Planar chiral ferrocene salen-type ligands featuring additional central and axial chirality

We report on novel chiral tridentate [NO₂]H₂ and tetradentate [N₂O₂]H₂ Schiff base ligands containing a planar chiral ferrocene moiety linked to hydroxyl-imine or diimine donors with central or axial chirality. Structurally, these ligands resemble half-salen and salen systems designed for stereoselective applications of their transition metal complexes in homogeneous catalysis. The modular synthesis involves diastereoselective metalation of chiral ferrocene or pentamethylferrocene acetals, followed by stereoconservative hydroxyalkylation and condensation with chiral hydroxyamines or diamines, respectively. In comparison to salen-type systems, an important advantage of these ligands is their tunable steric protection of the alkoxide donor site. A total of 18 different ligands varying in electronic and steric properties have been prepared and fully characterized by NMR, IR, mass spectroscopy and by single crystal structure analysis of nine precursors and representatives.     

Über die Reduktion cyclischer Acylale mit LiAlH4

Zusammenfassung Reduktion der cyclischen Acylale1 (a bzw.b) mit LiAlH₄ führt zu den erwarteten Diolen5 (a bzw.b). Bei2 hingegen wird lediglich die olefinische Doppelbindung reduziert, was durch die Ausbildung eines gegen weiteren H^–-Angriff stabilisierten, mesomeren Anions zu erklären ist. Auch die Verbindung4 ist gegen LiAlH₄ stabil.

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Reduction of the cyclic acylals1 (a andb) with LiAlH₄ yields the expected diols5 (a andb). In contrast, only the olefinic double bond of2 is reduced, owing to the formation of a mesomeric anion which resists further attack by hydride ion. The compound4 is also stable to LiAlH₄.

     

From homoleptic to heteroleptic double stranded Copper(I) helicates: the role of self-recognition in self-assembly processes

The ligands 2,9-bis[(6-methyl-2, 2'-bipyridin-6'-yl)methyleneoxymethylenyl]-1,10-phenanthroline (6), 6' ',6' "-bis[(6-methyl-2, 2'-bipyridin-6'-yl)methyleneoxymethylenyl)]-2' ',2' "-bipyridine (2), 5,5'-bis[(6-methyl-2,2'-bipyridin-6'yl)methyleneoxymethylenyl]-2, 2'-bithiophene (7), and 6,6'-bis[(6-methyl-2, 2'-bipyridin-6'-yl)methyleneoxymethylenyl]-2,2'-biphenyl (8) and their respective homo- and heteroleptic double-stranded copper(I) complexes were prepared and characterized in order to estimate the importance of self-recognition in the self-assembly processes of double-stranded copper complexes. The homoleptic double-stranded copper complexes of 2, 6, 7, and 8 were characterized by NMR, FAB-MS, and electrochemistry. It was found that 6 and 2 each form a single double-stranded helicate having the structure of [(L)(2)Cu(3)](3+) (L = 2 or 6), 7 forms two double-stranded [(7)(2)Cu(3)](3+) complexes, and 8 results in a mixture of at least two [(8)(2)Cu(2)](2+) complexes. The potential shift, DeltaE degrees (,) of the Cu(+)/Cu(2+) redox process of these complexes reflects the binding affinity of the different binding sites to the copper cation. The electrochemical data show that the central units have a higher affinity to Cu(+) as compared to the off-center binding sites. NMR was used to determine the actual complex composition obtained from different mixtures of 2, 6, or 7 with Cu(+). Interestingly, we have found that, although 6, 2, and 7 each form homoleptic double-stranded complexes, no heteroleptic double-stranded copper complexes were formed from the mixtures of 7 with either 6 or 2. However, when mixtures of 6 and 2 are used, helicate distributions seem to follow simple statistics. These results are discussed in terms of the relative importance of self-recognition in the self-assembly of double-stranded helicates.     

Über die Einwirkung von Thiolen und Sulfinsäuren auf Chinolacetate, 2. Mitt

Zusammenfassung In Fortsetzung einer früheren Arbeit wird die Addition von H₂S und Verbindungen der Typen RSH und RSO₂H (RC₆H₅) in verschiedenen Lösungsmitteln mit verschiedenen basischen Katalysatoren an verschiedene o-Benzochinolacetate und auch an ein o-Benzochinondiacetat untersucht. Zum Unterschied von C₆H₅SH geben die oben erwähnten Thiole auch m-.bzw. o-Substitution. Die Methansulfinsäure wird wie die Benzolsulfinsäure in 1,4-Stellung addiert. Die Abhängigkeit der Additionsstelle vom Lösungsmittel und Katalysator ist von theoretischem Interesse, weil sie zeigt, daß die hier beschriebenen Additionsreaktionen nicht durch Grenzstrukturen beschrieben werden können, wie sie sonst mit Erfolg bei Additionsreaktionen acyclischer , -ungesättigter Ketone verwendet werden.     

Arithmetical conservation results

In this paper we present a proof of Goodman’s Theorem, a classical result in the metamathematics of constructivism, which states that the addition of the axiom of choice to Heyting arithmetic in finite types does not increase the collection of provable arithmetical sentences. Our proof relies on several ideas from earlier proofs by other authors, but adds some new ones as well. In particular, we show how a recent paper by Jaap van Oosten can be used to simplify a key step in the proof. We have also included an interesting corollary for classical systems pointed out to us by Ulrich Kohlenbach.     

Die Konstitution des Phlorrhizins

Ohne Zusammenfassung     

Über Carbonyl-bis-aminosäuren und deren Umwandlungsprodukte II

Ohne Zusammenfassung