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1

Kwas winowy i jego pochodne we współczesnej chemii organicznej

Grajewski J.

Wiadomości Chemiczne

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2013

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[Z] 67, 5-6

495--519

EN

The tartaric acid and its salts have been present in chemistry for almost 350 years, since Pierre Seignette isolated Rochelle salt in 1675. Since that time tartaric acid and its derivatives have been often used in chemistry due to their accessibility, enantiopurity, relatively low cost and presence of different functional groups which easily allow to modify the molecule. Many tartaric acid derivatives serve as catalysts in important stereoselective transformations such as Sharpless asymmetric epoxidation or asymmetric Rousch aryloboronation. In many others reactions tartaric acid have been employed as a chiral building block for natural products synthesis, highly functionalized molecules or ligand design such as well known TADDOL or its analogues. Its polar functional groups allow to form crystals with amines and aminoalcohols what is widely used for their enantiopurification and resolution. The relatively new subdiscipline is the use of tartaric acid in chiral recognition and chiral discrimination in nanochemistry and enantioselective chromatography. The other, recent applications of tartaric acid include functionalization of metal layers, antibacterial and antifungal activity among many others. The significance of tartaric acid is evident – since 2000, words “tartaric acid” or “tartrates” can be found in databases over four thousand times. Taking that into account this short review is concentrated on selected applications of tartaric acid and its derivatives in organic chemistry in recent several years.

2

Synthesis of Complex Bicyclo[4.3.0]nonene Derivatives from Sugar Allyltins; Sugar Mimetics Derived from D-Glucose

Jarosz S., Jędra S.

Polish Journal of Chemistry

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2009

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Vol. 83, nr 10

1757-1764

EN

Controlled decomposition of sugar allyltin: methyl 2,3,4-tri-O-benzyl- 6,7,8- tri -deoxy-8-(tri-n-butyl)stannyl-alfa-D-gluco-oct-6(E)-eno-hexo-1,5-pyranoside af forded the corresponding dienoaldehyde with the D-xylo-configuration and the E-geometry across the internal double bond. Reaction of this intermediate with Ph3P=CH-CO2Me provided a triene, which under went cyclization to the bicyclic products: derivatives of bicyclo[4.3.0]nonatriene. Stereochemical aspects of this cyclization, as well as some transformations leading to carbobicyclic sugar mimics, are discussed.

3

The Structure of Nystatin A2

Pawlak J., Tabin P., Sowiński P., Borowski E.

Polish Journal of Chemistry

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2005

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Vol. 79 / nr 10

1673-1679

4

The Structure of Levorin A3, a Minor Component of Levorin Complex

Pawlak J., Sowiński P., Bieszczad T., Borowski E.

Polish Journal of Chemistry

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2005

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Vol. 79 / nr 10

1667-1672

EN

The structure of aromatic heptaene macrolide Levorin A3was established on the basis of MSandNMRstudies withDQF-COSYandROESYexperiments. The relative configuration of Levorin A3 chiral centers was assigned as: 9R*,11S*,13S*,15R*,17S*,18R*,19S*,21R*, 36S*,37R*,38S*,40S* and 41S*. The geometry of the heptaene chromophore was defined as: 22E, 24E, 26Z, 28Z, 30E, 32E and 34E.

5

Środki ochrony roślin o budowie chiralnej

Morzycka B., Morzycki J. W.

Wiadomości Chemiczne

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2003

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[Z] 57, 9-10

855--876

EN

The agrochemical industry is continuously searching for new active compounds to combat pests. The main aim of this research is to develop new substances with lower application rates, increased selectivity and decreased undesired ecological impact. Most synthetic agrochemicals with chiral structure are marketed as racemates even though the desired biological activity may be derived from only one enantiopure isomer. However, some newly introduced compounds are marketed as the most biologically active stereoisomers. When agrochemicals have chiral structures, efforts should be made to define the mode of action, toxicity, and metabolic pathway of each enantiopure isomer. If there are large differences in the biological activities of individual stereoisomers, it is desirable to use only the most active one. In this review article some stereochemical aspects of several groups of important agrochemicals including aryloxypropanoate herbicides, acylanilides, triazine herbicides, ureas and cyanoacrylates, triazole fungicides, morpholine derivatives, organochlorine insecticides, pyrethroid insecticides, pheromones and antifeedants, and organophosphorus compounds, will be discussed.

