Strukturelle Abwandlungen an partiell silylierten Kohlenhydraten mittels Triphenylphosphan/Azodicarbonsäurediethylester, 4. Mitt.: Transformationen an Mannose und Galaktose

Reaction of methyl -D-galactopyranoside (1) with two equivalents oft-butyldimethylchlorosilane yields methyl 2,6-bis-O-(tBDMSi)--D-galactopyranoside (1 b), methyl 3,6-bis-O-(tBDMSi)--D-galactopyranoside (1 c) and methyl 4,6-bis-O-(tBDMSi)--D-galactopyranoside (1 d). Likewise methyl -D-mannopyranoside (6) affords methyl 2,6-bis-O-(tBDMSi)--D-mannopyranoside (6 d) and methyl 3,6-bis-O-(tBDMSi)--D-mannopyranoside (6 b), which can be isomerised withTPP/DEAD to methyl 4,6-bis-O-(tBDMSi)--D-mannopyranoside (6 f). Methyl 6-O-(tBDMSi)--D-galactopyranoside (1 a) and methyl 6-O-(tBDMSi)--D-mannopyranoside (6 a) can be prepared from1 or6 with one equivalent oft-butyldimethylchlorosilane.Without an external nucleophile the sugar derivatives1 a and1 b react withTPP/DEAD to form the 3,4-carbonato--D-galactopyranosides1 h and1 i and the 3,4-carbonato-2-O-ethoxycarbonyl--D-galactoside (1 j). In contrast to the formation of the compound1 i by means ofTPP/DEAD the reaction of1 a withTPP and Di-t-butyl-azodicarboxylate (DTBAD) yields the 2,3-anhydro--D-taloside (4 b) and only a small amount of1 i. The epoxide4 b can be cleaved withp-nitrobenzoylchloride/pyridine to the 3-chloro-3-deoxy-2,6-di-O-p-nitrobenzoyl--D-idoside (5). Reaction of1 c and1 d withTPP/DEAD yields the 2,3-anhydro--D-gulopyranoside (2), which can be transformed with NaN₃/NH₄Cl to the 2-azido-2-deoxy--D-idopyranoside (3).Likewise6 a and6 d can be converted to the 3,4-anhydro--D-talosides (7 a and7 b). Reaction of7 b or6 d withTPP/DEAD/NH₃ leads to 3,4-anhydro-2-azido-2-deoxy--D-galactopyranoside (8) and 3-azido-3-deoxy--D-altropyranoside (10), resp.The epoxide7 b is opened with NaN₃/NH₄Cl to the 4-azido-4-deoxymannosides (11 a and11 c) and the 3-azido-3-deoxy--D-idopyranoside (12), while the epoxide8 affords the 2,4-di-azido-2,4-dideoxy--D-glucopyranoside (9).Structures were elucidated by¹H-NMR-analysis of the corresponding acetates.

H. H. Brandstetter undE. Zbiral, Helv., im Druck.     

Über N-(α-Aminoacyl)-sulfonamide, 2. Mitt.

Zusammenfassung Es wird über die Synthese von N-(-Aminoacyl)-p-toluolsulfonamiden und N-(-Aminoacyl)-methansulfonamiden berichtet, deren Acylreste sich vonl-Tyrosin,d,l--Methyl-tyrosin undd,l-3,4-Dihydroxy-phenylalanin ableiten.

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The synthesis of N-(-aminoacyl)-p-toluenesulfonamides and N-(-aminoacyl)-methanesulfonamides containing the acyl groups ofl-tyrosine,d,l--methyltyrosine andd,l-3,4-dihydroxy-phenylalanine is described.

     

Steroid compounds from the Pacific starfishesLuidia quinaria andDistolasterias elegans

One new and four previously known steroid compounds were identified from the Pacific starfishesLuidia quinaria andDistolasterias elegans. The structure of the new steroid was established from spectral data and chemical correlations with other steroids such as 5-cholestane-3,5,6,15,16,26-hexaol 3-sulfate (1). The previously known compounds were identified as 5-cholestane-3,5,6,15,26-pentaol 15-sulfate (2) fromLuidia quinaria and sodium (24S)-O-(-d-giucopyranosyll-5-cholestane-3,6,8,15,24-pentaol 6-sulfate (3), sodium (24S)-5-cholestane-3,6,8,15,24-pentaol 24-sulfate (4), and sodium tornasterol A sulfate (5).Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 473–476, February, 1996.     

