POLISH JOURNAL OF CHEMISTRY
Volume 73 Number 1 January 1999
Pages 1-243


Proceedings of the Polish-German Workshop on Organic Chemistry and Spectroscopy
Stare Jabłonki, May 30 - June 3, 1998


CONTENTS

Page

1 FOREWORD
SYNTHETIC ORGANIC CHEMISTRY
3 Biogenetically Patterned Enantioselective Synthesis
— Goldenstein K., Nerenz F. and Winterfeldt E.
15 Stereoselective Syntheses of Chiral Heterocycles and Alkaloids Using Carbohydrate Auxiliaries
— Kunz H., Weymann M., Follmann M., Allef P., Oertel K., Schultz-Kukula M. and Hofmeister A.
29 The Use of Furan Derivatives in Asymmetric Synthesis and Transformation
— Jurczak J., Kobrzycka E. and Raczko J.
43 [2+2]Cycloaddition of Chlorosulfonyl Isocyanate to Chiral Vinyl Ethers
— Furman B., Kałuża Z., Łysek R. and Chmielewski M.
55 Epoxy Pyranoses, Chiral Synthons for Versatile Regio- and Stereocontrolled Functionalizations
— Voelter W., Thuermer R., Al-Qawasmeh R.A., Al-Tel T.H., Abdel-Jalil R.J. and Al-Abed Y.
71 Anhydro Sugars to Enantiomerically Pure Building Blocks: Efficient Syntheses of -Lactones and Furanoids
— Al-Qawasmeh R.A., Al-Tel T.H., Abdel-Jalil R.J., Thuermer R. and Voelter W.
77 From Furan to Open-Chain Systems. Studies Towards the Synthesis of Tylonolide
— Raczko J.
89 Synthesis of RNAse Active Site Model Systems Using a Steroid Template
— Kalesse M. and Oost T.
101 Total Synthesis of the Nephritogenoside Glycopeptide
— Zhang H., Wang Y., Thuermer R., Al-Qawasmeh R.A. and Voelter W.
117 Model Studies of the Maillard Reaction of Arg-Lys with D-Glucose
— Al-Abed Y., Callaway D., Kapurniotu A., Holak T., Voelter W. and Bucala R.
125 Carbohydrate Chains and Their Binding Sites in Mistletoe Lectin I
— Stoeva S., Maier T., Soler M.H. and Voelter W.
135 Cyclobutadienes and Phosphaalkynes - Tools for the Development of Heteroaromatic
Compounds and Their Valence Isomers

— Regitz M. and Bergstraesser U.
151 Oxidative Nucleophilic Substitution of Hydrogen in Nitroarenes.
A Short Review

— M±kosza M. and Staliński K.
NMR SPECTROSCOPY
163 Structure Elucidation of Saponins and Related Natural Products by NMR Spectroscopy
— Duddeck H.
173 Investigation of Some Intramolecular Hydrogen Bonds by Nitrogen Magnetic Resonance Methods
— Stefaniak L.
181 NMR Analysis of a Rigid Carbohydrate Structural Motif
— Geyer A., Hummel G., Reinhardt S. and Schmidt R.R.
193 The Solvation of Carbohydrates in Dimethylsulfoxide and Water
— Berger S., Diaz M.D. and Hawat Ch.
199 Some Derivatives of Mesoionic 1,2,3,4-Thiatriazolo-5-aminide
Interaction with Metal Cations

— Jaźwiński J.
CD SPECTROSCOPY
209 Helical Twisting Power and Circular Dichroism as Chirality Observations.
Development of a sector rule for the intermolecular chirality transfer in a liquid crystal phase

— Kuball H.-G. and Tuerk O.
229 Assignment of the Absolute Configuration
of Hydroxy and Amino Carboxylic Acids by Circular Dichroism of Their Transition Metal Complexes

— Frelek J.
241 A Note on the Determination of Absolute Configuration of Acetogenins by Circular Dichroism
— Gawroński J. and Wu Y.-C.