6

Stereokontrolowana synteza tlenowych analogów penicylin i cefalosporyn

Łysek R., Furman B., Borsuk K., Chmielewski M.

Wiadomości Chemiczne

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2003

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[Z] 57, 5-6

391--433

EN

Synthesis of oxacephalotin and oxacephamandol which are more active then natural, containing sulfur congeners, and isolation of clavulanic acid, a patent inhibitor of (3-lactamase enzymes, directed attention of academic and industrial laboratories to the synthesis of oxygen analogs of penicillins and cephalosporins. The present review directs attention to the stereocontrol of a desired configuration in the formation of the bridgehead carbon atom. Five possible methods leading to basic skeletons of the title compounds are discussed (Scheme 1). Three of them involve nucleophilic substitution at C-4 of the azetidin-2-ones performed as inter or intramolccular process, and two of them involve cycloaddition reactions between ketenes and iminoethers, or between vinyl ethers and isocyanates. Owing to the general application stereospecificity, and high asymmetric induction, the last method seems to be most advantageous. The weak point of the nucleophilic substitution methodology is that a nuclcophilc enters 3-substituted azetidin-2-one ring preferentially anti to the existing substituent or if there is no substitutent at C-3, stereoselectivity in generation of a new stereogcnic center at C-4 is low. All methods arc illustrated by examples taken from the literature.

7

Physical Image vs. Structure Relation. 9. Synthesis and Structural Study of Some 2,5-Bis-alkoxysubstituted 3-Oxolenes and Oxolanes: An Experimental and Theoretical Approach

Nazarski R., Skowroński R.

Polish Journal of Chemistry

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2003

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Vol. 77 / nr 4

415-426

EN

Two 2,5-bis-substituted 3-oxolenes 2 stable only in anhydrous, acid-free solutions were obtained in the Clauson-Kaas reaction. An immediate catalytic hydrogenation of theE/Z isomeric mixture of oxolene 2a, followed by chromatography, afforded one geometrical form of oxolane diol 4 (isomer I), which was subsequently submitted to several attempts of cyclization to an unknown bis-spiroacetal of succinic anhydride (6). Arationalization of this process failure and the Z geometry of product I exhibiting interesting spectroscopic features were inferred from theoretical results (HF/6-31G** calculations) and experimental data for solution (NMR, IR). Some additional ab initio GIAO-CPHF NMR computations concerning relevant model bis-acetals 3 and 5 were performed, as well.

8

Z badań nad spektroskopią UV-VIS kompleksów metali przejściowych z zasadami Schiffa w roztworach

Kurzak K., Kuźniarska-Biernacka I.