Steroid compounds from the starfish Lysastrosoma anthosticta collected in the Sea of Japan

Six polyhydroxylated steroids and their derivatives were isolated from the starfish Lysastrosoma anthosticta collected in the Posyet Bay, Sea of Japan. These include a new glycoside of the steroid polyol, lysastroside A (1), which was identified as (25S)-26-O--d-xylopyranosyl-5-cholestane-3,6,8,15,16,26-hexaol, and the previously known pycnopodioside C monoglycoside (2), marthasterone sulfate (3), (25S)-5-cholestane-3,6,8,15,16,26-hexaol (4), (25S)-5-cholestane-3,6,7,8,15,16,26-heptaol (5), and (25S)-5-cholestane-3,6,7,8,15,16,26-heptaol (6). The compounds were tested for the haemolytic activity and the action on the embryogenesis of the sea urchin Strongylocentrotus intermedius.     

Synthese neuer Indolderivate

The synthesis of the ,-unsaturated ketones4, 5 und6 via the regiospecific aldol- andWittigreaction with some indolealdehydes is described.4 and5 are stable enough for NaBH₄-reduction to the corresponding alcohols.

     

Substitution of halogen atom in α-halonitro compounds of the aliphatic series

Ethyl -halo--nitropropionate and -butyrate were prepared by alkylating ammonium salts of ethyl bromo- and chloronitroacetates. The addition of alkyl acrylates to alkyl chloronitroacetates or their salts gives dialkyl -chloro--nitroglutarates. Sodium salts of ethyl -nitro--sulfo--hydroxypropionate and -butyrate were obtained by the sulfodehalogenation of ethyl -chloro--nitro--hydroxypropionate and -butyrate with sodium dithionite. Esters of -amino acid hydrochlorides were prepared by the reduction of alkyl -chloro--nitrocarboxylates. The hydrogenation of alkyl nitrosulfoacetates leads to the corresponding disodium salts of alkyl aminodisulfoacetates and piperazine-2,5-dione.For communication 5 seeIvz. Akad. Nauk SSSR, Ser. Khim., 1990, 2012 [Bull. Acad. Sci. USSR, Div. Chem. Sci., 1990,39, 1826].Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 872–876, May, 1994.     

Über die Synthese von N,N′-disubstituierten α-Iminophenyl-glyoxylsäurethionamiden und deren Reduktion mit Schwefelwasserstoff zu Phenylessigsäurethionamiden

Zusammenfassung Durch Umsetzung von ,-Dichloracetophenon mit überschüss. prim. Amin und Schwefel in äther. Lösung unter Zusatz von K₂CO₃ (Reaktionszeit 140 Stdn., Reaktionstemp. max. 20°) können N,N-disubstituierte -Iminophenylglyoxylsäurethionamide (1–3) in guten Ausbeuten synthetisiert werden.-Iminoglyoxylsäurethionamide (4–6), die am Imin- bzw. Aminstickstoff auch unterschiedlich substituiert sein können (4, 6), erhält man aus den entsprechenden Phenylglyoxylsäurethionamiden durch Umsetzung mit überschüss. primären Aminen.Die -Iminophenylglyoxylsäurethionamide können bereits bei Raumtemp. glatt durch H₂S zu den entsprechenden Phenylessigsäurethionamiden reduziert werden.

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Synthesis of N,N-disubstituted -iminophenyl-thioglyoxylic amides, and their reduction by means of H₂S to phenyl-thioacetic amides (Willgerodt—Kindler reaction, V.)

N,N-Disubstituted -iminophenylthioglyoxylamides (1–3) can be synthesized in good yields by the reaction of ,-dichloroacetophenone with excess primary amine and sulphur in eth. solution in the presence of potassium carbonate (reaction period 140 hours, reaction temperature max. 20°C).-Iminothioglyoxylamides (4–6), which may be differently substituted at the imine and amine nitrogen atoms (4, 6), may be obtained from the corresponding phenylthioglyoxylamides by reaction with an excess of primary amines.The -iminophenylthioglyoxylamides can be reduced smoothly at room temperature by hydrogen sulphide to the corresponding phenylthioacetamides.

