π-Facial Selectivities in Hydride Reductions of Hindered Endocyclic Iminium Ions

J Org Chem. 2019 Jan 4;84(1):273-281. doi: 10.1021/acs.joc.8b02603. Epub 2018 Dec 19.

Abstract

The origins of π-facial selectivities in the borohydride reduction of endocyclic iminium ions have been elucidated by density functional theory calculations. In reductions of conjugated ("thermodynamic") iminium ions, the π-facial preference of the hydride attack was found to be due to torsional steering. Attack at the favored π-face leads to a lower-energy "half-chair"-like conformation of the tetrahydropyridine product, whereas attack at the other π-face results in an unfavorable "twist-boat" conformation. In reductions of nonconjugated ("kinetic") iminium ions, torsional distinction is small between the top- and bottom-face attacks, and the π-facial selectivity of the hydride approach is primarily due to steric hindrance.

Publication types

  • Research Support, N.I.H., Extramural
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Borohydrides / chemistry*
  • Models, Molecular
  • Molecular Conformation
  • Nitrogen / chemistry*
  • Stereoisomerism
  • Thermodynamics

Substances

  • Borohydrides
  • Nitrogen