ABSTRACTS


3-14

Biogenetically Patterned Enantioselective Synthesis

by K. Goldenstein, F. Nerenz and E. Winterfeldt
Institut fuer Organische Chemie der Universitaet Hannover,
Schneiderberg 1B, D-30167 Hannover, Germany
E-mail: winterfeldt@mbox.oci.uni-hannover.de

(Received July 8th, 1998)

Biogenetically orientated enantioselective syntheses of the bicyclic-ether substructure of Azadirachtin and of the spirocyclohexenone building block for the Agelorines are communicated. In the first case the kinetic resolution of a cyclopentenone starting material is exercised in a high pressure Diels-Alder cycloaddition and in the second case the cycloadduct of a prochiral spirocyclohexadienone is used for the differentiation of enantiotopic groups.

15-27

Stereoselective Syntheses of Chiral Heterocycles
and Alkaloids Using Carbohydrate Auxiliaries

by H. Kunz, M. Weymann, M. Follmann, P. Allef, K. Oertel,
M. Schultz-Kukula and A. Hofmeister
Institut fuer Organische Chemie, Johannes Gutenberg-Universitaet Mainz, D-55099 Mainz, Germany
E-mail: hokunz@mail.Uni-Mainz.de

(Received July 8th, 1998)

N-Glycosyl imines show an efficient diastereofacial differentiation in their reactions with nucleophiles. Coordination to suitable Lewis acids enhances this effect, which is demonstrated in the enantioselective syntheses of -amino acids, homoallylamines and -amino acids. Asymmetric aza Diels-Alder and tandem Mannich-Michael reactions have been applied for the enantioselective synthesis of chiral piperidine derivatives including alkaloids, e.g. anabasin, gephyrotoxin 167B, pumiliotoxin C and its 4a-epimer.

29-41

The Use of Furan Derivatives in Asymmetric
Synthesis and Transformation

by J. Jurczak1,2, E. Kobrzycka1 and J. Raczko1
1Institute of Organic Chemistry, Polish Academy of Sciences, 01-224 Warsaw, Poland
2Department of Chemistry, Warsaw University, 02-093 Warsaw, Poland

(Received July 8th, 1998; revised manuscript August 17th, 1998)

Asymmetric syntheses of furyl alcohols and amines, as well as kinetic resolution of racemic mixtures of furylcarbinols are described. Some examples of asymmetric alkyl-
ation of furan derivatives and preparation of butenolides are also presented.

43-54

[2+2]Cycloaddition of Chlorosulfonyl
Isocyanate to Chiral Vinyl Ethers

by B. Furman, Z. Kałuża, R. Łysek, and M. Chmielewski
Institute of Organic Chemistry of the Polish Academy of Sciences, 01-224 Warsaw, Poland

(Received July 8th, 1998)

The asymmetric [2+2]cycloadditions of chlorosulfonyl isocyanate to vinyl ethers derived from sugars and hydroxy acids are presented. The account focuses on various aspects of the cycloaddition and on the transformations of the resulting [2+2]cycloadducts into clavams and 1-oxacephams. In order to rationalize the results of direction and magnitude of [2+2]cycloaddition, the stereochemical models of this reaction are discussed.

55-69

Epoxy Pyranoses, Chiral Synthons for Versatile
Regio- and Stereocontrolled Functionalizations

by W. Voelter, R. Thuermer, R.A. Al-Qawasmeh, T.H. Al-Tel,
R. Abdel-Jalil and Y. Al-Abed
Abteilung fuer Physikalische Biochemie, Physiologisch-chemisches Institut der Universitaet Tuebingen, Hoppe-Seyler-Strasse 4, D-72076 Tuebingen, Germany

(Received July 28th, 1998)

From epoxy sugars, neighbouring an O-triflyl residue, efficient short-cut new routes to aminodeoxy, (amino acid)-deoxy, cyclopropanated, -hydroxyketo or -butyrolactone pyranoses are developed.

71-75

Anhydro Sugars to Enantiomerically Pure Building Blocks: Efficient Syntheses of -Lactones and Furanoids by R.A. Al-Qawasmeh, T.H. Al-Tel, R.J. Abdel-Jalil,
R. Thuermer and W. Voelter
Abteilung fuer Physikalische Biochemie des Physiologisch-chemischen Instituts der Universitaet Tuebingen, D-72076 Tuebingen, Germany

(Received July 8th, 1998)

Efficient and economic syntheses of multifunctional dihydrofurans, tetrahydrofurans and -lactones are described. The regiochemistry of the ring junctions of the annulated oxa ring systems are controlled using temporary or permanent protection of the C-4 hydroxyl group.