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4. Mitt.:F. Asinger, A. Saus undA. Mayer, Mh. Chem.98, 825 (1967).

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Vgl. auchF. Asinger undH. Offermanns, Angew. Chem.79, 953 (1967).     

Reaction of the nitrile of 3,3-diphenyl-2-propenic acid with the carbanions of some α-branched nitriles Short communication

Reaction of the nitrile of 3,3-diphenyl-2-propenic acid with -branched nitriles in the presence of lithium amide in liquid ammonia does not give the correspondingMichael adducts but the ,-unsaturated nitriles6. Conc. sulfuric acid transforms these nitriles into the -lactones7.

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Reaktion von 3,3-Diphenyl-2-propensäurenitril mit den Carbanionen einiger -verzweigter Nitrile (Kurze Mitteilung)

Zusammenfassung Die Reaktion von 3,3-Diphenyl-2-propensäurenitril mit -verzweigten Nitrilen in Gegenwart von Lithiumamid in flüssigem Ammoniak führt nicht zu den entsprechendenMichael-Addukten, sondern zu den ,-ungesättigten Nitrilen6. Durch Einwirkung von konz. Schwefelsäure entstehen aus diesen Nitrilen die -Lactone7.

     

N-methyI-N-(triethoxysilylmethyl) andN-methyl-N-(silatran-1-ylmethyl) substituted glycine and alanine

Organosilicon derivatives of glycine, - and -alanine, and -methylalanine were prepared by the reaction of methyl esters of - and -halocarboxylic acids withN-methylaminomethyltriethoxysilane in the presence of triethylamine. The compounds synthesized were converted into the correspondingN-silatran-l-ylmethyl derivatives. Trimethylsilyliodoacetate reacts withN-methylaminomethyltrietoxysilane to give 2,2-diethoxy4-methyl-1-oxa-4-aza-2-silacyclohexane-6-one. Its reaction with triethanolamine leads toN-methyl-N-(silatran-l-ylmethyl)glycine.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 341–343, February, 1995.     

Optisch aktive,aromatische Spirane, 8. Mitt.: Darstellung optisch aktiver, 5, 5′, 6′-trisubstituierter 2,2′-Spirobiindane bekannter Chiralität und enantiomerer Reinheit

Starting from (+) (2R) methyl 5-ethyl-2,2-spirobiindane-5-carboxylate of known enantiomeric purity 79 optically active, configurationally correlated 5,5,6-trisubstituted 2,2-spirobiindanes (2–7) were prepared for the purpose of testing a shortened polynomal Ansatz for chirality functions. Their optical rotations and¹H-nmr spectra are reported.In this context several 6-substituted 5-ethylindanes (1) were prepared as model compounds for synthetic transformations.

     

A novel synthesis of N-acetyl-α-d-fucosamine 1-phosphate and uridine 5"-diphospho-N-acetyl-α-d-fucosamine

In connection with studies on the biosynthesis of capsular polysaccharides from Staphylococcus aureus, a new synthesis of uridine 5"-(2-acetamido-2,6-dideoxy--d-galactopyranosyl diphosphate) (uridine 5"-diphospho-N-acetyl--d-fucosamine) using 2-azido-3,4-di-O-acetyl-2,6-dideoxy--d-galactopyranosyl nitrate as the key intermediate was carried out. The reaction of this product with cesium dibenzyl phosphate smoothly affords the corresponding -glycosyl dibenzyl phosphate, which undergoes anomerization on treatment with BF₃·Et₂O and 2-bromopyridine to give -glycosyl dibenzyl phosphate in high yield. This product was then transformed into 2-amino-3,4-di-O-acetyl-2,6-dideoxy--d-galactopyranosyl phosphate, subsequently converted into 2-acetamido-2,6-dideoxy--d-galactopyranosyl phosphate and the target nucleoside diphosphate sugar.     

