Fusaspirols A-D,novel oxaspirol derivatives isolated from Fusarium solani B-18

Four novel compounds with γ-methylidene-spirobutanolide core, fusaspirols A-D, were isolated from the brown rice culture of Fusarium solani B-18. Their structures were established by extensive spectroscopic analyses of 1D/2D-NMR, HRESITOFMS, and chemical derivatization. The absolute configurations of secondary alcohols in fusaspirols A and D were determined using modified Mosher's ester method. Fusaspirol A and 4,9-di-O-acetylfusaspirol A activated a signaling pathway in osteoclastic differentiation of murine macrophage derived RAW264.7?cells.     

Catalytic Synthesis of a Monodisperse Olefin Block Copolymer Using a Living Polymerization System

Polymerization of norbornene has been conducted with [t‐BuNSiMe₂(3,6‐t‐Bu₂Flu)]TiMe₂ ( 1 ) in toluene at 20 °C using modified methylaluminoxane that contained 0.4 mol‐% of triisobutylaluminium (TIBA) (dMMAO(0.4)) or 1.8 mol‐% of TIBA (dMMAO(1.8)). The 1 ‐dMMAO(0.4) catalytic system undergoes a living polymerization of norbornene. The catalysis of norbornene and propylene with the 1 ‐dMMAO(1.8) catalytic system gives markedly different results because of differences in transfer times of the polymers from Ti to TIBA. The successive addition of norbornene and propylene before the complete consumption of the norbornene in the 1 ‐dMMAO(1.8) system gives monodisperse PNB‐block‐poly(propylene‐ran‐norbornene)‐block‐PP terminated with a Ti–PP bond, which is exchanged with TIBA. Hence the repeated addition of the same amount of norbornene and propylene realizes the catalytic synthesis of monodisperse block copolymer in this system.

     

New nickel(II) diimine complexes bearing phenyl and sec‐phenethyl groups: synthesis,characterization and ethylene polymerization behaviour

A series of nickel(II) catalysts containing phenyl and chiral sec‐phenethyl groups, {[(4‐R₁‐2‐R₂C₆H₂N?C)₂Nap]NiBr₂} (Nap: 1,8‐naphthdiyl, R₁ = Me, R₂ = Ph ( 3a ); R₁ = Me, R₂ = sec‐phenethyl ( 3b ); R₁ = Cl, R₂ = sec‐phenethyl ( 3c ); R₁ = Me, R₂ = Me ( 3d ) were synthesized and characterized. All organic compounds were fully characterized by FT‐IR and NMR spectroscopy and elemental analysis. The single crystal for X‐ray crystallography was isolated from 3a in CH₂Cl₂/n‐hexane under air; the crystal structure showed a binuclear complex 3a ′, in which each nickel atom was six‐coordinate. The two nickel atoms together with two bromine atoms form a planar four‐membered ring, with a bromine and H₂O axial ligands. These complexes, activated by diethylaluminum chloride and chiral nickel pre‐catalysts rac‐ 3c , exhibited good activities (up to 2.85 × 10⁶ g PE (mol Ni h bar)^?1) for ethylene polymerization, and produced polyethylene products with a high degree of branching (up to 117 branched per 1000 carbons) at high temperature. The type and amount of branches of the polyethylenes obtained were determined by ¹H and ¹³C NMR spectroscopy. Copyright © 2014 John Wiley & Sons, Ltd.     

Copolymerization of 1,3‐butadiene and isoprene with cobalt dichloride/methylaluminoxane in the presence of triphenylphosphine

The homopolymerization and copolymerization of 1,3‐butadiene and isoprene were achieved at 0 °C with cobalt dichloride in combination with methylaluminoxane and triphenylphosphine (Ph₃P). For 1,3‐butadiene, highly cis‐specific and 1,2‐syndiospecific polymerization proceeded in the absence or presence of Ph₃P, respectively, although the activity with Ph₃P was much higher than that without Ph₃P. Only a trace of the polymer was, however, obtained in isoprene polymerization when Ph₃P had been added. For copolymerization, the polymer yield in the presence of Ph₃P was about three times higher than that in its absence. Copolymerization in the presence of Ph₃P was, therefore, investigated in more detail. Unimodal gel permeation chromatography elution curves with narrower polydispersity (weight‐average molecular weight/number‐average molecular weight ≈ 1.5) indicated that the propagation reaction proceeded by single‐site active species. Both the yield and molecular weight of the copolymer decreased with an increasing amount of isoprene in the feed, and this was followed by an increase in the isoprene content in the copolymer. The monomer reactivity ratios, r₁ (1,3‐butadiene) and r₂ (isoprene), were estimated to be 2.8 and 0.15, respectively. Although the 1,3‐butadiene content in the copolymer was strongly dependent on the comonomer composition in the feed, the ratio of 1,2‐inserted units to 1,4‐inserted units of 1,3‐butadiene was constant. Concerning the isoprene unit, the percentage of 1,2‐ and 3,4‐inserted units was increased at the expense of 1,4‐inserted units with an increasing isoprene content in the feed. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3086–3092, 2002     

