Research

Dearomatized BIAN alkaline-earth alkyl catalysts for the intramolecular hydroamination of hindered aminoalkenes


Reference:

Arrowsmith, M., Hill, M. S. and Kociok-Kohn, G., 2014. Dearomatized BIAN alkaline-earth alkyl catalysts for the intramolecular hydroamination of hindered aminoalkenes. Organometallics, 33 (1), pp. 206-216.

Related documents:

[img] PDF (Selective dearomatisation of a BIAN ligand with group 2 dialkyls_Revision) - Requires a PDF viewer such as GSview, Xpdf or Adobe Acrobat Reader
Download (0B)
    [img]
    Preview
    PDF (Selective dearomatisation of a BIAN ligand with group 2 dialkyls_Revision) - Requires a PDF viewer such as GSview, Xpdf or Adobe Acrobat Reader
    Download (984kB) | Preview

      Official URL:

      http://dx.doi.org/10.1021/om400955v

      Related URLs:

      Abstract

      Reaction of a sterically encumbered bis(imino)acenapthene (dipp-BIAN) with either potassium alkyl or the heavier alkaline-earth dialkyl [Ae{CH(SiMe3)2}2(THF)2] (Ae = Mg, Ca, Sr) reagents results in dearomatization of the aromatic ligand. The heteroleptic alkaline-earth alkyl species show enhanced stability toward Schlenk-type redistribution but undergo solution exchange when the bis(trimethylsilyl)methyl substituent is replaced by an anionic ligand of lower overall steric demands. In contrast, analogous reactions performed with [Ba{CH(SiMe3)2} 2(THF)] evidenced facile solution redistribution and resulted in an unusual C-C coupling reaction which is suggested to result from a sterically induced reductive process. An assessment of the Mg, Ca, and Sr alkyl compounds as precatalysts for the intramolecular hydroamination of aminoalkenes evidenced enhanced reactivity, which is ascribed to the greater solution stability of the catalytically active species. Most notably the calcium species may even be applied to the high-yielding cyclization of substrates bearing alkyl substitution at either of the alkenyl positions.

      Details

      Item Type Articles
      CreatorsArrowsmith, M., Hill, M. S. and Kociok-Kohn, G.
      DOI10.1021/om400955v
      Related URLs
      URLURL Type
      http://www.scopus.com/inward/record.url?scp=84892595979&partnerID=8YFLogxKUNSPECIFIED
      DepartmentsFaculty of Science > Chemistry
      Research CentresCentre for Sustainable Chemical Technologies
      Publisher StatementSelective_dearomatisation_of_a_BIAN_ligand_with_group_2_dialkyls_Revision.pdf: This document is the Accepted Manuscript version of a Published Work that appeared in final form in Organometallics, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/doi/abs/10.1021/om400955v
      RefereedYes
      StatusPublished
      ID Code38484

      Export

      Actions (login required)

      View Item

      Document Downloads

      More statistics for this item...