Silylenolether-Funktionalisierung, 3. Mitt. Regioselektive Acylierung von Trimethylsilylenolethern mit 2-Alkoxy-1,3-dioxolanen — Synthese von α- und γ-geschützten Dicarbonylverbindungen

Acylation of silylenol ethers1 and9 yield with 2-alkoxy-2-alkyl(or aryl)-1,3-dioxolanes5 in a simple way by zinc dichloride-diethyl ether-catalysis regioselectively the - and -protected dicarbonyl derivatives6,7, and10. The enhanced reactivity of the cyclic orthoesters5 in this reaction is discussed in comparison with acyclic reagents. The yield is influenced by steric effects at the reaction center.

     

Struktur/Geruchs-Beziehungen von mit β-Santalol verwandten Verbindungen:E-Homo-β-santalol undE-Dehydrohomo-β-santalol

Summary To study the structure/odour relationships of -santalol analogues two homologous -santalol derivatives5 and6 were synthesized. The key steps thereby were the -alkylation of the bicyclic starting ketones8 and14 accomplished by using more drastic conditions as usual. The odours of5 and6 are described in detail.

Auszugsweise vorgetragen am 19th International Symposium on Essential Oils and Other Substrates, 9. September 1988, Greifensee/Dübendorf, Schweiz     

Die Acetalgruppe, 1. Mitt. Acetale von Halogenmethyl-arylcarbinolen

Several halomethyl-arylcarbinols were prepared, and the influence of substituents on enantiomer selectivity in the acetalisation reaction with [2S-(2,3a,4,7,7a)]-octahydro-7,8,8-trimethyl-4,7-methanobenzofuran-2-ol was examined.

Unserem sehr verehrten Lehrer, Herrn Prof. Dr.Otto Hromatka, mit den besten Wünschen zum 80. Geburtstag gewidmet.     

Synthesis of some 5′-O-amino acid derivatives of uridine as potential inhibitors ofUDP-glucuronosyltransferase

Summary In an attempt to develop potential inhibitors ofUDP-glucuronosyltransferase, some 5-O-amino acid derivatives of uridine were synthesized. N-protectedL-amino acids were coupled at the 5-O-position of 2,3-O-isopropylideneuridine by esterification employing the method of symmetrical anhydrides in presence of 4-dimethylaminopyridine, 5-O-(N-benzyloxycarbonyl-O-tert.butyl-L-threonl)-23-O-isopropylideneuridine (1), 5-O-(N-tert.butyloxycarbonyl-O-benzyl-L-seryl)-2,3-O-isopropylideneuridine and (2), 5-O-(N-tert.butyloxycarbonyl-L-valyl)-2,3-O-isopropylideneuridine (3), and 5-O-(N-tert.butyloxycarbonyl-L-valyl)-2,3-O-isopropylideneuridine (4) were obtained in good yield after column chromatography on silica gel. The treatment of2 withTFA/CH₂Cl₂ (6:1) at room temperature for 30 min led to a selective removal of theBoc group without deblocking of the 2,3-O-isopropylidene group of uridine. Treatment of2 withTFA/H₂O (5:1) at room temperature for 1 h, however, released bothBoc and 2,3-isopropylidene groups. TheZ group of1 was deprotected by catalytic hydrogenolysis over 10% Pd/C/ammonium formate.

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Synthese von 5-O-Aminosäurederivaten des Uridins als potentielle Inhibitoren derUDP-Glukuronosyl-Transferase

