Chemoselective Removal of Protecting Groups from O-Glycosyl Amino Acid and Peptide (Methoxyethoxy)ethyl Esters Using Lipases and Papain

The selective C-terminal deprotection of O-glycopeptide (methoxyethoxy)ethyl esters is achieved under mild conditions (pH 6.6, 37 degrees C) by enzymatic hydrolysis using papain or lipase M from Mucor javanicus to give building blocks useful for chain-extending glycopeptide synthesis. On the other hand, the selective removal of acetyl protecting groups from the saccharide portion of glycopeptides is accomplished by alternative enzymatic hydrolysis with lipase WG from wheat germ to furnish model substrates for enzymatic glycosyl transfer reactions in order to extend the carbohydrate side chain of these conjugates.     

The mass spectra of TMS-ethers of deuterated polyalcohols. A contribution to the structural investigation of sugars

Aldoses, ketoses, deoxy-aldoses, deoxy-keto-aldoses, lactones, deoxy-lactones and other similar compounds are readily reduced by NaBD₄ to the corresponding polyalcohol. Their trimethylsilyl ethers show characteristic mass spectra which allow firm assignments of the position of deuteration and hence of the nature of the starting sugar compound. The g.c./m.s. coupling technique even allows trace analysis since full information can be derived from the most intense fragments of the mass spectra.     

Minimization of empirical energy functions in proteins including hydrophobic surface area effects

We present analytical expressions to calculate the gradient of the water-accessible surface area of proteins with respect to Cartesian coordinates and dihedral angles. A detailed mathematical analysis leads to corrected equations for the gradient calculation used previously in the ANAREA program. To study the hydrophobic effect of solvent-protein interactions, our expressions have been implemented to further improve the program package FANTOM. We used this version of FANTOM to minimize the ECEPP/2 and the hydrophobic energy of tendamistat. © 1993 John Wiley & Sons, Inc.     

The mass spectra of small-ring hetero-cycles—II. Aziridinones (α-lactams)

The mass spectra of six aziridinones (α-lactams) are presented. The six aziridinones exhibit the same general fragmentation pattern, the primary processes being loss of the N-t-butyl group, loss of carbon monoxide and loss of t-butyl isocyanate. Several additional rearrangement or fragmentation processes are observed with specific α-lactams.     

Photochemische synthese von H2Fe3-komplexen und ihre aktivität bei der photokatalytischen hydrierung von olefinen und dienen

The photochemical reaction of the trinuclear complex Fe₃(CO)₁₀NSi(CH₃)₃ under hydrogen leads to substitution of the bridging carbonyl group by two hydrogens. The resulting complex H₂Fe₃(CO)₉NSi(CH₃)₃ acts as a catalyst in the photochemical hydrogenation of olefins and dienes.     

Zur Synthese sulfonierter Derivate von 4-Amino-1,3-dimethylbenzol und 2-Amino-1,3-dimethylbenzol

