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  • 1
    Publication Date: 2015-12-12
    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 (+)-(2 R ,2′ R )-1,1′-bis(2-pyridylmethyl)-2,2′-bipyrrolidine (( R , R ′)-PDP). Beilstein J. Org. Chem. 2015, 11, 2549–2556. doi:10.3762/bjoc.11.275
    Keywords: CH activationhydroxyaminationiron catalysisnitroso-ene
    Electronic ISSN: 1860-5397
    Topics: Chemistry and Pharmacology
    Published by Beilstein-Institut
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  • 2
    Publication Date: 2015-07-31
    Description: The rapid development of new and emerging science & technologies (NESTs) brings unprecedented challenges, but also opportunities. In this paper, we use bibliometric and social network analyses, at country, institution, and individual levels, to explore the patterns of scientific networking for a key nano area – nano-enabled drug delivery (NEDD). NEDD has successfully been used clinically to modulate drug release and to target particular diseased tissues. The data for this research come from a global compilation of research publication information on NEDD directed at brain cancer. We derive a family of indicators that address multiple facets of research collaboration and knowledge transfer patterns. Results show that: (1) international cooperation is increasing, but networking characteristics change over time; (2) highly productive institutions also lead in influence, as measured by citation to their work, with American institutes leading; (3) research collaboration is dominated by local relationships, with interesting information available from authorship patterns that go well beyond journal impact factors. Results offer useful technical intelligence to help researchers identify potential collaborators and to help inform R&D management and science & innovation policy for such nanotechnologies.
    Electronic ISSN: 2190-4286
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics , Technology
    Published by Beilstein-Institut
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  • 3
    Publication Date: 2015-12-11
    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).
    Print ISSN: 2195-951X
    Electronic ISSN: 1860-5397
    Topics: Chemistry and Pharmacology
    Published by Beilstein-Institut
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