Notiz über einen Zugang zu β, γ-ungesättigten Carbonsäurederivaten mit Hilfe der Amidacetal-Claisenumlagerung. Über synthetische methoden, 17. Mitteilung

Note on a preparation of β, γ-unsaturated carboxylic acid derivatives using the amide acetal Claisen rearrangement 3-(Trimethylsilyl)allyl alcohols smoothly undergo the amide acetal Claisen rearrangement furnishing allyl silanes. Subsequent protolysis with HF at ?20° provides a convenient, stereoselective method for the preparation of β, γ-unsaturated carboxylic acid derivatives. Three model examples illustrate the procedure.     

Zur Kenntnis des Faktors F430 aus methanogenen Bakterien: Struktur des proteinfreien Faktors

Factor F430 from Methanogenic Bacteria: Structure of the Protein-free Factor Factor F430, the porphinoid nickel-containing coenzyme of the methylcoenzyme-M reductase of metanogenic bacteria is shown to be the 3³,8³,12²,13³,18²-pentaacid derivative of the pentamethylester F430M, the structure of which had been determined previously (see structural formulae 1 and 2 ). The structure assignment rests on chromatographic, UV/VIS-, CD-, IR-, and ¹³C-NMR-spectroscopic as well as FAB-mass spectral comparision of F430 with F430M and the pentaacid prepared by acid-catalyzed hydrolysis of F430M. In the cells of Methanobacterium thermoautotrophicum, factor F430 is present in a ‘bound’ and also, depending on the growth conditions, in ‘free’ form, the latter being defined as the part of total F430 that can be extracted from the cells under extremely mild conditions (80% EtOH at 0–4°). From the (protein)-‘bound’ form, F430 is extracted by subsequently treating the cells at 0–4° with 80% EtOH containing (e.g.), 2m LiCi. From both sources, the extracted factor is the same pentaacid, and there is no indication for the existence of a protein-free F430 species that would contain additional (covalently bound) structural elements.     

Non-trivial behavior of palladium(II) acetate

Reaction of activated palladium metal with a HNO3/acetic acid mixture produces both orange Pd3(OAc)6, 1, and purple Pd3(OAc)5(NO2), 2. Compound has a trinuclear structure derived from that of the well-known triangular complex 1 in which one acetate group has been replaced by a nitrite group which is bonded to one palladium atom by the nitrogen atom and to another Pd atom using one of the oxygen atoms. Highly pure 1 can be made by continuous removal of the nitric oxides from the reaction mixture using a flow of N2. 1H NMR spectra of solutions of 1 in CDCl3 and C6D6 show several signals of various intensities when a small amount of water is present in the deuterated solvents but only one signal when the solvents are thoroughly dried. These results are consistent with the occurrence of one or more hydrolysis processes when the solvents contain water and suggest that hypotheses about various [Pd(OAc)2]n aggregates that have previously been brought forward in the literature to explain the complexity of the spectrum of 1 are unnecessary, especially for nonpolar solvents. Compound 2 does not hydrolyze, and in wet or dried solvents shows a 1H NMR spectrum that consists of five equal-intensity signals due to the five nonequivalent acetate groups.     

2,6-diaminopurine in TNA: effect on duplex stabilities and on the efficiency of template-controlled ligations

Replacement of adenine by 2,6-diaminopurine-two nucleobases to be considered equivalent from an etiological point of view-strongly enhances the stability of TNA/TNA, TNA/RNA, or TNA/DNA duplexes and efficiently accelerates template-directed ligation of TNA ligands. [reaction: see text]     

Characterisation of botulinum toxins type C, D, E, and F by matrix-assisted laser desorption ionisation and electrospray mass spectrometry

