Carboxy-Signal bei 6 = 166.3, was die E-Konfiguration der Mesaconsaurediester-Teilstruktur D bestatigt.Da sich in Cyclobutan-Derivaten die 3JHH-Kopplungen cis-und trans-standiger Protonen zu wenig unterscheiden [' I, wurde die relative Konfiguration dieses Rings durch H,H-NOE-Differenzspektroskopie bestimmt. Deutliche Kern-Overhauser-Effekte fur cis-Beziehungen findet man m ischen den Protonen bei 6 = 4.45 und 4.96 sowie 4.13 und 2.03 (Methyl). Sattigung der Resonanz bei 6 = 2.03 fiihrt auch zu einem NOE bei den N-Methyl-Protonen des Tropan-Rings B (6 = 2.46). Damit lassen sich die Teilstrukturen gemaD 1 zusammenfiigen. Wahrscheinlich baut die an sonnigen Standorten wachsende Pflanze den Cyclobutan-Ring durch [2 + 21-Cycloaddition aus Mesaconsaurediester (linke Halfte in 1) und Zimtsaureester (rechte Halfte) auf.
An Li2N2O bicyclo[1.1.1]pentane‐type structure is characteristic of the trilithiated N,N'‐diphenylethylenediamine in the presence of hexamethylphosphortriamide (HMPA). Li⊕ ions bridge the two N⊖ centers in this “ion triplet” in an‐asymmetric fashion. Each of the Li⊕ ions is also coordinated to a terminal HMPA ligand (only the O atom of which is shown in the illustration to the right) and further bridged by a third HMPA ligand. The structural principles underlying this complex were predicted by ab initio calculations, and they can be rationalized in terms of a simple electrostatic model.
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