Über Verbindungen mit Urotropin‐Struktur, XXIII¹⁾ Synthese des 2‐Thia‐ adamantans

Abstract

Von einer Reihe von Versuchen zur Synthese des 2‐ Thia‐adamantans erwies sich ein Syntheseweg, ausgehend von Bicyclo[1.3.3]nonandion‐(2.6) das mit Pyrrolidin in das Bis‐Enamin übergeführt wurde, als erfolgreich. Die anschließende Kondensation mit Schwefeldichlorid ergab 2‐Thia‐adamantandion‐(4.8), aus dem durch Wolff‐Kishner‐Reduktion 2‐ Thia‐adamantan selbst zugänglich ist.

An Approach to Helical Tubular Self-Aggregation Using C2-Symmetric Self-Complementary Hydrogen-Bonding Cavity Molecules

“…We found that repeated fermentation with Baker's yeast for prolonged time afforded virtually the single enantiomer (+)- 2 (ee >99% GC). The racemic dione (±)- 2 was prepared from Meerwein's ester by an improved procedure reported by Lightner. , …”

Enolate Ions as Intermediates

“…Sodium hydride (50 % dispersion in mineral oil, 10.2 g, 0.21 mole) is added and the mineral oil is removed by four washes with 25-ml portions of benzene, the benzene being removed by pipet after the hydride settles. The flask is charged with 150 ml of absolute ethanol, and sodium (11.5 g, 0.5 g-atom) is added cautiously (stirring un necessary) to prepare a solution of sodium ethoxide.…”

Synthesis and isotopic labeling of a naturally occurring alkyl-thiadiamondoid

“…5 Decarboxylation of the methylated Meerwein's ester (2) gives diketone 3. Cyclization of the unsubstituted analogue of our target with SCl 2 could be accomplished through the intermediacy of a bis-enamine adduct, 6 but this approach failed in our substituted case and we redirected our efforts towards the bis silylenol ether 4, accessed in quantitative yield upon treatment with tert-butyldimethylsilyl trifluoromethanesulfonate in the presence of triethylamine. The bis-enol ether affords diketone 5 upon treatment with SCl 2 in the presence of pyridine.…”