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Qichao Zhang, Jian Lv, Sujia Li, Sanzhong Luo
The carbocation salt [Ph3 C][BArF] has been identified as a viable Lewis acid catalyst for the Diels-Alder reactions between anthracene derivatives and unsaturated carbonyl compounds with good selectivity and high efficiency.
March 30, 2018: Organic Letters
Pablo Ríos, Hugo Fouilloux, Pietro Vidossich, Josefina Díez, Agustí Lledós, Salvador Conejero
The platinum complex [Pt(It Bui Pr')(It Bui Pr)][BArF ] interacts with tertiary silanes to form stable (<0 °C) mononuclear PtII σ-SiH complexes [Pt(It Bui Pr')(It Bui Pr)(η1 -HSiR3 )][BArF ]. These compounds have been fully characterized, including X-ray diffraction methods, as the first examples for platinum. DFT calculations (including electronic topological analysis) support the interpretation of the coordination as an unusual η1 -SiH. However, the energies required for achieving a η2 -SiH mode are rather low, and is consistent with the propensity of these derivatives to undergo Si-H cleavage leading to the more stable silyl species [Pt(SiR3 )(It Bui Pr)2 ][BArF ] at room temperature...
March 12, 2018: Angewandte Chemie
Weihao Chen, Yang Li, Yang Chen, Chun-Yu Ho
Cross-hydroalkenylation of a vinyl ether (1) with an α-olefin (2) was first achieved by a set of [NHC-Ni(allyl)]BArF (NHC=N-heterocyclic carbene) catalysts. Both 1,2- and 1,3-disubstituted allyl ethers were obtained, highly selectively, by using NHCs of different sizes. In contrast, the chemoselectivity (i.e., 1 as acceptor and 2 as donor) was controlled mostly by electronic effects through the catalyst-substrate interaction. Sterically bulkier alkenes (2) were used as preferred donors compared to smaller alkenes...
March 1, 2018: Angewandte Chemie
Assia L Angelova, Milena Barf, Karsten Geletneky, Andreas Unterberg, Jean Rommelaere
Glioblastoma, one of the most aggressive primary brain tumors, is characterized by highly immunosuppressive microenvironment. This contributes to glioblastoma resistance to standard treatment modalities and allows tumor growth and recurrence. Several immune-targeted approaches have been recently developed and are currently under preclinical and clinical investigation. Oncolytic viruses, including the autonomous protoparvovirus H-1 (H-1PV), show great promise as novel immunotherapeutic tools. In a first phase I/IIa clinical trial (ParvOryx01), H-1PV was safe and well tolerated when locally or systemically administered to recurrent glioblastoma patients...
December 15, 2017: Viruses
Ana Zamorano, Nuria Rendón, Joaquín López-Serrano, Eleuterio Álvarez, Ernesto Carmona
We report the synthesis and structural characterization of five-coordinate complexes of rhodium and iridium of the type [(η5 -C5 Me5 )M(N^N)]+ (3-M+ ), where N^N represents the aminopyridinate ligand derived from 2-NH(Ph)-6-(Xyl)C5 H3 N (Xyl = 2,6-Me2 C6 H3 ). The two complexes were isolated as salts of the BArF anion (BArF = B[3,5-(CF3 )2 C6 H3 ]4 ). The M-Namido bond of complexes 3-M+ readily activated CO, C2 H4 , and H2 . Thus, compounds 3-M+ reacted with CO under ambient conditions, but whereas for 3-Rh+ , CO migratory insertion was fast, yielding a carbamoyl carbonyl species, 4-Rh+ , the stronger Ir-Namido bond of complex 3-Ir+ caused the reaction to stop at the CO coordination stage...
