Preparation of novel analgesics via diastereoselective nucleophilic addition to 1-dimethylamino-2-methylpentan-3-one

The diastereoselective synthesis of naphthyl amino alcohols via nucleophilic addition to racemic 1-dimethylamino-2-methylpentan-3-one was studied. The use of the appropriate experimental conditions allowed the synthesis of both diastereoisomers. The relative configurations were established via NOESY experiments.     

Rhythmic growth of ring‐banded spherulites in blends of liquid crystalline methoxy‐poly(aryl ether ketone) and poly(aryl ether ether ketone)

Rhythmic growth of ring‐banded spherulites in blends of liquid crystalline methoxy‐poly(aryl ether ketone) (M‐PAEK) and poly(aryl ether ether ketone) (PEEK) has been investigated by means of differential scanning calorimetry (DSC), polarized light microscopy (PLM), and scanning electron microscopy (SEM) techniques. The measurements reveal that the formation of the rhythmically grown ring‐banded spherulites in the M‐PAEK/PEEK blends is strongly dependent on the blend composition. In the M‐PAEK‐rich blends, upon cooling, an unusual ring‐banded spherulite is formed, which is ascribed to structural discontinuity caused by a rhythmic radial growth. For the 50:50 M‐PAEK/PEEK blend, ring‐banded spherulites and individual PEEK spherulites coexist in the system. In the blends with PEEK as the predominant component, M‐PAEK is rejected into the boundary of PEEK spherulites. The cooling rate and crystallization temperature have great effect on the phase behavior, especially the ring‐banded spherulite formation in the blends. In addition, the effects of M‐PAEK phase transition rate and phase separation rate on banded spherulite formation is discussed. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 3011–3024, 2007     

An efficient phosphine-free palladium coupling for the synthesis of new 2-arylbenzo[b]thiophenes

Straightforward and rapid access to 2-arylbenzo[b]thiophenes has been developed. It involved a catalytic coupling of 3-activated benzo[b]thiophenes with several aryl halides in the presence of a phosphine-free palladium system. In case of fragile functional groups such as aldehydes, a quaternary ammonium was used as an additive as with the other substrates, the coupling performed better and faster in the presence of a crown ether, the best one being DCH-18-C-6, with good yields and low reaction times. This method would provide a direct access to novel structures of biological interest.     

Darstellung und Molekülstrukturen von oligofunktionalen Dirheniumcarbonylderivaten aus Dirheniumnonacarbonylphosphan

Preparation and Molecular Structures of Oligofunctional Dirhenium Carbonyl Derivatives from Dirhenium Nonacarbonylphosphane Starting with dirheniumdecacarbonyl, one CO-Ligand was eliminated oxidatively and substituted by the labile acetonitrile ligand. As an intermediate eq-Re₂(CO)₉NCCH₃ was received. The reaction of this labilised carbonyl with tris(trimethylsilyl)phosphine and subsequent methanolysis gave ax-Re₂(CO)₉PH₃, which was isolated and characterized for the first time. Photochemical and thermal reaction of ax-Re₂(CO)₉PH₃ led to the new bi- and trinuclear complexes Re₂(μ-H)(μ₃-PHRe(CO)₅)(CO)₈, Re₂(μ-PH₂)₂(CO)₈ and Re₂(μ-H) · (μ-PH₂)(CO)₈, which were characterized by IR-, ¹H- and ³¹P-NMR spectroscopy. The structures of ax-Re₂(CO)₉PH₃, Re₂(μ-H)(μ₃-PHRe(CO)₅)(CO)₈ and Re₂(μ-PH₂)₂(CO)₈ were confirmed by single-crystal X-ray analysis. ax-Re₂(CO)₉PH₃ has a very short Re? P bond length of 228(2) pm.     

Synthesis of aromatic poly(thioether ketone)

Aromatic poly(thioether ketone)s were prepared by the direct polycondensation of aromatic dicarboxylic acids with aryl compounds containing ether or sulfide structures using phosphorus pentoxide/methanesulfonic acid (PPMA) as a condensing agent and solvent. Polycondensation proceeded smoothly and produced aromatic poly(thioether ketone)s with inherent viscosities up to 0.73 dL/g. The synthesis of substituted aryl ketones by the reaction of substituted benzoic acids with aryl compounds in PMMA was studied in detail to demonstrate the feasibility of the reaction for polymer formation. The thermogravimetry of the aromatic poly(thioether ketone)s showed a 10% weight loss in air and nitrogen at around 450 and 460°C, respectively. © 1992 John Wiley & Sons, Inc.     

Preparation and Characterization of a Cobalt‐Containing Mono‐Phosphine Ligand and its Coordinated Molybdenum Complex

A cobalt‐containing monodentate phosphine [(μ₂‐PPh₂CH₂PPh₂‐κ²P)Co₂(CO)₄][μ₂‐η²‐PhC≡CP(i‐Pr)₂] 2f , was prepared from the reaction of (μ₂‐PPh₂CH₂PPh₂‐κ²P)Co₂(CO)₆ 1 with PhC≡CP(i‐Pr)₂. It was accompanied by an oxidized compound, [(μ₂‐PPh₂CH₂PPh₂‐κ²P)Co₂(CO)₄][μ₂‐η²‐PhC≡CP(=O)(i‐Pr₂)] 2fo during the chromatographic process. Further reaction of 2f with Mo(CO)₆ resulted in the formation of a 2f ‐ligated molybdenum complex 4 , [(μ₂‐PPh₂CH₂PPh₂‐κ²P)Co₂(CO)₄][μ₂‐η²‐PhC≡CP(i‐Pr₂)‐κP]‐Mo(CO)₅.     

Rh(Ⅰ),Co(Ⅰ)和Ru(Ⅱ)双齿磷氢化物的合成.结构表征和催化加氢活性

膦配位的过渡金属氢化物被看作是烯烃及其他一些不饱含有机化合物催化加氢反应及氢甲酰化反应的催化活性物种,关于它们的结构与催化活性关系的研究,有着重要的理论意义和实际意义,通常单齿膦配位表现出较高的催化活性,而不同的金属中心在催化活性和选择性上也表现出明显的差别,反映了催化功能与催化活性物种的电子结构和空间结构之间存在着依存关系.膦配体过渡金属氢化物,通常是以它们的相应卤化物经氢化锂铝或硼氢化钠或肼还原得     

非螯合型手性双膦铑对脱氢苯丙氨酸的不对称催化加氢反应

报道从Ｄ－甘露醇出发合成手性双膦（２Ｓ，５Ｓ）－３，６－双（二苯膦）－１，４：３，６－双脱水－２，５－双去氧－Ｌ－艾杜醇，原位下ＢＤＰＩ与３种铑配合物作用生成手性非螯合型双膦铑催化剂，常压下对４种脱氢苯丙氨酸衍生物进行不对称催化化反主尖，对反应结果及ｅ．ｅ．值进行了讨论。     

Adducts of Rh2[MTPA]4 with some phosphine chalcogenides: nature of binding and ligand exchange

Adducts of four phosphine chalcogenides with the chiral dirhodium complex ([Rh-Rh]) were investigated by variable-temperature 1H and 31P NMR spectroscopy in order to compare their properties as axial ligands. Whereas the selenide (1) and the sulfide (2) are strong ligands with electrostatic attraction and, in addition, a significant orbital (HOMO-LUMO) interaction, the phosphine oxide compounds (P=O) bind primarily via electrostatic attraction and are relatively weak donors. Moreover, the overall bond strength in these adducts depends on steric congestion around the P=O group.