77-87

From Furan to Open-Chain Systems.
Studies Towards the Synthesis of Tylonolide

by J. Raczko
Institute of Organic Chemistry, Polish Academy of Sciences,
01-224 Warsaw, Kasprzaka 44/52, Poland
E-mail: Raczko@ichf.edu.pl

(Received July 8th, 1998; revised manuscript August 26th, 1998)

The fragment C1-C9 of tylonolide was synthesized by stereoselective functionalization of the acyclic enedione 71, obtained via transformation of a 2-methylfuran derivative 68.

89-99

Synthesis of RNAse Active Site Model Systems
Using a Steroid Template

by M. Kalesse and T. Oost
Institut fuer Organische Chemie, Universitaet Hannover,
Schneiderberg 1B, D-30167 Hannover, Germany

(Received July 8th, 1998; revised manuscript September 11th, 1998)

The evaluation of RNAse active site model systems based on rigid steroid templates is described. Our preliminary work on steroid derived RNAse model systems showed that preorientation of guanidinium groups and one imidazole moiety leads to active compounds. We found that within the corticosterone derived steroid series, the C11--configurated compounds were superior to their -diastereomers. In order to evaluate the influence of the conformational flexibility of the imidazole group, a flexible side chain was introduced at C17. The fact that this more flexible imidazole group leads to a decrease in the hydrolytic behavior of the steroid derivative further validates our approach of establishing a preorientated RNAse model system for an efficient RNA hydrolysis.

101-115

Total Synthesis of the Nephritogenoside Glycopeptide

by H. Zhang, Y. Wang, R. Thuermer, R.A. Al-Qawasmeh and W. Voelter
Abteilung fuer Physikalische Biochemie, Physiologisch-chemisches Institut der Universitaet Tuebingen, D-72076 Tuebingen, Germany

(Received July 22nd, 1998; revised manuscript August 31st, 1998)

A mild three-dimensional orthogonal protection scheme, based on Nps/Fmoc-groups for -amino, benzyl residues for hydroxyl and carboxyl protection and 2-chlorotrityl esters as anchoring linkage proved to be a new effective approach for the synthesis of glycopeptides. The oligosaccharide moiety of the nephritogenoside glycopeptide is conveniently assembled via phenyl thioglycosides as glycosyl acceptors and phenyl thioglycosyl sulfoxides as donors, readily accessible from the thioglycosides by oxidation with m-chloroperbenzoic acid.

117-123

Model Studies of the Maillard Reaction
of Arg-Lys with D-Glucose

by Y. Al-Abed1,2, D. Callaway1, A. Kapurniotu2, T. Holak3,
W. Voelter2 and R. Bucala1
1The Picower Institute for Medical Research, 350 Community Drive, Manhasset, New York 11030, U.S.A.
2Department of Physical Biochemistry, University of Tuebingen, 72076 Tuebingen, Germany
3Max Plank Institute for Biochemistry, 82152 Martinsried, Germany

(Received July 8th, 1998)

Possible routes leading from Amadori product precursors to glucose-derived protein crosslinks has been suggested by model studies examining the fate of the Amadori products in vitro. For instance, the Amadori product can undergo dehydration to give 1,4-dideoxy-1-alkylamino-2,3-hexodiulose (AP-dione), which has been isolated by trapping with aminoguanidine. In a model reaction, we selected as an AGE target the dipeptide N-Z-arg-lys. The proximity of the arginine and lysine residues to each other promotes stable intramolecular crosslink formation. Incubation of N-Z-arg-lys with 10 equivalents of glucose in 0.2 M phosphate buffer (pH 7.4) at 37°C for five weeks produces at least 25 distinct reaction products upon fractionation of this mixture by HPLC. Each fraction was isolated, concentrated, and analyzed for its reactivity with a polyclonal anti-AGE antibody (RU) that has been shown previously to recognize a class of AGEs that increase as a consequence of hyperglycemia and which are inhibited from forming in human subjects by treatment with the advanced glycation inhibitor aminoguanidine. The products present within one fraction (1.5% yield) were found to block antibody binding in a dose-dependent fashion. Further purification of this fraction by HPLC revealed the presence of one major (0.6% yield) immunoreactive compound. Characterization of this adduct by UV, ESMS and 1H-NMR spectra revealed the presence of intramolecular arg-lys-imidazole crosslink. This crosslink is non-fluorescent and acid labile and may represent an important class of immunoreactive AGE-crosslinks that form in vivo.