January 2, 2018: Inorganic Chemistry
Tjeerd Barf, Todd Covey, Raquel Izumi, Bas van de Kar, Michael Gulrajani, Bart van Lith, Maaike van Hoek, Edwin de Zwart, Diana Mittag, Dennis Demont, Saskia Verkaik, Fanny Krantz, Paul G Pearson, Roger Ulrich, Allard Kaptein
Several small-molecule Bruton tyrosine kinase (BTK) inhibitors are in development for B cell malignancies and autoimmune disorders, each characterized by distinct potency and selectivity patterns. Herein we describe the pharmacologic characterization of BTK inhibitor acalabrutinib [compound 1, ACP-196 (4-[8-amino-3-[(2S)-1-but-2-ynoylpyrrolidin-2-yl]imidazo[1,5-a]pyrazin-1-yl]-N-(2-pyridyl)benzamide)]. Acalabrutinib possesses a reactive butynamide group that binds covalently to Cys481 in BTK. Relative to the other BTK inhibitors described here, the reduced intrinsic reactivity of acalabrutinib helps to limit inhibition of off-target kinases having cysteine-mediated covalent binding potential...
November 2017: Journal of Pharmacology and Experimental Therapeutics
David H Dreyfus
Epstein-Barr virus, a ubiquitous human herpesvirus, is associated through epidemiologic evidence with common autoimmune syndromes and cancers. However, specific genetic mechanisms of pathogenesis have been difficult to identify. In this review, the author summarizes evidence that recently discovered noncoding RNAs termed microRNA encoded by Epstein-Barr virus BARF (BamHI A right frame) termed BART (BamHI A right transcripts) are modulators of human immune response genes and genome stability in infected and bystander cells...
2017: Journal of Immunology Research
Shuang Yang, Wen Che, Hui-Ling Wu, Shou-Fei Zhu, Qi-Lin Zhou
We developed neutral iridium catalysts with chiral spiro phosphine-carboxy ligands (SpiroCAP) for asymmetric hydrogenation of unsaturated carboxylic acids. Different from the cationic Crabtree-type catalysts, the iridium catalysts with chiral spiro phosphine-carboxy ligands are neutral and do not require the use of a tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (BArF(-)) counterion, which is necessary for stabilizing cationic Crabtree-type catalysts. Another advantage of the neutral iridium catalysts is that they have high stability and have a long lifetime in air...
March 1, 2017: Chemical Science
Karsten Kempker, Arne Güssow, Andrea M Cook, Markus Rick, Reto Neiger
Two dogs with increased thyroxin concentrations compatible with hyperthyroidism were referred for further examinations. One dog displayed clinical signs of hyperthyroidism. Based on history, clinical examination, laboratory evaluation and scintigraphy an alimentary thyrotoxicosis was identified. It was caused by feeding a BARF diet containing thyroidal tissue in one dog and by conventional dog food in the other patient. After changing the diet the clinical signs resolved in the affected dog. A control examination revealed thyroxin concentrations within the reference range in both dogs...
June 20, 2017: Tierärztliche Praxis. Ausgabe K, Kleintiere/Heimtiere
Subrata K Ghosh, Kyle G Lewis, Anil Kumar, John A Gladysz
Aerobic reactions of CoX2 (X = OAc, Cl) or Co(ClO4 )2 with (S,S)-1,2-diphenylethylenediamine [(S,S)-dpen] in CH3 OH, followed by HCl or HClO4 additions, give the diastereomeric lipophobic salts Λ-[Co((S,S)-dpen)3 ]3+ 3Cl- [Λ-(S,S)-13+ 3Cl- ] or Δ-(S,S)-13+ 3ClO4 - (60-65%) with high degrees of selectivity. Anion metatheses (room temperature) and equilibrations (charcoal, CH3 OH, 70 °C) show that the former is more stable than Δ-(S,S)-13+ 3Cl- , and the latter is more stable than Λ-(S,S)-13+ 3ClO4 - . Additional anion metatheses lead to large families of lipophilic salts Λ- and Δ-(S,S)-13+ 2X- X'- [X/X' = Cl/BArf [BArf = B(3,5-C6 H3 (CF3 )2 )4 ], PF6 /BArf , BF4 /BArf , PhBF3 /BArf , Cl/BArf20 [BArf20 = B(C6 F5 )4 ], BArf /BArf , BArf20 /BArf20 , BF4 /BF4 , PF6 /PF6 ]...