Zusammenfassung In einem Versuch, potentielle Inhibitoren derUDP-Glukuronosyl-Transferase zu entwickeln, wurden einige 5-O-Aminosäurederivate des Uridins synthetisiert. N-GeschützteL-Aminosäuren wurden durch Veresterung mit der 5-O-Position des 2,3-isopropylidenuridins gekuppelt (Methode der symmetrischen Anhydride in der Gegenwart von 5-Dimethylaminopyridin). Solcherweise wurden 5-O-(N-Benzyloxycarbonyl-O-tert.butyl-L-threonly)-2,3-O-isopropylidenuridin (1), 5-O-(N-tert.Butyloxycarbonyl-O-benzyl-L-seryl)-2,3-O-isopropylidenuridin (2), 5-O-(N-tert.Butyloxycarbonyl-L-leucyl)-2,3-O-isopropylidenuridin (3) und 5-O-(N-tert.Butyloxycarbonyl-L-valyl)-2,3-O-isopropylidenuridine (4) nach Säulenchromatographie (Kieselgel) in guter Ausbeute hergestellt. Die Behandlung von2 mitTFA/CH₂Cl₂ (6:1) bei Zimmertemperatur (30 min) führte zu einer selektiven Abspaltung derBoc-Gruppe ohne Deblockierung der 2,3-O-Isopropylidengruppe des Uridins. Eine Behandlung von2 mitTFA/H₂O (5:1) bei Zimmertemperatur für 1 Stunde führte hingegen zur Abspaltung sowohl derBoc als auch der 2,3-O-Isopropylidengruppe. DieZ-Gruppe von1 wurde durch katalytische Hydrogenolyse auf 10% Pd/C/Ammoniumformiat abgespalten.

     

Stereochemie von Metallocenen, 27. Mitt.: Optisch aktive Biferrocenyl-derivate: Konformation,Konfiguration, optische Rotationsdispersion und Circulardichroismus

Zusammenfassung Ausgehend von den stereoisomeren ,'-Bis-(dimethylamino-methyl)-biferrocenylen (1, 15) wurden etwa 20 optisch aktive Biferrocenyl-derivate dargestellt. Die Ergebnisse der Racematspaltung erlaubten die Zuordnung der Konfigurationen:1=Mesoform,15=Racemat. AusUV- undNMR-Spektren sowie Dipolmomentmessungen ergibt sich für1 eine annähernd koplanare (s-trans-) Konformation, während in15 (und seinen Derivaten) die beidenF _c-Ebenen gegeneinander verdreht sind. Damit existiert zwischen zwei Konformeren mit jeweils inhärent chiraler Struktur ein Gleichgewicht, dessen Lage aus der Temperaturabhängigkeit desCD von optisch aktivem ,'-Dimethylbiferrocenyl (20) berechnet werden konnte. Dieser Atropisomerie (in15 bzw.20) ist die Ferrocenchiralität überlagert, die in den optisch aktiven Derivaten von1 allein maßgebend ist.Die absoluten Konfigurationen ließen sich (mit einiger Sicherheit) durch optischen Vergleich und kinetische Racematspaltung ermitteln.CD ORD und der optisch aktiven Biferrocenyle werden mitgeteilt.

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Stereochemistry of metallocenes, XXVII. (Ferrocenes, XLVIII). Optically active derivatives of biferrocenyl: Conformations, Configurations, optical rotatory dispersion and circular dichroism

Starting from the stereoisomeric ,'-bis-(dimethylamino-methyl)biferrocenyls (1, 15) 20 optically active biferrocenyls were prepared. The results of the optical resolutions allowed the assignment of the configurations:1=meso form,15=racemate. FromUV andNMR spectra and dipol moment measurements for1 a nearly coplanar (s-trans) conformation was deduced, whilst in15 (and its derivatives) theF _c-planes are twisted from coplanarity. Hence, between two conformers with inherently chiral structures an, equilibrium exists, the position of which was computed from the temperature dependence of theCD of optically active ,'-dimethyl biferrocenyl (20). Onto this atropisomerism (in15 and20, resp.) the ferrocene chirality is super-imposed, which is solely decisive in optically active derivatives of1.The absolute configurations were established (with some certainty) by means of optical comparison and kinetic resolution.CD andORD of the optically active biferrocenyls are reported.

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Mit 4 Abbildungen

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Auszugsweise vorgetragen bei der IV. Intern. Conference on Organometallic Chemistry (Bristol, 27.7.–1.8. 1969).

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26. Mitt. (47. Mitt. über Ferrocenderivate):H. Falk undO. Hofer, Mh. Chem.100, 1507 (1969).     