Syntheses of Sulfonated Derivatives of 4-Amino-1, 3-dimethylbenzene and 2-Amino-1, 3-dimethylbenzene Direct sulfonation of 4-amino-1, 3-dimethylbenzene (1) and sulfonation of 4-nitro-1,3-dimethylbenzene ( 4 ) to 4-nitro-1,3-dimethylbenzene-6-sulfonic acid ( 3 ) followed by reduction yield 4-amino-1,3-dimethylbenzene-6-sulfonic acid ( 2 ). The isomeric 5-sulfonic acid ( 5 ) however is prepared solely by baking the acid sulfate salt of 1 . Reaction of sulfur dioxide with the diazonium chloride derived from 2-amino-4-nitro-1,3-dimethylbenzene ( 7 ) leads to 4-nitro-1,3-dimethylbenzene-2-sulfonyl chloride ( 8 ), which is successively hydrolyzed to 4-nitro-1,3-dimethylbenzene-2-sulfonic acid ( 9 ) and reduced to 4-amino-1, 3-dimethylbenzene-2-sulfonic acid ( 6 ). Treatment of 4-amino-6-bromo-1,3-dimethylbenzene ( 12 ) and 4-amino-6-chloro-1, 3-dimethylbenzene ( 13 ), the former obtained by reduction of 4-chloro-6-nitro-1,3-dimethyl-benzene ( 10 ) and the latter from 4-chloro-6-nitro-1, 3-dimethylbenzene ( 11 ), with oleum yield 4-amino-6-bromo-1,3-dimethylbenzene-2-sulfonic acid ( 14 ) and 4-amino-6-chloro-1,3-dimethylbenzene-2-sulfonic acid ( 15 ) respectively; subsequent carbon-halogen hydrogenolyses of 14 and 15 lead also to 6 (Scheme 1). Baking the acid sulfate salt of 2-amino-1, 3-dimethylbenzene ( 17 ) gives 2-amino-1, 3-dimethylbenzene-5-sulfonic acid ( 16 ), whereas the isomeric 4-sulfonic acid ( 18 ) can be prepared by either of the following three possible pathways: Sulfonation of 2-nitro-1,3-dimethylbenzene ( 20 ) to 2-nitro-1,3-dimethylbenzene-4-sulfonic acid ( 21 ) followed by reduction or sulfonation of 2-acetylamino-1,3-dimethylbenzene ( 19 ) to 2-acetylamino-1,3-dimethylbenzene-4-sulfonic acid ( 22 ) with subsequent hydrolysis or direct sulfonation of 17 . Further sulfonation of 18 yields 2-amino 1,3-dimethylbenzene-4,6-disulfonic acid ( 23 ), the structure of which is independently confirmed by reduction of unequivocally prepared 2-nitro- 1,:3-dimethylbenzene-4,6-disulfonic acid ( 24 )(Scheme 2).     

MO-LCAO-Berechnungen an schwefelhaltigen π-Elektronensystemen

Zusammenfassung Mercaptosubstituierte Ionen von Schwefelheterocyclen, die iso--elektronisch mit dem Mercaptotropyliumion sind, zeigen mehrere charakteristische Absorptionsmaxima im Ultravioletten, die sich mehr oder weniger von den Absorptionen der unsubstituierten Heterocyclen unterscheiden. Diese Verbindungen werden durch Protonierung iso--elektronischer Thiotropene erhalten. Halbempirische SCF-LCI-Rechnungen mit früher abgeleiteten Parametern geben die experimentellen Ergebnisse gut wieder. Der Einfluß einer Methylsubstitution am exocyclischen Schwefel läßt sich durch eine Änderung des Parameters U _s abschätzen.

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MO-LCAO-calculations on sulfur containing -electron systemsXX. PPP-calculations on the mercapto-tropylium ion and iso--electronic sulfur-heterocycles

Iso--electronic thiotropones are converted by means of protonisation into mercaptosubstituted ions of the analogous heterocycles. These ions show various characteristic absorption maxima in the UV-region. Semiempirical SCF-LCI-calculations using parameters derived formerly reflect the experimental results satisfactory. By appropriate adjustment of the parameter U _s it is possible to estimate the influence of methyl substitution on the exocyclic sulfur atom.

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Résumé Des thiotropones isolélectroniques sont par protonation converties en ions mercapto-substitués des hétérocycles correspondants. Ces ions présentent différents maxima d'absorption caractéristiques dans le spectre U.V. Des calculs semi-empiriques SCF-LCI, utilisant des paramètres précédemment obtenus, reflètent d'une manière satisfaisante les résultats expérimentaux. Par un ajustement convenable du paramètre U _s il est possible d'estimer l'influence de la substitution méthylique sur l'atome de soufre exocyclique.

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19. Mitteilung: Hartmann, H., u. J. Fabian (im Druck).     

Photoreduction of Triplet Benzophenone by Tertiary Amines: Amine molecular structure and ketyl radical yield

The photoreduction of triplet benzophenone by 14 tertiary amines was investigated. The ketyl radical yields do not correlate with the quenching rate constants, nor with the electron donor propensity of the amines. Individual structural features of the amines seem to determine the photoreduction yields.