4,4-Dimethyl Effect. (6). The Ring A Conformation of 4,4-Dimethyl-3-keto Steroids and Triterpenoid-3-ketones: Predicted and Observed Geometries and Their Chiroptical Properties

Yoshisuke Tsuda, Fumiyuki Kiuchi

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

The ring A conformations of 4,4-dimethyl-3-keto steroids can be classified into various geometries on the basis of their torsion angle sign sequence (TASS) of the ring; however, only three were predicted to be possible from theoretical considerations; i.e., C, FB3 and T1 (T2also occurs in the case of 5-enes) (for details, see the text). They were actually observed by X-ray analyses. The ring A conformation is so flexible that it can readily changes from chair to T1 when a remote structural change such as introduction of an 8β-methyl occurs. Corresponding to this conformational change, the circular dichroism (CD) spectrum of the compound changes its sign from negative to positive. Ring A can also equilibrate in solution with various contributions of chair and T1conformations depending on their relative energy difference. This equilibrium is greatly affected by remote changes in the structure and also by the solvent, and is sensitively reflected in the CD spectrum which, more or less, shows a double-humped character. The typical double-humped CD spectra of some compounds can thus be well explained. Those compounds should have FC to FB3conformations at ring A.

Original languageEnglish
Pages (from-to)4806-4819
Number of pages14
JournalChemical and Pharmaceutical Bulletin
Volume32
Issue number12
DOIs
Publication statusPublished - 1984 Jan 1
Externally publishedYes

Keywords

  • 4,4-dimethyl effect
  • 4,4-dimethyl-3-keto steroid
  • A-ring conformation
  • CD spectrum
  • asymmetry parameter
  • conformational transmission
  • non-chair conformation
  • ring geometry
  • torsion angle sign sequence
  • triterpenoid-3-ketone

ASJC Scopus subject areas

  • Chemistry(all)
  • Drug Discovery

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