February 20, 2017: Inorganic Chemistry
Laura Ortega-Moreno, Riccardo Peloso, Joaquín López-Serrano, Javier Iglesias-Sigüenza, Celia Maya, Ernesto Carmona
Complex [PtMe2 (PMe2 ArDipp2 )] (1), which contains a tethered terphenyl phosphine (ArDipp2 =2,6-(2,6-(i) Pr2 C6 H3 )2 C6 H3 ), reacts with [H(Et2 O)2 ]BArF (BArF(-) =B[3,5-(CF3 )2 C6 H3 ]4(-) ) to give the solvent (S) complex [PtMe(S)(PMe2 ArDipp2 )](+) (2⋅S). Although the solvent molecule is easily displaced by a Lewis base (e.g., CO or C2 H4 ) to afford the corresponding adducts, treatment of 2⋅S with C2 H2 yielded instead the allyl complex [Pt(η(3) -C3 H5 )(PMe2 ArDipp2 )](+) (6) via the alkyne intermediate [PtMe(η(2) -C2 H2 )(PMe2 ArDipp2 )](+) (5)...
March 1, 2017: Angewandte Chemie
Mathew B Kiberd, Suzanne K Clarke, Jill Chorney, Brandon d'Eon, Stuart Wright
BACKGROUND: Postoperative nausea and vomiting (PONV) is one of the most common postoperative complications of general anesthesia in pediatrics. Aromatherapy has been shown to be effective in treating PONV in adults. Given the encouraging results of the adult studies, we planned to determine feasibility of doing a large-scale study in the pediatric population. METHODS: Our group conducted a pilot randomized controlled trial examining the effect of aromatherapy on post-operative nausea and vomiting in patients 4-16 undergoing ambulatory surgery at a single center...
November 9, 2016: BMC Complementary and Alternative Medicine
Michael P Smith, Claudia Wellbrock
Targeting hyperactive MAPK signaling has proven to be an effective treatment for a variety of different cancers. Responses to the BRAF inhibitors vemurafenib and dabrafenib and the MEK inhibitors trametinib and cobimetinib are, however, transient, and complete remission is rarely observed; rather, outgrowth of resistant clones within progressed tumors appears inevitable. These resistant tumors display great heterogeneity, which poses a major challenge to any salvage therapy. Recent focus has, therefore, been on the early dynamics of inhibitor response during tumor regression...
December 15, 2016: Clinical Cancer Research: An Official Journal of the American Association for Cancer Research
Pablo Ríos, Josefina Díez, Joaquín López-Serrano, Amor Rodríguez, Salvador Conejero
The low-electron-count cationic platinum complex [Pt(ItBu')(ItBu)][BArF ], 1, interacts with primary and secondary silanes to form the corresponding σ-SiH complexes. According to DFT calculations, the most stable coordination mode is the uncommon η1 -SiH. The reaction of 1 with Et2 SiH2 leads to the X-ray structurally characterized 14-electron PtII species [Pt(SiEt2 H)(ItBu)2 ][BArF ], 2, which is stabilized by an agostic interaction. Complexes 1, 2, and the hydride [Pt(H)(ItBu)2 ][BArF ], 3, catalyze the hydrosilation of CO2 , leading to the exclusive formation of the corresponding silyl formates at room temperature...
November 14, 2016: Chemistry: a European Journal
Julia K Mack, Ellen Kienzle
Anamnesis: A litter of Bernese Mountain Dog-puppies (6 weeks of age) was meant to be fed a "BARF" (bones and raw food) diet. The breeder asked for advice regarding the nutritional adequacy of the feeding plans that she had compiled for the different growth stages. The anamnesis showed the puppies to be underweight for their age and expected adult body mass at the time of request for a ration check. The bitch had almost stopped lactating. Ration check: The review of the feeding plans for the different growth stages revealed a deficient energy supply for all stages and at times an inadequate protein supply...
