Active Site Design in a Chemzyme: Development of a Highly Asymmetric and Remarkably Temperature-Independent Catalyst for the Imino Aldol Reaction**

The asymmetric aldol reaction of an enolate or enolate equivalent with an imine is a reaction of established synthetic importance for the synthesis of chiral amines in general and bamino esters in particular. [1] The development of chiral catalysts for this reaction has proven to be a difficult task and had eluded all attempts until recently when Kobayashi and co-workers examined imines derived from o-aminophenol. [2±4] Their method involves the catalysis of the reactions of these imines and ketene acetals with a catalyst generated from zirconium(iv) tert-butoxide and two equivalents of (R)-6,6'-dibromoBINOL (BINOL 1,1'-binaphth-2-ol). Our interest in the synthesis of chiral amines led us to investigate the use of VAPOL-derived catalysts A comparison of catalysts prepared from BINOL, 6,6'-dibromoBINOL and VAPOL ligands on the asymmetric induction in the reaction of the phenyl-substituted imine 1 and acetal 2 is summarized in [2] The VAPOL catalyst could be prepared in either methylene chloride or toluene, but for solubility reasons, the BINOL catalysts were prepared in methylene chloride. The VAPOL and Br 2 BINOL catalysts were superior to the BINOL catalyst at À 45 8C. The asymmetric induction dropped for the Br 2 BINOL catalyst when the temperature was raised from À 45 8C to room temperature, but curiously, the asymmetric induction for the VAPOL catalyst was essentially unchanged over this same temperature range. Only a small drop-off is noted (85 % ee) when the temperature is raised to 41 8C and the substrate-to-catalyst ratio is raised to 200:1 (entry 5). Both the R enantiomers of BINOL and Br 2 BINOL ligands give the R enantiomer of the product 3, whereas with the VAPOL ligand, it is the S enantiomer that gives the R product. This reversal is not unexpected given the structures of the ligands where the zirconium is in the minor groove of the BINOL ligands and in the major groove of the VAPOL ligand. [2g] It is clear from the examination of space-filling CPK models that it is possible to bind two VAPOL ligands to one zirconium atom but only with a facial arrangement of the four oxygen atoms as is illustratred by structure 6 in Scheme 1. This is supported by 1 H NMR experiments on a catalyst generated from zirconium tetraisopropoxide and VAPOL in the presence of two equivalents of N-methyl imidiazole. A clean spectrum is only observed with two equivalents of VAPOL relative to zirconium and the spectrum is consistent with a single C 2 -symmetrical species were performed by using the TEXSAN [13] crystallographic software package. Crystallographic data (excluding structure factors) for the structure reported in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC-153832. Copies of the data can be obtained free of charge on application to CCDC

Tris(Methylquecksilber)amin und verwandte Verbindungen

Darstellung und Eigenschaften von N(HgCH3)3 werden beschrieben und das Massenspektrum, 1H-Kernresonanzspektrum sowie das Schwingungsspektrum (IR und RAMAN) mitgeteilt und zugeordnet. Während das Amin im festen Zustand die sehr niedrige Molekülsymmetrie C1 aufweist, besitzt es in Lösung trigonalpyramidale Struktur (Symmetrie C3v). Demgegenüber gehört das mit dem Amin isoelektronische [O(HgCH3)3]+1-Kation (als Azid) auch im kristallinen Zustand zur Punktgruppe D3h. Das Schwingungsspektrum von O(HgCH3)2 wird erneut vermessen und zugeordnet.Preparation and properties of N(HgCH3)3 are described and the mass spectrum. 1H-nmr spectrum and the vibrational spectrum (IR, RAMAN) were recorded and assigned. In the solid state N(HgCH3)3 belongs to the point group C1, whereas in solution the molecule becomes more symmetric (C3v). On the contrary, the structure of the isoelectronic [O(HgCH3)3]+1 is trigonal planar (D3h). The vibrational spectrum of O(HgCH3)2 has been reinvestigated

Neue Quellen fuer die Gasphasenepitaxie/Schichtstrukturen fuer Detektoren: Alternative Gruppe V-Ausgangsstoffe fuer die Herstellung von InP-basierenden Detektorstrukturen mit Hilfe der MOVPE Abschlussbericht

SIGLEAvailable from TIB Hannover: DtF QN1(68,54) / FIZ - Fachinformationszzentrum Karlsruhe / TIB - Technische InformationsbibliothekBundesministerium fuer Bildung, Wissenschaft, Forschung und Technologie, Bonn (Germany)DEGerman

Starch biosynthesis and modification of starch structure in transgenic plants

Starch is synthesised through the ADP-glucose pathway, involving the three enzymes ADP-glucose pyrophosphorylase, starch synthase and starch branching enzyme. ADP-glucose pyrophosphorylase is the key enzyme of the pathway, determining the flux of carbon into starch. It generates ADP-glucose, which is the substrate for the starch synthases, from glucose-1-phosphate and ATP releasing pyrophosphate. The enzyme is stimulated by 3-phosphoglycerate and inhibited through inorganic phosphate. The starch synthases, which catalyse the transfer of glucose from ADP-glucose to the nonreducing end of a growing alpha-1,4-glucan, are divided into two classes, the granule-bound starch synthases (GBSS) and the soluble starch synthases (SS). In both classes several isoforms have been described from many different plant species. The branching enzyme, which introduces branchpoints into the amylopectin, can also occur in different isoforms. Other enzymes present in plants, which also act on alpha-1,4-glucans, such as the starch phosphorylases, disproportionating enzyme and different starch hydrolases, might also be important for dertermining the starch structure and, therefore, its processibility. Many aspects of starch synthesis are not fully understood to date. Starch metabolism can be manipulated through genetic engineering, either by the ectopic expression of different heterologous genes, or through the repression of the expression of endogenous genes using antisense RNA technology. This not only allows the functional analysis of starch biosynthetic proteins, but also the manipulation of starch structure in order to widen its industrial applications. In this way many different potato lines have been generated, containing either different amounts of starch, or which synthesize a structurally modified starch. These structural changes relate to the amylose content, the phosphate content, or the gelatinisation and gelation characteristics of the starch

Entwicklung von metallorganischen Arsenverbindungen und deren Einsatz in der metallorganischen Gasphasenepitaxie Abschlussbericht

Available from TIB Hannover: F95B2233+a / FIZ - Fachinformationszzentrum Karlsruhe / TIB - Technische InformationsbibliothekSIGLEBundesministerium fuer Forschung und Technologie (BMFT), Bonn (Germany)DEGerman