In a follow-up of the earlier characterisation of botulinum toxins type A and B (BTxA and BTxB) by mass spectrometry (MS), types C, D, E, and F (BTxC, BTxD, BTxE, BTxF) were now investigated. Botulinum toxins are extremely neurotoxic bacterial toxins, likely to be used as biological warfare agent. Biologically active BTxC, BTxD, BTxE, and BTxF are comprised of a protein complex of the respective neurotoxins with non-toxic non-haemagglutinin (NTNH) and, sometimes, specific haemagglutinins (HA). These protein complexes were observed in mass spectrometric identification. The BTxC complex, from Clostridium botulinum strain 003-9, consisted of a 'type C1 and D mosaic' toxin similar to that of type C strain 6813, a non-toxic non-hemagglutinating and a 33 kDa hemagglutinating (HA-33) component similar to those of strain C-Stockholm, and an exoenzyme C3 of which the sequence was in full agreement with the known genetic sequence of strain 003-9. The BTxD complex, from C. botulinum strain CB-16, consisted of a neurotoxin with the observed sequence identical with that of type D strain BVD/-3 and of an NTNH with the observed sequence identical with that of type C strain C-Yoichi. Remarkably, the observed protein sequence of CB-16 NTNH differed by one amino acid from the known gene sequence: L859 instead of F859. The BTxE complex, from a C. botulinum isolated from herring sprats, consisted of the neurotoxin with an observed sequence identical with that from strain NCTC 11219 and an NTNH similar to that from type E strain Mashike (1 amino acid difference with observed sequence). BTxF, from C. botulinum strain Langeland (NCTC 10281), consisted of the neurotoxin and an NTNH; observed sequences from both proteins were in agreement with the gene sequence known from strain Langeland. As with BTxA and BTxB, matrix-assisted laser desorption/ionisation (MALDI) MS provided provisional identification from trypsin digest peptide maps and liquid chromatography-electrospray (tandem) mass spectrometry (LC-ES MS) afforded unequivocal identification from amino acid sequence information of digest peptides obtained in trypsin digestion.     

Cob(I)alamin-Catalyzed Skeletal Migrations Observed during the Reduction of 4β-(tert-Butyl)-1α-(1-methylvinyl)cyclohexanecarbaldehyde

The cob(I) alamin (1(I)) -catalyzed² transformation of the aldehyde 2 has been studied (cf. Table 1). Kinetic examinations showed a rapid isomerization of 2 to 3 (cf. Fig. 1 and 2). From the transformations in glacial AcOH, the two cyclopropanols 5 and 7 were isolated as main products (cf. Tables 1–3 and Fig. 1 and 2). Using large amounts of 1(I) , the aldehyde 4 was very slowly transformed. Accepting the intermediate formation of 6 interconnected Co-complexes, i. e. A , B , C , D , E and F (cf. Scheme), the generation of all the products observed can be explained.     

Nitration studies of naphtho[2,3-c][1,2,5]thiadiazole

Nitration of naphtho[2,3-c][1,2,5]thiadiazole gives the 5-nitro derivative in 61–66% yield. Chlorination of this product apparently gives an unstable addition product which loses hydrogen chloride on recrystallization to give 4-chloro-8-nitronaphtho[2,3-c][1,2,5]thiadiazole. Thus, naphtho[2,3-c][1,2,5]thiadiazole under nitrating conditions behaves as a 2-substituted naphthalene rather than as an anthracene analog.     

HPLC monitored synthesis of R2NCH2 substituted benzene derivatives used as (C,N)-ligands for organometallic compounds

2-(Diethylaminomethyl)phenyl bromide and 1,3-bis(dimethylaminomethyl)-benzene, useful ligands for the synthesis of hypervalent organometallic compounds, were prepared and characterized by NMR (¹H, ¹³C, 2D experiments) spectroscopy. Their synthesis was monitored by the HPLC method. The compounds were eluted on a Nucleosil 120 Si column (5 μm, 25×0.4 cm) with n-hexane at room temperature using a 1.0 ml/min flow-rate. The maximum values of absorbance for the studied compounds, excepting the diethylamine, were located in a narrow range around 212 nm, the wavelength used for their UV detection. The diethylamine was detected at 190 nm. The calibration curves are straight lines with correlation factors r>0.995. The HPLC data are in good agreement with those provided by NMR spectroscopy.     