Wiadomości Chemiczne

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2001

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[Z] 55, 9-10

913--931

EN

Metal complexes derived from Schiff bases have been known for one hundred years. The complexes have occupied a central role in the development of coordination chemistry. This situation is manifested by huge number of publications ranging from the physicochemical to biochemical relevant studies of these complexes. The reason for this sustained interest in those compounds are undoubtedly many but important among them must be their general ease to preparation, and diverse properties, e.g., their ability to reversibly bind oxygen, catalytic activity, photochromic and thermochromic properties. Schiff base are those compound containing the azomethine group (-RHC=N-) and usually formed by the condensation of amine with carbonyl compound. Bases which are effective as coordinating ligands bear a functional group, usually -OH, sufficiently near the site of condensation that a five- or six membered chelate ring can be formed upon reaction with a metal ion. Tautomeric equilibrium of three tautomers is possible for Schiff base compounds: imine, enamine and keto-imine. The presence of the imine and enamine tautomeric forms depends on the formation of intramolecular hydrogen bond. It is claimed that enamine form is dominant in napthaldimines while imine form in salicylaldimines. The distribution of the tautomeric equilibrium is strongly depend on the solvents. The presence of keto-imine form is insignificant for Schiff base compounds, but is found in the case of b-diketones and arylimines of b-ketoethers. The most significant complexes of the salicylaldimines are of the types: bi-, tri- and tetracoordinateSchemat 3. The geometry of Schiff base complexes depends on substituent at the coordinating nitrogen atoms. For tetra-coordinate copper(II) complexes different types of geometry is possible. A planar structure has been established for the copper(II) complexes (with bidentate Schiff base) where the substituent is hydrogen atom, hydroxyl, methyl, n-butyl or n-amyl group. In the other hand the copper(II) complexes where the substituent is isopropyl or tert-butyl are pseudo-tetrahedral. For tetra-coordinate cobalt(II), either a square-planar or pseudo-tetrahedral geometry is possible. A pseudo-tetrahedral structure has been established for the cobalt(II) complexes (with bidentate Schiff base) where the substituent is n-propyl, isopropyl, n-butyl, tert-butyl, cyclohexyl or aryl group. Cobalt(II) complexes with bidentate Schiff bases where the substituent is hydrogen atom or hydroxyl group have a planar geometry, because of formation hydrogen bonding between hydrogen (from hydroxyl group) and oxygen (from aldehyde linkage). Geometry of this type is characteristic for cobalt(II) complexes witch Schiff base tetradentate (e.g., with salicylidene-ethylenediamine). The aim of this account is to summarize the result of studies of structural and spectroscopic properties on Schiff bases and their complexes. These have been reviewed based on 104 articles.

9

Physical image vs. structure relation, 5 [1]. Multinuclear NMR structural study on some hydrazones of O,O-Dialkyl 1-Oxoalkanephosphonates

Nazarski R. B., Gralak D. K., Kudzin Z. H.

Bulletin of the Polish Academy of Sciences. Chemistry

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2000

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Vol. 48, No. 1

27-33

EN

An unambiguous method for determination of the configuration of any single 0,0-dialkyl 1-oxoalkanephosphonate hydrazones based on H, C, P NMR data has been elaborated; the use of 1 JCp (P-C=N) couplings is the most fruitful. The 12C/13C isotope effects on the P chemical shifts of selected compounds have been measured. For primary hydrazones the E/Z isomerisation with stabilisation of their Z forms through an intramolecular H-bonding has been proven. In addition, for the latter stereoisomers small scalar couplings between H-bonded groups N-H.. .O=P have been found, JHP 2.4-3.4 Hz. The possibility of the across H-bridge transfer of spin-spin interactions in these forms is also discussed.

10

Symetria molekuł a stereochemia

Stępień M.

Wiadomości Chemiczne

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1999

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[Z] 53, 1-2

17-64

EN

Stereochemistry, often regarded merely as a descriptive discipline, is an inexhaustible source of mathematical problems. Group theory, topology, graph theory, etc. Are widely applied to the description of molecular architecture and conformational dynamics, to isomer counting and labelling, interpretation of spectra and more. Both mathematics and stereochemistry benefit from their marriage: new theorems are proved and new molecules synthesised. This review is concentred with molecular symmetry, an idea which, appropriately generalised, is central to stereochemistry. Depending on what we imagine a molecule to be, whether a rigid body, a set of nuclei, or a graph, the nature of symmetry operations changes. Our attempt is to demonstrate how various symmetry models work, explore their capabilities, and show how they are interrelated by virtue of their common group theoretical framework. Points groups, derived in the opening section, are by far the most popular symmetry description albeit applicable only to instantaneous configurations of molecules. Point groups, providing little information on the actual structure of a molecule, canbe extended into so called framework groups which detail the distribution of atoms over sites of different local symmetry. From the structure of minimal framework groups the frequency of various point symmetries amongst molecules can be inferred. This is illustrated with a number of examples. The following section introduces the idea of permutational symmetry and its application to non-rigid molecules. The permutation-inversion (PI) group of Longuet-Higgins is defined and exemplified, its semidirect product structure being discussed in some depth. The PI group is then used for the description of selected dynamic processes, such as the rearrangements of bullvalene or 'racemization' of Mislow's ester. Finally, the classification of nuclei used in NMR spectroscopy is expressed in terms of equivalence classes within the PI group. The final section deals with topological properties of molecules. The principles of graph theoretical approach to molecular symmetry are outlined. Topological stereoisomerism is then defined, and the synthetic philosophy of topological stereochemistry and its achievements are briefly reviewed. We end with a discussion of symmetry properties of topologically non-trivial species, paying partucular attention to realizability of automorphisms and chirality of graphs.

