Origin of diastereoselectivity in the organolanthanide-mediated intramolecular hydroamination/cyclisation of aminodienes: A computational exploration of constrained geometry CGC-Ln catalysts

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Abstract

The regulation of ring-substituent diastereoselectivity in the intramolecular hydroamination/cyclisation (IHC of a-substituted aminodienes by constrained geometry CGC-lanthanide catalysts (CGC=[Me4Si5(eta(5)-Me4C5)(tBuN)](2-)) has been elucidated by means of a reliable DFT method. The first survey of relevant elementary steps for the 1-methyl-(4E,6)-heptadienylamine substrate (1) and the [{Me2Si(eta(5)-Me4C5(tBuN)}Sm(N(TMS)(2)}] starting material (2) identified the following general mechanistic aspects of Ln-catalysed aminodiene IHC. The substrate-adduct 3-S of the active CGC-Ln-amidodiene compound represents the catalyst's resting state, but the substrate-free form 3' with a chelating amidodiene functionality is the direct precursor for cyclisation. Ibis step proceeds with almost complete regioselectivity through exocyclic ring closure by means of a frontal trajectory, giving rise to the CGC-Ln-azacycle intermediate 4. Subsequent protonolysis of 4 is turnover limiting, whilst the ring-substituent diastereoselectivity is dictated by exocyclic ring closure. Unfavourable close interatomic contacts between the substrate's alpha-substituent and the catalyst backbone have been shown to largely govern the trans/cis selectivity. Substituents of sufficient bulk in the a-position of the substrate have been identified as being vital for stereochemical induction. The present study has indicated that the diastereoselectivity of ring closure can be considerably modulated. The variation of the lanthanide's ionic radius and introduction of extra steric pressure at the substrate's cc-position and/or the CGC N centre have been identified as effective handles for tuning the selectivity. The quantification of these factors reported herein represents the first step toward the rational design of improved CGC-Ln catalyst architectures and will thus aid this process.

Original languageEnglish
Pages (from-to)9127-9136
Number of pages10
JournalChemistry - A European Journal
Volume13
DOIs
Publication statusPublished - 2007

Keywords

  • density functional calculations
  • diastereoselectivity
  • hydroamination
  • lanthanides
  • reaction mechanisms
  • UNPROTECTED AMINO OLEFINS
  • EFFECTIVE IONIC-RADII
  • CONJUGATED AMINODIENES
  • AMINOALKENE HYDROAMINATION/CYCLIZATION
  • REGIOSPECIFIC CYCLIZATION
  • 1,2-DISUBSTITUTED ALKENES
  • ZIRCONOCENE CATALYST
  • COMPLEXES
  • CHEMISTRY
  • MECHANISM

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