In situ crystallization of bacterial cellulose II. Influences of different polymeric additives on the formation of celluloses Iα and Iβ at the early stage of incubation

Effects of polymeric additives with different degrees of polymerization (DP) or substitution (DS) on the crystallization of celluloses I and I have been examined at an early stage of the incubation of Acetobactor xylinum by using newly developed FT-IR spectroscopy. It was found that the mass fraction of cellulose I is greatly decreased with increasing concentrations of carboxymethyl cellulose sodium salt (CMC) or xyloglucan (XG) in the incubation medium. Such a decrease in the mass fraction of cellulose I, which corresponds to the enhanced crystallization of cellulose I, is more prominent for CMC or XG with lower DPs, but the additives with too low DPs are not so effective probably due to higher solubility and the lower adhesion on the surface of microfibrils. Moreover, the mass fractions of celluloses I and I are highly correlated with the crystallite size of microfibrils, indicating that I is crystallized in larger-size microfibrils while I is produced in smaller-size microfibrils. On the basis of these experimental results, the mechanism of the crystallization of celluloses I and I is discussed in the Acetobactor xylinum system.     

Substituierte 3-Amino-thiophene und 3-Amino-selenophene aus β-Chlor-α-cyan-zimtsäurenitril

Summary -Chloro--cyano-cinnamonitrile (1) reacts in one step with -oxo-thioles3 or successively with sodium sulphide and -chlorocarbonyl compounds4 to form the 5-substituted 4-amino-2-phenyl-thiophene-3-carbonitriles5. Analogously, the successive reactions of -chloro cinnamonitrile1 with sodium selenide — produced in situ from selene and sodium boronhydride — and -chlorocarbonyl compounds4 yields the 5-substituted 4-amino-2-phenyl-selenophene-3-carbonitriles6.

     

1H-NMR Studies of the Inclusion Complexes between α-Cyclodextrin and Adamantane Derivatives Using Both Exchangeable Hydroxy Protons and Non-Exchangeable Aliphatic Protons

The inclusion complexes between -cyclodextrin (-CD) and adamantane, 1-adamantanol, 1-(hydroxymethyl)-adamantane, 2-adamantanol, and 1,3-adamantanediol in aqueous solution have been studied by ¹H-NMR spectroscopy using both non-exchangeable and exchangeable protons. The complexation-induced ¹H-NMR shifts (CIS) and NOEs of non-exchangeable protons, as well as the CIS, NOEs, temperature coefficients, and linewidth of signals from exchangeable hydroxy protons have been determined. The stoichiometry of the adamantane/-CD complex could not be determined due to the low solubility of adamantane. However, for 0.11 equivalent of adamantane added, two sets of separate ¹H signals for the free and bound -CD were observed. The signal from O(3)H in the complexed form appeared narrow and upfield shifted with a low-temperature coefficient indicating reduced hydration inside the hydrophobic cavity of -CD. Both 1-adamantanol, and 1-(hydroxymethyl)-adamantane formed 1:1 inclusion complexes with -CD and only one set of NMR signals was observed. The CIS and NOEs suggested that both complexes had similar structures. The O(2)H signal of -CD was broadened at low temperature and became narrower as the temperature raised. The broadening increased with higher concentration of guest suggesting interaction between O(2)H of -CD and the guest molecules. The stoichiometry of the -CD/2-adamantanol complex could not be determined with certainty, but the NMR data suggested equilibrium between 2:1 and 1:1 complex. As with adamantane, a sharp and upfield shifted O(3)H signal with a very low-temperature coefficient was observed. No inclusion complex was formed between 1,3-adamantanediol and -CD. This study showed how the hydroxy protons of -CD could be used to obtain complementary information on the geometry and stability of inclusion complexes of -CD.     

Triterpenoid Glycosides of Fatsia japonica. II. Isolation and Structure of Glycosides from the Leaves

The previously known triterpenoid 3-O--L-arabinopyranosides of oleanolic and echinocystic acids and hederagenin, 3-O--D-glucopyranosyl-(12)-O--L-arabinopyranosides of oleanolic acid and hederagenin, in addition to 28-O--L-rhamnopyranosyl-(14)-O--D-glucopyranosyl-(16)-O--D-glucopyranosyl ethers of the 3-O--L-arabinopyranoside of hederagenin, and 3-O--D-glucopyranosyl-(12)-O--L-arabinopyranosides of oleanolic acid and hederagenin, respectively, are isolated from leaves ofFatsia japonica(Araliaceae). The structures of the glycosides are confirmed by chemical methods and ¹³ C NMR spectroscopy