling | doaj.art-1a0cc420687447a9ae2b24def4dc4f8d2022-12-21T17:26:22ZengBeilstein-InstitutBeilstein Journal of Organic Chemistry1860-53972015-12-011112549255610.3762/bjoc.11.2751860-5397-11-275Iron complexes of tetramine ligands catalyse allylic hydroxyamination via a nitroso–ene mechanismDavid Porter0Belinda M.-L. Poon1Peter J. Rutledge2School of Chemistry F11, The University of Sydney, NSW 2006, AustraliaSchool of Chemistry F11, The University of Sydney, NSW 2006, AustraliaSchool of Chemistry F11, The University of Sydney, NSW 2006, AustraliaIron(II) complexes of the tetradentate amines tris(2-pyridylmethyl)amine (TPA) and N,N′-bis(2-pyridylmethyl)-N,N′-dimethylethane-1,2-diamine (BPMEN) are established catalysts of C–O bond formation, oxidising hydrocarbon substrates via hydroxylation, epoxidation and dihydroxylation pathways. Herein we report the capacity of these catalysts to promote C–N bond formation, via allylic amination of alkenes. The combination of N-Boc-hydroxylamine with either FeTPA (1 mol %) or FeBPMEN (10 mol %) converts cyclohexene to the allylic hydroxylamine (tert-butyl cyclohex-2-en-1-yl(hydroxy)carbamate) in moderate yields. Spectroscopic studies and trapping experiments suggest the reaction proceeds via a nitroso–ene mechanism, with involvement of a free N-Boc-nitroso intermediate. Asymmetric induction is not observed using the chiral tetramine ligand (+)-(2R,2′R)-1,1′-bis(2-pyridylmethyl)-2,2′-bipyrrolidine ((R,R′)-PDP).https://doi.org/10.3762/bjoc.11.275CH activationhydroxyaminationiron catalysisnitroso-ene |
| spellingShingle | David Porter Belinda M.-L. Poon Peter J. Rutledge Iron complexes of tetramine ligands catalyse allylic hydroxyamination via a nitroso–ene mechanism Beilstein Journal of Organic Chemistry CH activation hydroxyamination iron catalysis nitroso-ene |
| title | Iron complexes of tetramine ligands catalyse allylic hydroxyamination via a nitroso–ene mechanism |
| title_full | Iron complexes of tetramine ligands catalyse allylic hydroxyamination via a nitroso–ene mechanism |
| title_fullStr | Iron complexes of tetramine ligands catalyse allylic hydroxyamination via a nitroso–ene mechanism |
| title_full_unstemmed | Iron complexes of tetramine ligands catalyse allylic hydroxyamination via a nitroso–ene mechanism |
| title_short | Iron complexes of tetramine ligands catalyse allylic hydroxyamination via a nitroso–ene mechanism |
| title_sort | iron complexes of tetramine ligands catalyse allylic hydroxyamination via a nitroso ene mechanism |
| topic | CH activation hydroxyamination iron catalysis nitroso-ene |
| url | https://doi.org/10.3762/bjoc.11.275 |
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