11

Novel A-Hydroxyphosphonates - Enol Phosphates Rearrangement

Wróblewski A., Karolczak W.

Polish Journal of Chemistry

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1999

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vol. 73 nr 7

1191-1202

12

Wspomnienia o profesorze Jerzym Suszce i szkic jego dokonań naukowych

Antkowiak W.Z.

Wiadomości Chemiczne

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1998

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[Z] 52, 7-8

473-509

EN

A quarter of a century has already passed since the most distinguished Polish pioneer in both natural products chemistry and stereochemistry, scientist meritorious for chemistry education, Professor Jerzy Suszko, passed away. He was born in Silesia near Teschen in 1889 and studied at the Polytechnic of Prague where he finished his PhD thesis under the auspices of Paul Rabe at the age of 24. After World War I he took on research work at the Jagielloński University in Cracow collaborating with Karol Dziewoński at the beginning. Next, after passing a habilitation examination and spending three years at the Univerity of Lvov, he moved to Poznań, where he spent the second half of his life, working as a professor and the Head of the Organic Chemistry Department of the University of Poznań. Furthermore, he was to become the Head of the Laboratory of Alkaloids of the Institute of Organic Chemistry of the Polish Academy of Sciences. He also held some highly responsible and a Dean of the Mathematical and Natural Science Faculty for a few years. The main scientific achievements of Professor Jerzy Suszko were concerned with the chemistry of physiologically active natural products and with the spatial structure of organic molecules. From among the natural products, the alkaloids and especially those of cinchona bark were the most intensively studied mainly because of their pharmacological properties. His synthetic and structural studies analysed all the most reactive and stereochemically important fragments of the molecules of quinine and related alkaloids. This resulted analogues differing by the kind of substituent in the quinoline moiety as well as the corresponding stereoisomers. Further significant achievements in the same field comprised, among others, the elaboration of a convenient method of a reverse conversion of quinotoxine (the product of an acid treatment of quinine but also occurring as the key intermediate in the quinine synthesis) and related toxins to the natural cinchona alkaloids, the determination of the pattern of rearrangement within the vicinal amino-alcohol fragment, and the discoveries in the chemistry of derivatives with a modified vinyl side chain, especially those being intramolecular ethers. The structure and conversion studies of other alkaloids concerned those occurring in the genera Papaver (codeine and rheadine), Lupinus and Cortinarius. At the beginning of the thirties, J. Suszko, proposed a new method of determining the molecular symmetry, especially in the case of fused-ring polycyclic aromatic hydrocarbons. This method was next verified mainly on naphthalene molecules and was based on the binding of two identical chiral substituents to the ring system in different positions followed by an analysis of the resulting stereochemical mixture. Other stereochemical studies concerning stereocontrolled syntheses, conformation stability and configuration determination were carried out on various cyclic apliphatic hydrocarbons, including bornane derivatives. Professor Jerzy Suszko educated a great number of graduated students both in chemistry and pharmacy. From about forty people who got their PhD degrees under his scientific supervision many later reached the highest levels in their scientific careers. He was a founding member of the Polish Chemical Society and was very much engaged in its activities during his whole life. He served in some responsible offices therein, including the President of the Society. He was also a member of several foreign scientific societies, including the American Chemical Society.