C-Glycosylidene derivatives (exo-glycals): their synthesis by reaction of protected sugar lactones with tributylphosphonium ylids, conformational analysis and stereoselective reduction

Stabilised tributylphosphonium ylids Bu₃PCHCH(EWG), where EWG is CO₂Me, CO₂^tBu or CN, react with protected sugar lactones under mild conditions to give high yields of glycosylidene derivatives (4 and 5) with good Z/E selectivity. X-Ray crystallography shows that in the solid state the tetra-O-benzyl protected (Z)-glucosylideneacetonitrile (Z)-4c adopts a conformation intermediate between a boat and a twist-boat, whereas the isomeric galactose derivative (Z)-5c exists as a distorted chair. NMR data suggest that in solution chair-like conformations are again more favoured for galactosylidene derivatives than for their glucosylidene analogues. Solution phase NMR studies and molecular modelling show that the (E)-double bond geometry disfavours the chair-like geometry of the ring, even in the galactose series; this is consistent with the avoidance of allylic 1,3-strain. Reduction of the glycosylidene double bond to give stereoselective formation of β-C-glycoside derivatives may be achieved by using Et₃SiH-CF₃CO₂H or Et₃SiH-BF₃·Et₂O.     

One-pot two-step microwave-assisted reaction in constructing 4,5-disubstituted pyrazolopyrimidines

[reaction: see text] A microwave-assisted reaction was developed to facilitate the construction of 4,5-disubstituted pyrazolopyrimidines. This one-pot two-step process involves a sequential S(N)Ar displacement of the C4 chloro substituent with various anilines and amines, followed by a Suzuki coupling reaction with different boronic acids. Using microwave irradiation leads to high product conversion, low side product formation, and shorter reactions.     

Heme-protein active site models via self-assembly in water

[structure: see text] Water-soluble models of heme-protein active sites are obtained via the self-assembly of cationic porphyrins 1 and tetrasulfonato calix[4]arene 2 (K(1.2)() = 10(5) M(-)(1)). Selective binding of ligands either outside or inside the cavity of assemblies 1.2 via coordination to the zinc center has been observed. Small ligands such as 4-methylpyridine and 1-methylimidazole are encapsulated, while the bulkier caffeine is bound outside. Assemblies Co-1.2, in which the Zn porphyrin moiety has been replaced by a Co(II) porphyrin, can act as O(2) carriers.     

Carbohydrate-protein interactions at interfaces: synthesis of thiolactosyl glycolipids and design of a working model for surface plasmon resonance

Thiolactosyl lipids designed for carbohydrate-protein binding studies have been synthesised. One representative was selected for binding studies with a plant lectin RCA120, the agglutinin from Ricinus communis. The interactions were measured quantitatively in real time using a BIAcore surface plasmon resonance instrument. Removal of much of the galactose from the thiolactosyl lipid in situ with beta-galactosidase showed that the lectin binding was highly specific. A dissociation constant KD = 8.77 x 10(-8) M was measured for 1-[2-[2-(2-[beta-D-galactopyranosyl-(1-->4)-1-thio-beta-D -glucopyranosyl]ethoxy)ethoxy]ethoxy]octadecane 30 which is four orders of magnitude greater than that determined for binding to lactose in solution. A concentration of lactose of > 80 mM was required to block the lectin binding to thiolactosyl lipid in a neomembrane.     

Agglomération contrôlée de latex par formation de complexes tensioactifs anioniques : copolymères à blocs à base de poly(oxyde d’éthylène)

