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Acyl Bond (acyl + bond)
Selected AbstractsO -Acylated 2-Phosphanylphenol Derivatives , Useful Ligands in the Nickel-Catalyzed Polymerization of EthyleneEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 9 2009Dmitry G. Yakhvarov Abstract The title ligands were prepared by O -acylation of 2-diphenylphosphanyl-4-methylphenol (1) or directly by double lithiation of 2-bromo-4-methylphenol and stepwise coupling with ClPPh2 and ClP(O)Ph2 or RC(O)Cl (R = Me, tBu, Ph, 4-MeOC6H4) to afford diphenylphosphinate 2 and carboxylic esters 3a,d. X-ray crystal structure analyses of 3b,d show conformations in which the P -phenyl substituents are rotated away from the ester group and the C(O)O , planes are nearly perpendicular to the phenol ring , plane. O -Acylated phosphanylphenols 2 and 3a,d form highly active catalysts with Ni(1,5-cod)2 (as does 1) for polymerization of ethylene, whereas phosphanylphenyl ethers do not give catalysts under the same conditions. The reason is the cleavage of the O -acyl bond upon heating with nickel(0) precursor compounds in the presence of ethylene. The precursors are P-coordinated Ni0 complexes, which are formed at room temperature, such as 4d obtained from 3d and Ni(cod)2 (in a 2:1 molar ratio), and characterized by multinuclear NMR spectroscopy. Upon heating in the presence of ethylene, the precatalysts are activated. Catalysts 2Ni and 3a,dNi convert ethylene nearly quantitatively, 2Ni slowly, and 3a,dNi rapidly, into linear polyethylene with vinyl and methyl end groups, and in the latter case, C(O)R end groups are also detectable. This proves insertion of Ni0 into the O,C(O)R bond of 3a,d ligands for formation of the primary catalyst. Termination of the first chain growing cycle by ,-hydride elimination changes the mechanism to the phosphanylphenolate,NiH initiated polymerization providing the main body of the polymer. A small retardation in the ethylene consumption rate with 3a,dNi catalysts relative to that observed for 1Ni and stabilization of the catalyst, which gives rise to reproducibly high ethylene conversion, is observed. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Phospholipase stimulates lipogenesis in SZ95 sebocytesEXPERIMENTAL DERMATOLOGY, Issue 7 2008S. Schagen Introduction:, With progressing ageing human sebocytes reduce lipid production. However, the influence of certain aging mechanisms on sebaceous lipid synthesis as well as ways to influence the latter is not fully identified. Certain lipids act as ligands of nuclear receptors such as PPAR. Phospholipase (PLA2) catalyzes the hydrolysis of the sn-2 fatty acyl bond of phospholipids to yield free fatty acid and lysophospholipid. It has been hypothesized that PPAR may be activated by hydrolysis products of phospholipids and also by eicosanoids obtained through PLA2 activity. Materials and Methods:, A method to quantify sebaceous lipid synthesis of SZ95 sebocytes in vitro was established and the cells were treated by snake venom Bothrops moojeni gel filtration fractions (Botmo GF). Botmo GF fractions were further purified by RP-HPLC, and a fraction with PLA2 activity (Botmo GF11-117) and a fraction without enzymatic activity (Botmo GF11-101) were identified and additionally tested. Results:, Botmo GF fractions increased lipogenesis in SZ95 sebocytes without inducing apparent toxic or apoptotic effects. Botmo GF11-101 (1 ,g/ml) enhanced neutral lipid synthesis by up to 170% and polar lipid synthesis by up to 120%. The enzymatically active PLA2 Botmo GF11-117 (1 ,g/ml) increased synthesis of neutral lipids by up to 200%, and polar lipids by up to 120% compared to untreated SZ95 sebocytes. Conclusion:, PLA2 activation or suppression could be important for human sebaceous lipogenesis. PLA2 modifiers may be attractive for skin lipid research and pharmacological/cosmetic products. [source] Insertion Reactions of 1,2-Disubstituted Olefins with an , -Diimine Palladium(II) ComplexHELVETICA CHIMICA ACTA, Issue 8 2006Carla Carfagna Abstract The migratory insertions of cis or trans olefins CH(X)CH(Me) (X,=,Ph, Br, or Et) into the metal,acyl bond of the complex [Pd(Me)(CO)(iPr2dab)]+ [B{3,5-(CF3)2C6H3}4], (1) (iPr2dab,=,1,4-diisopropyl-1,4-diazabuta-1,3-diene,=,N,N, -(ethane-1,2-diylidene)bis[1-methylethanamine]) are described (Scheme,1). The resulting five-membered palladacycles were characterized by NMR spectroscopy and X-ray analysis. Experimental data reveal some important aspects concerning the regio- and stereochemistry of the insertion process. In particular, the presence of a Ph or Br substituent at the alkene leads to the formation of highly regiospecific products. Moreover, in all cases, the geometry of the substituents in the formed palladacycle was the same as in the starting olefin, as a consequence of a cis addition of the Pd,acyl fragment to the CC bond. Reaction with CO and MeOH of the five-membered complex derived from trans-, -methylstyrene (=,[(1E)-prop-1-enyl]benzene) insertion, yielded the 2,3-substituted , -keto ester 9 with an (2RS,3SR)-configuration (Scheme,3). [source] Structure analysis of triterpene saponins in Polygala tenuifolia by electrospray ionization ion trap multiple-stage mass spectrometryJOURNAL OF MASS SPECTROMETRY (INCORP BIOLOGICAL MASS SPECTROMETRY), Issue 7 2007Jiangyun Liu Abstract Eighteen different triterpene saponins isolated from Polygala tenuifolia were investigated by electrospray ionization ion trap multiple-stage mass spectrometry (ESI-ITMSn) in positive and negative ion modes. MS1 -MS3/MS4 spectra of the both modes were analyzed, and they all gave fragments in line and shared common fragmentation patterns. Key fragments from MSn spectra of both the modes and their proposed fragmentation pathways were constructed with examples illustrated for the formation of characteristic fragments in the saponins. Two special fragmentation patterns were proposed: (1) the formation of fragments by cleavage of CH2O from ,12 -14,-CH2OH of the oleanene-type saponin aglycone in both positive and negative MSn (n , 2) modes; (2) the occurrence of fragments by cleavage of CO2 and 3-glucose as the characteristic structure feature of 23-COOH at the oleanene-type saponin aglycones coupled with 3-Glc substitutes in the negative MSn (n , 2) modes. Peak intensities in MSn spectra were also correlated with structural features and fragmentation preferences of the investigated saponins, which are discussed in detail. In general, fragments formed predominantly by cleavages of glycosidic bonds in the positive mode, while selective cleavages of acyl bonds preceded that of glycosidic bonds in negative MSn (n , 2) mode, both of which could well be applied to the structural analysis of these saponins. Interpretation of MSn spectra presented here provided diagnostic key fragment ions important for the structural elucidation of saponins in P.tenuifolia. Copyright © 2007 John Wiley & Sons, Ltd. [source] | ||||||||||