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Nitrile anions: solvent-dependent cyclizations.

Fraser F Fleming1, Brian C Shook

  • 1Department of Chemistry & Biochemistry, Duquesne University, Pittsburgh, Pennsylvania 15282-1530, USA. flemingf@duq.edu

The Journal of Organic Chemistry
|April 27, 2002
PubMed
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Solvent choice profoundly impacts intramolecular nitrile anion alkylations. The study reveals a spectrum of transition states, influencing the stereochemical outcome of cyclization reactions to form cis- and trans-decalins.

Area of Science:

  • Organic Chemistry
  • Reaction Mechanisms
  • Stereochemistry

Background:

  • Intramolecular alkylations are crucial for synthesizing cyclic compounds.
  • Nitrile anions are versatile nucleophiles in organic synthesis.
  • Solvent effects significantly influence reaction pathways and outcomes.

Purpose of the Study:

  • To investigate the solvent sensitivity of intramolecular nitrile anion alkylations.
  • To correlate transition state geometry with cyclization stereochemistry.
  • To elucidate the nature of nitrile anion transition states.

Main Methods:

  • Performing extensive cyclization reactions in various hydrocarbon and polar solvents.
  • Analyzing the stereochemical products (cis- and trans-decalins).

Related Experiment Videos

  • Correlating stereochemistry with orbital orientation of the nitrile anion.

    • Main Results:

    • Demonstrated a profound solvent sensitivity in intramolecular nitrile anion alkylations.
    • Showcased how S(N)i cyclizations impose steric constraints, linking transition state to orbital orientation.
    • Observed selective formation of cis- and trans-decalins based on transition state geometry.

    Conclusions:

    • Nitrile anion transition states exist on a continuum from planar to pyramidal.
    • Transition state geometry dictates the stereochemical outcome (cis- vs. trans-decalin formation).
    • Solvent plays a critical role in modulating transition state structure and reaction selectivity.