Enantio- and Diastereoselective Aldol-Reaction of 2,6-Dimethylphenyl Propionate Using Titanium-Carbohydrate Complexes

Chloro(cyclopentadienyl)bis(1,2:5,6-di-O-isopropylidene-α-D -glucofuranos-3-O-yl)titanium ( 1 ) is used for the transmetallation of Li-enolates obtained from propionyl derivatives. While such Ti-enolates of ketones and hydrazones appear to be unreactive, the (E)enolate 13 of 2,6-dimethylphenyl propionate ( 11 ) adds to the re-side of aldehydes, affording various syn-aldols 14 with high dia- and enantioselectivity (92–97% ds, 91–97% ee, cf. Scheme 2 and Table 1). Racemic syn-aldols (±)- 14 are obtained analogously from the achiral bis(2-propyloxy)-Ti-enolate 15 (Scheme 2 and Table 2). In contrast to the unstable Li-enolate 10 , the Ti-enolates 13 and 15 isomerize at ?30°, presumably to the thermodynamically more stable (Z)-enolates (Scheme 4), While the diastereoselectivity of the achiral enolate 15 is lost upon this equilibration, the chiral (Z)-enolate 27 quite unexpectedly affords anti-aldols 12 of high optical purity (94–98% ec) and, in most cases, with acceptable-to-good diastereoselectivity (82–90% ds). Notable exceptions are branched unsaturated and aromatic aldehydes which form a greater proportion of synepimers of moderate optical purity (Scheme 5 and Table 3). Consistent with these findings, re-facial-and ami -selective aldol-addition is also exhibited by the (Z)-configurated Ti-enolate 22 of N-propionyl-oxazolidi-none 19 (Scheme 3).     

The magnetic hyperfine field of bromine in iron by NMR/ON

Nuclear magnetic resonance of⁸²Br oriented at low temperature in iron has been observed with a sample prepared by ion implantation atT<0.2 K. The asymmetric resonance signal can be decomposed in a broad background signal and a narrow line of FWHM=1.8 (4) MHz which can be attributed to⁸²Br in undisturbed substitutional sites of Fe. From the center frequency of this narrow line (B _ext=0)=201.86(13) MHz we derive the magnetic hyperfine field asB _hf(BrFe)=81.38(6) T. This value is considerably larger than the result of theoretical calculations.     

Untersuchungen über Enzymaktivitäten der Leberzelle bei Vitamin-E-Mangel

The enzymatic elongation of acyl-CoA esters by malonyl-CoA, respectively de novo synthesis of fatty acids from malonyl-CoA by liver microsomes and non particulate fraction of α-tocopherol deficient rats is diminished versus controls. However, liver microsomes of vitamin E deficient rats synthesize more eicosatetraenic acid from γ-linolenic acid and more γ-linolenic acid from linolic acid than do those of tocopherol supplemented animals. It has often been shown that the liver phosphatides of tocopherol deficient rats contain more arachidonic acid than those of controls, a fact which can be explained now by increased activity of the enzymes involved in the biosynthesis of arachidonic acid. Certain polyenic fatty acids are more rapidly synthesized in the absence of naturally occuring antioxidants. Some enzymes of the respiratory chain have also been examined. No vitamin E deficiency effect has been found on enzymes such as gluconate-6-P-dehydrogenase, isocitrate-dehydrogenase, malate-dehydrogenase and lactate dehydrogenase contained in the non particulate fraction. Sonicated mitochondria of tocopherol deficient rats show a greater activity towards cytochrome, oxydase and β-hydroxy-acetyl-CoA-dehydrogenase than controls, possibly due to ultrastractural alteration of this particle.     

Organometallic Syntheses with Diazoalkanes

In recent years, aliphatic diazo compounds have proved to be more and more versatile as reagents in the preparative chemistry of organometallic complexes. As readily accessible compounds, they are not only suitable for the synthesis of known kinds of metal complexes but also open fresh routes to novel complex systems. The comparatively new field of diazoalkane complex chemistry exhibits numerous unexpected and novel reactions, and introduces interesting and promising aspects into the chemistry of carbonylmetal compounds.     

Construction of Large Carbocyclic Rings by Ireland-Claisen Rearrangement of O-Silylated Lactone Enolates: Synthesis of (±)-muscone

(±)-Muscone (5) has been synthesized from methyl 13-(chloroformyl)tridecanoate (6) in nine steps in an overall yield of 24%. The key steps involve an efficient transformation of the readily accessible 14-hydroxy-15-methyl-15-hexadecenoic acid (9) into the tetradecanolide 1 and a subsequent Ireland-Claisen rearrangement of its triethylsilyl enolate 2 to a 8:1-mixture of the stereoisomeric 15-membered carbocycles 4 and 10 (Scheme 4).     

An improved method for the synthesis of cellulose membrane-bound peptides with free C termini is useful for PDZ domain binding studies

SPOT synthesis permits parallel synthesis and screening of thousands of cellulose membrane-bound peptides to study protein-protein interactions in a proteomic context. Recognition of C-terminal residues is one of the most common binding features of PDZ domains. Unfortunately, most solid support-bound peptide libraries lack a free C terminus due to C-terminal fixation on the solid support. To overcome this restriction, we developed a robust methodology based on our previous strategy for generating peptides with authentic C termini. To validate this improved method, we screened a human peptide library of 6223 C termini with the syntrophin PDZ domain. Furthermore, using the same library, new peptide ligands derived from membrane proteins and receptors were found for the ERBIN PDZ domain. Finally, we identified the protein kinase breakpoint cluster region, which is known as a negative regulator of cell proliferation and oncogenic transformation, as an ERBIN ligand.