For polystyrene–poly(ethylene oxide) (PS–PEO) diblock copolymers, as micellar dispersions in aqueous medium, the formation of complexes with anionic surfactants, such as sodium dodecylsulfate (SDS) could be confirmed. The number of SDS molecules fixed per EO unit is close to the values reported for the SDS–PEO homopolymer interaction. Advantage of this type of complexation was taken to develop a controlled agglomeration process for SDS stabilized PS and PVC latexes by using as agglomerants ‘hairy’ latexes of PS and PVC that have been synthesized in the presence of PS–PEO block copolymers and that carry therefore a fringe of PEO sequences on their surface. The complexation of SDS by these surface-anchored PEO chains leads to the destabilization of the anionic latex, which has a tendency to precipitate onto the surface of the agglomerant latex. The average particle size and the size distribution of the agglomerated particles were studied as a function of the weight and number ratio of the two types of latexes involved in the agglomeration process, as well as in function of the surface coverage by SDS and PEO respectively. By adjusting these parameters, it was possible to obtain, with an efficiency of almost 100%, latex agglomerates with a monomodal distribution in the size range of 1 to 40 μm. An agglomeration mechanism could be outlined taking into account the complexation capacity and the specific surface of the agglomerating ‘hairy’ latex. To cite this article: P. Peter et al., C. R. Chimie 6 (2003).     

Polysulfonylamine. CLXIII [1] Kristallstrukturen von Metall‐di(methansulfonyl)amiden. 12 [1] Das orthorhombische Doppelsalz Na2Cs2[(CH3SO2)2N]4·3H2O: Ein dreidimensionales Koordinationspolymer aus (Caesium‐Anion‐Wasser)‐Schichten und intercalierten Natriumionen

Polysulfonylamines. CLXIII. Crystal Structures of Metal Di(methanesulfonyl)amides. 12. The Orthorhombic Double Salt Na₂Cs₂[(CH₃SO₂)₂N]₄·3H₂O: A Three‐Dimensional Coordination Polymer Built up from Cesium‐Anion‐Water Layers and Intercalated Sodium Ions The packing arrangement of the three‐dimensional coordination polymer Na₂Cs₂[(MeSO₂)₂N]₄·3H₂O (orthorhombic, space group Pna2₁, Z′ = 1) is in some respects similar to that of the previously reported sodium‐potassium double salt Na₂K₂[(MeSO₂)₂N]₄·4H₂O (tetragonal, P4₃2₁2, Z′ = 1/2). In the present structure, four multidentately coordinating independent anions, three independent aquo ligands and two types of cesium cation form monolayer substructures that are associated in pairs to form double layers via a Cs(1)—H₂O—Cs(2) motif, thus conferring upon each Cs⁺ an irregular O₈N₂ environment drawn from two N, O‐chelating anions, two O, O‐chelating anions and two water molecules. Half of the sodium ions occupy pseudo‐inversion centres situated between the double layers and have an octahedral O₆ coordination built up from four anions and two water molecules, whereas the remaining Na⁺ are intercalated within the double layers in a square‐pyramidal and pseudo‐C₂ symmetric O₅ environment provided by four anions and the water molecule of the Cs—H₂O—Cs motif. The net effect is that each of the four independent anions forms bonds to two Cs⁺ and two Na⁺, two independent water molecules are involved in Cs—H₂O—Na motifs, and the third water molecule acts as a μ₃‐bridging ligand for two Cs⁺ and one Na⁺. The crystal cohesion is reinforced by a three‐dimensional network of conventional O—H···O=S and weak C—H···O=S/N hydrogen bonds.     

Neue neutrale und kationische Mono‐Aziridin‐Komplexe des Typs [CpMn(CO)2Az], [CpCr(NO)2Az]+ und [(Ph3P)(CO)4ReAz]+ über CO‐, Hydrid‐ und Chlorid‐Abspaltungsreaktionen