Synthesis of crystallizable sydiotactic-atactic stereoblock polypropylene using a living polymerization system

Propylene polymerizations were conducted by [t-BuNSiMe₂(3,6-t-Bu₂Flu)]TiMe₂ using dried modified methyaluminoxane as a cocatalyst in heptane, chlorobenzene (CB), and a mixture of heptane/CB (1:1 in volume) at 0°C. Postpolymerizations testified that the propylene polymerization proceeded in a living manner regardless of the solvent used. The heptane system gave highly syndiotactic crystalline polypropylene (PP), whereas the CB and heptane/CB mixture systems gave amorphous PP. After the first polymerization in heptane had been completed, the same amounts of propylene and CB were added for the second polymerization. This procedure gave the syndiotactic-atactic stereoblock PP with a melting point of 119°C. The text was submitted by the authors in English.     

Two new 5‐deoxyflavan‐3,4‐diol glucosides from roots of Albizia chevalieri

Phytochemical investigation of the roots of Albizia chevalieri led to the isolation of two new 5‐deoxyflavan‐3,4‐diol glucosides from roots of A. chevalieri, Chevalieriflavanosides A and B. Their structures were established by 2D NMR techniques, UV, IR, CD, and mass spectrometry. Cytotoxicity of the two compounds was evaluated against acute promyelocytic leukemia HL60 cells. The antibacterial activities of 1 and 2 also were evaluated against Pseudomonas aeruginosa and Staphylococcus aureus using the agar diffusion test. Copyright © 2016 John Wiley & Sons, Ltd.     

Copolymerization of ethylene with 1,1‐disubstituted olefins catalyzed by ansa‐(fluorenyl)(cyclododecylamido)dimethyltitanium complexes

A series of titanium complexes with ansa‐(fluorenyl)(cyclododecylamido) ligands, Me₂Si(η³‐R)(N‐c‐C₁₂H₂₃)TiMe₂ [R = fluorenyl ( 5 ), 2,7‐^tBu₂fluorenyl ( 6 ), 3,6‐^tBu₂fluorenyl ( 7 )], was synthesized. The crystal structure of complex 6 revealed η³‐coordination of the fluorenyl moiety to the metal. Upon activation with trialkylaluminum‐free modified methylaluminoxane, complexes 5 – 7 as well as the corresponding ^tBu amide complexes, Me₂Si(η³‐R)(N^tBu)TiMe₂ [R = fluorenyl ( 2 ), 2,7‐^tBu₂fluorenyl ( 3 ), 3,6‐^tBu₂fluorenyl ( 4 )], were adopted as the catalysts for the copolymerization of ethylene (E) and isobutylene (IB). Among these complexes, complex 6 was found to achieve the highest IB incorporation to produce alternating E‐IB copolymers. Complex 6 system also achieved copolymerization of E and limonene. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Synthesis of Uniquely Branched Polyethylene by Anilinonaphthoquinone Ligated Nickel Complex Activated with Tris(pentafluorophenyl)borane

Summary: A novel nickel complex ligated with 2‐(2,6‐diisopropylanilino)‐1,4‐naphthoquinone ( 1 ) was synthesized. The molecular structure of 1 determined by X‐ray analysis was a square‐planar geometry. Complex 1 conducted ethylene polymerization at 40 °C in a low activity to give linear polyethylene. On the other hand, 1 activated with 4 eq. of B(C₆F₅)₃ was highly active for ethylene polymerization and gave a polymer possessing short chain branches of methyl, ethyl and propyl groups formed by a chain walking mechanism, as well as long chain branches, of which the content was almost the same as the total content of short chain branches. These results suggest that the macromonomer formed via β‐hydride elimination should have effectively copolymerized with ethylene to give the long chain branches in the B(C₆F₅)₃‐activated system.