October 12, 2016: Tierärztliche Praxis. Ausgabe K, Kleintiere/Heimtiere
Evan E Joslin, Jan Paulo T Zaragoza, Regina A Baglia, Maxime A Siegler, David P Goldberg
The influence of remote peripheral substitution on the physicochemical properties and reactivity of phosphorus and manganese corrolazine (Cz) complexes was examined. The substitution of p-MeO for p-t-Bu groups on the eight phenyl substituents of the β-carbon atoms of the Cz ring led to changes in UV-vis transitions and redox potentials for each of the complexes. The oxygen atom transfer (OAT) and hydrogen atom transfer (HAT) reactivity of the Mn(V)(O) complexes was also influenced by p-MeO substitution. The OAT reactivity of Mn(V)(O)(MeOP8Cz) (MeOP8Cz = octakis(p-methoxyphenyl)corrolazinato(3-)) with triarylphosphine (PAr3) substrates led to second-order rate constants from 10...
September 6, 2016: Inorganic Chemistry
Mohammed N Alnajrani, Francis S Mair
New cationic enamine-β-diimine cobalt complex [LCoBr·THF][BArF] () and its neutral analogue [LCoBr2] () where L = [(2,4,6-Me3-C6H2)NHCMe[double bond, length as m-dash]C{CMe[double bond, length as m-dash](N-2,4,6-Me3(C6H2))}2] and BArF(-) = [{3,5-(CF3)2C6H3}4B](-), were synthesised and then characterized by single-crystal X-ray diffraction, MALDI-MS, IR and elemental analysis. These complexes, the first examples reported where putatively tridentate β-triketimines prefer a bidentate coordination mode, were examined as catalysts for the polymerization of isoprene, activated by diethylaluminium chloride (DEAC) or ethylaluminium sesquichloride (EASC)...
June 21, 2016: Dalton Transactions: An International Journal of Inorganic Chemistry
Georgette M Lang, Takanori Shima, Leyong Wang, Kyle J Cluff, Katrin Skopek, Frank Hampel, Janet Blümel, John A Gladysz
Reactions of trans-Fe(CO)3(P((CH2)mCH═CH2)3)2 (m = a/4; b/5, c/6, e/8) and Grubbs' catalyst (12-24 mol %, CH2Cl2, reflux) give the cage-like trienes trans- Fe(CO)3(P((CH2)mCH═CH(CH2)m)3 P) (3a-c,e, 60-81%). Hydrogenations (ClRh(PPh3)3, 60-80 °C) yield the title compounds trans- Fe(CO)3(P((CH2)n)3 P) (4a-c,e, 74-86%; n = 2m + 2), which have idealized D3h symmetry. A crystal structure of 4c suggests enough van der Waals clearance for the Fe(CO)3 moiety to rotate within the three P(CH2)14P linkages; structures of E,E,E-3a show rotation to be blocked by the shorter P(CH2)4CH═CH(CH2)4P linkages...
June 22, 2016: Journal of the American Chemical Society
Houhua Li, Clément Mazet
This Account presents the development of the iridium-catalyzed isomerization of primary allylic alcohols in our laboratory over the past 8 years. Our initial interest was driven by the long-standing challenge associated with the development of a general catalyst even for the nonasymmetric version of this seemingly simple chemical transformation. The added value of the aldehyde products and the possibility to rapidly generate molecular complexity from readily accessible allylic alcohols upon a redox-economical isomerization reaction were additional sources of motivation...
June 21, 2016: Accounts of Chemical Research
Laura Weston, Barnaby T Pownall, Francis S Mair, Joseph J W McDouall
A computational study is presented of a complex of thallium with a neutral β-triketimine ligand which was found to form dimers with close Tl-Tl interactions. Single point energies, using the crystallographic structures, suggest that the system is bound only when BArF counter ions are included in the calculations. Energy decomposition analysis of the system was carried out in order to investigate the nature of the bonding. Across the methods, calculations show the electrostatic interaction to be repulsive for the dimer with no counter ions, but attractive when BArF counter ions are included...
May 28, 2016: Dalton Transactions: An International Journal of Inorganic Chemistry
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