Novel Neutral and Cationic Mono‐Aziridine Complexes of the Type [CpMn(CO)₂Az], [CpCr(NO)₂Az]⁺, and [(Ph₃P)(CO)₄ReAz]⁺ via CO‐, Hydride‐, and Chloride‐Elimination Reactions The monoaziridine complexes 1 — 5 are obtained by three differently induced substitution reactions. The photolytically induced CO substitution reaction of [CpMn(CO)₃] with 2, 2‐dimethylaziridine leads to the neutral N‐coordinate aziridine complex [Cp(CO)₂Mn{$\overline{N(H)CMe₂C}$ H₂}] ( 1 ). The protonation of [(Ph₃P)(CO)₄ReH] with CF₃SO₃H and consecutive treatment with 2, 2‐dimethylaziridine or 2‐ethylaziridine gives the salt‐like aziridine complexes [(Ph₃P)(CO)₄Re{$\overline{N(H)CMe₂C}$ H₂}](CF₃SO₃) ( 2 ) or [(Ph₃P)(CO)₄Re{ H₂}](CF₃SO₃) ( 3 ) by hydride elimination reactions. The like‐wise salt‐like complexes [Cp(NO)₂Cr{$\overline{N(H)CMe₂C}$ H₂}](BF₄) ( 4 ) and [Cp(NO)₂Cr{ H₂}](CF₃SO₃) ( 5 ) are synthesized from [CpCr(NO)₂Cl] by chloride elimination with AgX (X = BF₄, CF₃SO₃) in the presence of 2, 2‐dimethylaziridine or 2‐ethylaziridine, respectively. As a result of X‐ray structure analyses, the metal atoms are trigonal pyramidally ( 1, 4, 5 ) or octahedrally ( 2, 3 , cis‐position) configurated; the intact three‐membered rings coordinate through the distorted tetrahedrally configurated N atoms. All compounds 1‐5 are stable with respect to the directed thermal alkene elimination to give the corresponding nitrene complexes; the IR, ¹H‐ and ¹³C{¹H}‐NMR, and MS spectra are reported and discussed.     

Polysulfonylamine. CLX [1] Kristallstrukturen von Metall‐di(methansulfonyl)amiden. 10 [2] Die dreidimensionalen Koordinationspolymere M[(CH3SO2)2N] mit M = Kalium,Rubidium, Caesium (isotype Strukturen für M = K,Rb)

Polysulfonylamines. CLX. Crystal Structures of Metal Di(methanesulfonyl)amides. 10. The Three‐Dimensional Coordination Polymers M[(CH₃SO₂)₂N], where M is Potassium, Rubidium, Cesium (Isotypic Structures for M = K, Rb) Low‐temperature X‐ray crystal structures are reported for KA (monoclinic, space group P2₁/c, Z′ = 1), RbA (isotypic and isostructural with KA), and CsA (monoclinic, P2₁/n, Z′ = 1), where A^— denotes the anion obtained by deprotonation of the strong nitrogen acid (MeSO₂)₂NH. In KA and RbA, the anion is distorted into a rare C₁ conformation, whereas the standard C₂ conformation is retained in the cesium complex. The structures consist of three‐dimensional coordination networks, in which each cation adopts an irregular (O₆N)‐heptacoordination by forming close contacts to one (O, N)‐chelating, one (O, O)‐chelating and three κ¹O‐bonding ligands; however, the coordination number for Cs⁺ is effectively increased to 8 by a very short Cs···Cs contact distance of 422.5 pm. The crystal packings of the isotypic compounds KA and RbA display lamellar layer substructures that involve six independent ligand‐metal bonds and comprise an internal cation lamella and peripheral regions built up from anion monolayers; the 3D framework is completed by one independent M—O bond cross‐linking the layer substructures. In contrast, CsA features anion monolayers that intercalate planar zigzag chains of cations (Cs···Cs alternatingly 422.5 and 487.5 pm, Cs···Cs···Cs 135.7°), whereby each chain is surrounded and coordinated by four anion stacks and each anion stack connects two cation chains. All structures exhibit close C—H···A interanion contacts consistent with weak hydrogen bonding.     

Automated molecule editing in molecular design

The ability to modify chemical structures in an automated and controlled manner is useful in molecular design. This Perspective introduces the MUDO molecule editor and shows how automated molecule editing can be used to standardize structures, enumerate tautomeric and ionization states, identify matched molecular pairs. Unlike its predecessor Leatherface, MUDO can also process 3D structures and this capability can be used to link non-covalently docked ligands to proteins.