125-133

Carbohydrate Chains and Their Binding
Sites in Mistletoe Lectin I

by S. Stoeva, T. Maier, M.H. Soler and W. Voelter
Abteilung fuer Physikalische Biochemie des Physiologisch-chemischen Instituts der Universitaet Tuebingen, D-72076 Tuebingen, Germany

(Received July 8th, 1998)

The carbohydrate moieties, linked to mistletoe lectin I (ML-I) are characterized by enzymatic digestion of the individual A and B chains (MLA and MLB), HPLC separation of the (glyco)peptide digests and their sequence and mass spectrometric analysis. All carbohydrate chains are linked via Asn residues to the MLA protein molecule. A xylomannose-type oligosaccharide (I) structure (Man3Xyl1Fuc1GlcNac2) is attached to the Asn112 residue of the A chain. Three different glycosylation sites are identified for the B chain: oligosaccharide (I) is bound to position 61, oligosaccharide II (Man6GlcNac2) is found to be linked to Asn96 as well as Asn136 residues. In homologous mistletoe lectins, isolated from different harvest batches, oligosaccharide III (Man5GlcNac2) is attached to Asn136 instead of oligosaccharide II

135-150

Cyclobutadienes and Phosphaalkynes - Tools
for the Development of Heteroaromatic Compounds and Their Valence Isomers [1]

by M. Regitz and U. Bergstraesser
Department of Chemistry, University of Kaiserslautern, D-67663 Kaiserslautern, Germany
E-mail: regitz@rhrk.uni-kl.de*

(Received July 28th, 1998)

The classical valence isomers of benzene, namely Dewar-benzene, benzvalene, and prismane, are well known. Phospha-, azaphospha-, and diphosphabenzenes as well as the Dewar and benzvalene derivatives with the same combinations of heteroatoms are described in this review. Phospha- and azaphosphaprismanes are now also known and discussed. Starting materials for these compounds are the kinetically stabilized cyclobutadienes, azacyclobutadienes, as well as the short-lived 1,3-diphosphacyclobutadienes which, upon reaction with phosphaalkynes, provide an access to the mentioned classes of compounds (Scheme 1).

151-161

Oxidative Nucleophilic Substitution
of Hydrogen in Nitroarenes. A Short Review

by M. M±kosza and K. Staliński
Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44, 01-224 Warsaw, Poland

(Received August 26th, 1998)

Selected examples of oxidative nucleophilic aromatic substitution in nitroarenes are discussed with emphasis on the authors results. Generalization of this process is attempted.

163-171

Structure Elucidation of Saponins and Related
Natural Products by NMR Spectroscopy

by H. Duddeck
Universitaet Hannover, Institut fuer Organische Chemie,
Schneiderberg 1B, D-30167 Hannover, Germany

(Received July 8th, 1998)

For a number of examples strategies are developed and explained how structures of complex natural products, such as triterpene glycosides and related compounds, can be efficiently elucidated by application of modern one- and two-dimensional NMR techniques.

173-180

Investigation of Some Intramolecular Hydrogen Bonds by Nitrogen Magnetic Resonance Methods

by L. Stefaniak
Institute of Organic Chemistry, Polish Academy of Sciences,
ul. Kasprzaka 44, 01-224 Warszawa 42, POB 58, Poland

(Received July 22nd, 1998; revised manuscript November 18th, 1998)

It was shown that nitrogen NMR is a powerful tool in the studies of different types of hydrogen bridges (NHN)+, (NHN)-, (NHN), and (NHO). Some of the NMR parameters, originally proposed by us, provide information about the charge redistribution and the extent of proton transfer. The character of hydrogen bonds depend upon solvent, temperature and the physical phase. The results of studies in the solid state using the 15N NMR CP MAS method were also discussed.

181-192

NMR Analysis of a Rigid Carbohydrate Structural Motif

by A. Geyer, G. Hummel, S. Reinhardt and R.R. Schmidt
Fakultaet fuer Chemie, Universitaet Konstanz, D-78457 Konstanz, Germany
E-mail:armin.geyer@uni-konstanz.de

(Received July 8th, 1998)

Several Lewis glycolipds were characterized by homo- and heteronuclear NMR methods. The experimental NOE data served as restraints in molecular dynamics simulations. The common structural motif was mimiced by a tetrasaccharide building block with a central trehalose moiety.

