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Synthesis of bridged heterocycles via sequential 1,4- and 1,2-addition reactions to α,β-unsaturated N-acyliminium ions: mechanistic and computational studies

Journal Article


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Abstract


  • Novel tricyclic bridged heterocyclic systems can be readily prepared from sequential 1,4- and 1,2-addition reactions of allyl and 3-substituted allylsilanes to indolizidine and quinolizidine α,β-unsaturated N-acyliminium ions. These reactions involve a novel N-assisted, transannular 1,5-hydride shift. Such a mechanism was supported by examining the reaction of a dideuterated indolizidine, α,β-unsaturated N-acyliminium ion precursor, which provided specifically dideuterated tricyclic bridged heterocyclic products, and from computational studies. In contrast, the corresponding pyrrolo[1,2-a]azepine system did not provide the corresponding tricyclic bridged heterocyclic product and gave only a bis-allyl adduct, while more substituted versions gave novel furo[3,2-d]pyrrolo[1,2-a]azepine products. Such heterocyclic systems would be expected to be useful scaffolds for the preparation of libraries of novel compounds for new drug discovery programs.

UOW Authors


  •   Yazici, Arife (external author)
  •   Wille, Uta (external author)
  •   Pyne, Stephen

Publication Date


  • 2016

Citation


  • Yazici, A., Wille, U. & Pyne, S. G. (2016). Synthesis of bridged heterocycles via sequential 1,4- and 1,2-addition reactions to α,β-unsaturated N-acyliminium ions: mechanistic and computational studies. Journal of Organic Chemistry, 81 (4), 1434-1449.

Scopus Eid


  • 2-s2.0-84959010917

Ro Full-text Url


  • http://ro.uow.edu.au/cgi/viewcontent.cgi?article=4693&context=smhpapers

Ro Metadata Url


  • http://ro.uow.edu.au/smhpapers/3670

Has Global Citation Frequency


Number Of Pages


  • 15

Start Page


  • 1434

End Page


  • 1449

Volume


  • 81

Issue


  • 4

Place Of Publication


  • United States

Abstract


  • Novel tricyclic bridged heterocyclic systems can be readily prepared from sequential 1,4- and 1,2-addition reactions of allyl and 3-substituted allylsilanes to indolizidine and quinolizidine α,β-unsaturated N-acyliminium ions. These reactions involve a novel N-assisted, transannular 1,5-hydride shift. Such a mechanism was supported by examining the reaction of a dideuterated indolizidine, α,β-unsaturated N-acyliminium ion precursor, which provided specifically dideuterated tricyclic bridged heterocyclic products, and from computational studies. In contrast, the corresponding pyrrolo[1,2-a]azepine system did not provide the corresponding tricyclic bridged heterocyclic product and gave only a bis-allyl adduct, while more substituted versions gave novel furo[3,2-d]pyrrolo[1,2-a]azepine products. Such heterocyclic systems would be expected to be useful scaffolds for the preparation of libraries of novel compounds for new drug discovery programs.

UOW Authors


  •   Yazici, Arife (external author)
  •   Wille, Uta (external author)
  •   Pyne, Stephen

Publication Date


  • 2016

Citation


  • Yazici, A., Wille, U. & Pyne, S. G. (2016). Synthesis of bridged heterocycles via sequential 1,4- and 1,2-addition reactions to α,β-unsaturated N-acyliminium ions: mechanistic and computational studies. Journal of Organic Chemistry, 81 (4), 1434-1449.

Scopus Eid


  • 2-s2.0-84959010917

Ro Full-text Url


  • http://ro.uow.edu.au/cgi/viewcontent.cgi?article=4693&context=smhpapers

Ro Metadata Url


  • http://ro.uow.edu.au/smhpapers/3670

Has Global Citation Frequency


Number Of Pages


  • 15

Start Page


  • 1434

End Page


  • 1449

Volume


  • 81

Issue


  • 4

Place Of Publication


  • United States