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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41. Mitt.:M. Benedikt undK. Schlögl, Mh. Chem.109, 805 (1978).
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Schlögl, K., Schölm, R. Stereochemie von Metallocenen, 42. Mitt.: Optisch aktives π-Fluorenon-tricarbonylchrom — Darstellung, enantiomere REinheit, absolute Konfiguration und Versuche zur Racemisierung. Monatshefte für Chemie 109, 1227–1240 (1978). https://doi.org/10.1007/BF00913024
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DOI: https://doi.org/10.1007/BF00913024