Chemie von α-Aminonitrilen. 13. Mitteilung. Über die Bildung von 2-Oxoethyl-phosphaten (“Glycoladehyd-phosphaten”) aus rac-Oxirancarbonitril und anorganischem Phosphat und über (formale) Konstitutionelle Zusammenhänge zwischen 2-Oxoethyl-phosphaten und Oligo (hexo- und pentopyranosyl)nucleotid-Rückgraten

Chemistry of α-Aminonitriles. Formation of 2-Oxoethyl Phosphates (“Glycolaldehyde Phosphates”) from rac-Oxiranecarbonitrile and on (Formal) Constitutional Relationships between 2-Oxoethyl Phosphates and Oligo(hexo- and pentopyranosyl)nucleotide Backbones Oxiranecarbonitrile in basic acqueous solution at room temperature reacts regioselectively with inorganic phosphate to give the cyanohydrin of 2-oxoethyl phosphate (“glycolaldehyde phosphate”), a source of (the hydrate of) the free aldehyde, preferably in the presence of formaldehyde. In aqueous phosphate solution buffered to nearly neutral pH, oxiranecarbonitrile produces the phosphodiester of glycoladehyde as its bis-cyanohydrin in good yield. In contrast to mono- and dialkylation, trialkylation of phosphate with oxiranecarbonitrile is difficult, and the triester derivative is highly sensitive to hydrolysis. Glycolaldehyde phosphate per se is of prebiotic interest, since it had been shown [5] to aldomerize in basic aqueous solution regioselectively to rac-hexose 2, 4, 6-triphosphates and – in the presence of formaldehyde - mainly to rac-pentose 2, 4-diphosphates with, under appropriate conditions, rac-pentose 2, 4-diphosphates as the major reaction product. However, the question as to whether oxiranecarbonitrile itself has the potential of having been a prebiological natural constituent remains unanswered. Backbone structures of hexopyranosyl-oligonucleotides with phosphodiester linkages specifically between the positions 6′ → 4′, 6′ → 2′, or 4′ → 2′ of the sugar residues can formally be derived via the (hypothetical) aldomerization pathway, a combinatorial intermolecular aldomerization of glycoladehyde phosphate and bis(glycolaldehyde)-phosphodiester in a 1: 1 ratio. The constitutional relationships revealed by this synthetic analysis has played a decisive role as a selection criterion in the pursuit of our experimental studies toward a chemical etiology of the natural nucleic acids' structure. The Discussion in this paper delineates how the analysis contributed to the conception of the structure of p-RNA. The English Footnotes to Schemes 1–11 provide an extension of this summary.     

Magnetic properties of cyano-bridged Ln3+-M3+ complexes. Part I: trinuclear complexes (Ln3+ = La, Ce, Pr, Nd, Sm; M3+ = FeLS, Co) with bpy as blocking ligand

The reaction of Ln(NO3)3(aq) with K3[Fe(CN)6] or K3[Co(CN)6] and 2,2'-bipyridine in water/ethanol led to eight trinuclear complexes: trans-[M(CN)4(mu-CN)2{Ln(H2O)4(bpy)2}2][M(CN)6].8H2O (M = Fe3+ or Co3+, Ln = La3+, Ce3+, Pr3+, Nd3+, and Sm3+). The structures for the eight complexes [La2Fe] (1), [Ce2Fe] (2), [Pr2Fe] (3), [Nd2Fe] (4), [Ce2Co] (5), [Pr2Co] (6), [Nd2Co] (7), and [Sm2Co] (8) have been solved; they crystallize in the triclinic space group P and are isomorphous. They exhibit a supramolecular 3D architecture through hydrogen bonding and pi-pi stacking interactions. A stereochemical study of the nine-vertex polyhedra of the lanthanide ions, based on continuous shape measures, is presented. No significant magnetic interaction was found between the lanthanide(III) and the iron(III) ions.