Monatshefte für Chemie / Chemical Monthly

, Volume 109, Issue 5, pp 1227–1240 | Cite as

Stereochemie von Metallocenen, 42. Mitt.: Optisch aktives π-Fluorenon-tricarbonylchrom — Darstellung, enantiomere REinheit, absolute Konfiguration und Versuche zur Racemisierung

  • Karl Schlögl
  • Richard Schölm
Organische Chemie und Biochemie
Received:
Accepted:

Stereochemistry of metallocenes, 42: optically active π-fluorenone tricarbonylchromium—preparation, enantiomeric purity, absolute configuration and attempts tempts of racemization

Abstract

Racemic Fluorenone-Cr(CO)3 (1) was prepared from fluorenone ethyleneketal by complexation with Cr(CO)6 and subsequent cleavage of the dioxolane9. Asymmetric reduction of1 with a chiral Lithium hydride afforded both (+)-1 and the correspondingendo-carbinol (−)-7 a with optical yields up to 80% as established by the use of chiral nmr shiftreagents. Active1 could also be obtained by two other asymmetric reactions albeit with low optical yields. LiAlH4−AlCl3 reduction of (+)-1 gave traces of (+)-fluorene-Cr(CO)3 (2).

The absolute chirality of (+)-1 was deduced as (S) by application of the abovementioned asymmetric reduction to ferroceno indenone (11) of known configuration and byHoreau's method to (−)-7 a. Several attempts to racemize1 failed, which proves that no transanular shift of Cr(CO)3 takes place. The CD spectra of1 and2 are reported.

Some side reactions such as the reduction of7 a to2 with Cr(CO)6 in dibutylether (leading also to the formation of isomeric dimethylbenchrotrenes from the solvent) and the formation of a binuclear complex14 between1 and2 are briefly reported.

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Copyright information

© Springer-Verlag 1978

Authors and Affiliations

  • Karl Schlögl
    • 1
  • Richard Schölm
    • 1
  1. 1.Institut für Organische ChemieUniversität WienWienÖsterreich

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