193-197

The Solvation of Carbohydrates
in Dimethylsulfoxide and Water

by S. Berger, M.D. Diaz and Ch. Hawat
Institute of Analytical Chemistry, University Leipzig, Linnrstr. 3, D-04103 Leipzig, Germany
email: stberger@rz.uni-leipzig.de

(Received July 8th, 1998)

The solvation of sucrose and other carbohydrates in DMSO and water is probed by intermolecular NOE measurements. The NOE effects are interpreted in terms of specific binding of the solvent to certain sites of the molecules. It is shown that DMSO attaches to specific sites of the sucrose molecule, whereas for water such a clear differentiation cannot be proven.

199-208

Some Derivatives of Mesoionic 1,2,3,4-Thiatriazolo-5-
-aminide Interaction with Metal Cations

by J. Jaźwiński
Institute of Organic Chemistry, Polish Academy of Sciences,
ul. Kasprzaka 44/52, 01-224 Warszawa 42 POB 58, Poland

(Received July 8th, 1998; revised manuscript September 23rd, 1998)

Derivatives of mesoionic 1,2,3,4-thiatriazolo-5-aminides, 1 and 2, interact strongly with metal cations. The interactions with Pb(II), Fe(II), Fe(III), Cu(II) and Cd(II) were studied by means of UV-VIS spectroscopy, 1H and 113Cd NMR. The stoichiometry of the complex was determined by Job's method. Few species, being in equilibrium in the solution, are found in most cases. Some cations form insoluble materials with thiatriazoles 1 and 2. Ligand 2 interacts with cadmium acetate giving a 2:1 complex with a stability constant (4.3 ± 0.5) × 107 mol-2.

209-228

Helical Twisting Power and Circular Dichroism
as Chirality Observations
Development of a sector rule for the intermolecular
chirality transfer in a liquid crystal phase

by H.-G. Kuball and O. Tuerk
Fachbereich Chemie der Universitaet Kaiserslautern, D-67653 Kaiserslautern, Germany

(Received July 8th, 1998; revised manuscript August 17th, 1998)

Any chirality measurements, e.g. circular dichroism (CD) or helical twisting power (HTP), should offer a possibility to develop a method for the determination of the absolute configuration. Measurements of CD and optical rotatory dispersion (ORD) have been used as standard methods for decades. Since the HTP is very sensitive to variations in the molecular structure, the question of the conditions under which determination of HTP can also be used as a method for the determination of the absolute configuration has been analyzed. It has been found, that a sector rule can be developed for a specific class of compounds. A quadrant or octant rule can be applied successfully for mono- and bis-aminoanthraquinones, as has been shown by a correlation of HTP with the CD of the long-wavelength charge transfer band. However, a rule of this type breaks down for compounds with low HTP and CD values.

229-239

Assignment of the Absolute Configuration of Hydroxy and Amino Carboxylic Acids by Circular Dichroism of Their Transition Metal Complexes

by J. Frelek
Institute of Organic Chemistry of the Polish Academy of Sciences,
Kasprzaka 44, 01-224 Warsaw, Poland; e-mail: frelek@ichf.edu.pl

(Received July 8th, 1998; revised manuscript September 8th, 1998)

Optically active carboxylic acids can act as uni- or bidentate ligands in complexes of general formula [M2(O2CR)4]+k X-k (M = Mo, Rh or Ru). An in situ exchange of ligand(s) gives rise to several Cotton effects in the spectral range from 800 to 200 nm. In the case of molybdenum complexes with optically active hydroxy and amino acids a hexadecant rule is valid for the two Cotton effects between 400 and 300 nm. For rhodium and ruthenium complexes it was found that the sign of Cotton effects at around 600 nm can be correlated with the structure of investigated acids.

241-243

A Note on the Determination of Absolute
Configuration of Acetogenins by Circular Dichroism

by J. Gawroński1 and Y.-C. Wu2
1Faculty of Chemistry, A. Mickiewicz University, 60 780 Poznań, Poland
2Graduate Institute of Natural Products, Kaohsiung Medical College, Kaohsiung 807, Taiwan, ROC

(Received July 8th, 1998)


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