Metalated Nitriles: SNi and SNi′ Installation of Contiguous Quaternary–Tertiary and Quaternary–Quaternary Centers

Authors

  • Dr. Jesus A. Lujan-Montelongo,

    1. Department of Chemistry and Biochemistry, Duquesne University, Pittsburgh, PA 15282-1530 (USA), Fax: (+1) 412-396-5683
    Search for more papers by this author
  • Ping Lu,

    1. Department of Chemistry and Biochemistry, Duquesne University, Pittsburgh, PA 15282-1530 (USA), Fax: (+1) 412-396-5683
    Search for more papers by this author
  • Dr. Wang Liu,

    1. Chemical Abstracts Service, 2540 Olentangy River Road, Columbus, OH 43202 (USA)
    Search for more papers by this author
  • Prof. Fraser F. Fleming

    Corresponding author
    1. Department of Chemistry and Biochemistry, Duquesne University, Pittsburgh, PA 15282-1530 (USA), Fax: (+1) 412-396-5683
    • Department of Chemistry and Biochemistry, Duquesne University, Pittsburgh, PA 15282-1530 (USA), Fax: (+1) 412-396-5683
    Search for more papers by this author

Abstract

original image

“Black belt” SNi and SNi′: Deuterium labeling revealed an inherent preference of N- and C-metalated nitriles for SNi, rather than SNi′ displacement. The fundamental reactivity preferences are harnessed in a series of cyclizations to cis- and trans-decalins that install contiguous quaternary–tertiary and quaternary–quaternary stereocenters (see scheme).

Ancillary