bluuebunny/crossref_metadata_2025 huggingface dataset:
Intramolecular Alkene Aminocarbonylation Using Concerted Cycloadditions of Amino‐Isocyanates
Authors: Ivanovich Ryan A. , Clavette Christian , Vincent‐Rocan Jean‐François , Roveda Jean‐Grégoire , Gorelsky Serge I. , Beauchemin André M.
Published: April 2016

The ubiquity of nitrogen heterocycles in biologically active molecules challenges synthetic chemists to develop a variety of tools for their construction. While developing metal‐free hydroamination reactions of hydrazine derivatives, it was discovered that carbazates and semicarbazides can also lead to alkene aminocarbonylation products if nitrogen‐substituted isocyanates (N‐isocyanates) are formed in situ as reactive intermediates. At first this reaction required high temperatures (150–200 °C), and issues included competing hydroamination and N‐isocyanate dimerization pathways. Herein, improved conditions for concerted intramolecular alkene aminocarbonylation with N‐isocyanates are reported. The use of βN‐benzyl carbazate precursors allows the effective minimization of N‐isocyanate dimerization. Diminished dimerization leads to higher yields of alkene aminocarbonylation products, to reactivity at lower temperatures, and to an improved scope for a reaction sequence involving alkene aminocarbonylation followed by 1,2‐migration of the benzyl group. Furthermore, fine‐tuning of the blocking (masking) group on the N‐isocyanate precursor, and reaction conditions relying on base catalysis for N‐isocyanate formation from simpler precursors resulted in room temperature reactivity, consequently minimizing the competing hydroamination pathway. Collectively, this work highlights that controlled reactivity of aminoisocyanates is possible, and provides a broadly applicable alkene aminocarbonylation approach to heterocycles possessing the β‐aminocarbonyl motif.
Rhodium‐Catalyzed Enantioselective Arylation of Aliphatic Imines
Authors: Kato Naoya , Shirai Tomohiko , Yamamoto Yasunori
Published: April 2016

Chiral rhodium(I)‐catalyzed highly enantioselective arylation of aliphatic N‐sulfonyl aldimines with arylboronic acids has been developed. This transformation is achieved by the use of a rhodium/bis(phosphoramidite) catalyst to give enantiomerically enriched α‐branched amines (up to 99 % ee). In addition, this system enables efficient synthesis of (+)‐NPS R‐568 and Cinacalcet which are calcimimetic agents.
ChemInform Abstract: SELECTION OF METHODS FOR THE UNEQUIVOCAL SYNTHESIS OF ALKYNES. PART 3. ARYLACETYLENES AND 1‐ARYLALK‐1‐YNES
Authors: MESNARD D. , BERNADOU F. , MIGINIAC L.
Published: April 2016

Verschiedene Methoden zur Darstellung der Titelverbindungen, z.B. (V) [ausgehend von (I)], (IX) [ausgehend von (V)], (XIII) [ausgehend von (X)], (XVI) [ausgehend von den Li‐Derivaten (XIV) entsprechender Acetylene (IV)Abz.w. (IX)], (XIX).
ChemInform Abstract: TEMPLATE‐DRIVEN MACROLIDE CLOSURES
Authors: RASTETTER W. H. , PHILLION D. P.
Published: April 2016

Aus dem Mercaptokronenether (I) erhält man in Gegenwart von Carbodiimid als Kondensationsmittel mit den in Form der Silylether eingesetzten Hydroxy‐carbonsäuren (II) die entsprechenden Thioloester (IIIa), die zu (IIIb) gespalten werden.
ChemInform Abstract: TEMPLATE EFFECT OF INTRAMOLECULAR HYDROGEN‐BONDING IN THE SYNTHESIS OF (1.1.1)CRYPTATES
Authors: ANNUNZIATA R. , MONTANARI F. , QUICI S. , VITALI M. T.
Published: April 2016

Durch Behandlung von (I) mit einem Äquival.
ChemInform Abstract: REACTION OF (CH3)3ANM AND PH3SNM (M = LI, NA, K) WITH OPTICALLY ACTIVE 2‐OCTYL TOSYLATE, CHLORIDE, AND BROMIDE
Authors: SAN FILIPPO J. JUN. , SILBERMANN J.
Published: April 2016

Untersuchungen der Titelreaktion zwischen (I) und den Derivaten (II) von (R)‐2‐Octanol zeigen, daß diese Reaktionen stereoselektiv unter Inversion verlaufen und die optisch aktiven (S)‐2‐Octyl‐Derivate (S)‐(III) liefern.
ChemInform Abstract: CHEMICAL MODIFICATION OF MALTOSE. V. A NEW SYNTHESIS OF 2‐ACETAMIDO‐2‐DEOXY‐4‐O‐α‐D‐GLUCOPYRANOSYL‐α‐D‐GLUCOPYRANOSE (N‐ACETYLMALTOSAMINE)
Authors: MORI M. , TEJIMA S.
Published: April 2016

Für das N‐Acetylmaltosamin (III) wird ein neuer Syntheseweg vorgeschlagen, der vom Zuckerderivat (I) ausgeht und über die Zwischenstufe (II) verläuft.
ChemInform Abstract: THE REACTIONS OF SILYL NITRONATES WITH ORGANOLITHIUM REAGENTS
Authors: COLVIN E. W. , ROBERTSON A. D. , SEEBACH D. , BECK A. K.
Published: April 2016

Die Silylnitronate(I) reagieren mit Organo‐Lithiumverbindungen in verd. Lösung unter Kettenverlängerung zu den Oximen (II).
ChemInform Abstract: 2‐(ARYLMETHYL)ARYLACETIC ACIDS AS POTENTIAL ANTIINFLAMMATORY AGENTS
Authors: BRANCACCIO G. , LARIZZA A. , LETTIERI G. , MONFORTE P.
Published: April 2016

Die Indanone (I) ergeben die Arylindene (II), die oxidativ zu den Ketocarbonsäuren (III) gespalten werden.
ChemInform Abstract: REACTION OF PHENOLS WITH 2‐(2‐HYDROXYETHYL)PYRROLIDINE AND CARBOXYLIC ACIDS
Authors: DOBRZENIECKA R.
Published: April 2016

Kondensation der Phenole (I) mit dem Pyrrolidin (II) und den Carbonsäuren (III) liefert die N‐Acylderivate (IV).
ChemInform Abstract: SUBSTRATE‐REAGENT COMPLEXATION ABILITY IN ENANTIOSELECTIVE 1,4‐ADDITION REACTIONS
Authors: LEYENDECKER F. , JESSER F. , RUHLAND B.
Published: April 2016

Die beiden Prolinol‐Derivate (I) werden zusammen mit Methylmagnesiumhalogeniden und Cu‐Halogeniden zu 1,4‐Additionsreaktionen an die aJS‐ungesättigten Ketone(II) ‐(III) eingesetzt.
ChemInform Abstract: FUNCTIONALIZED ENAMINES. PART XXXI. BASE‐CATALYZED TRANSFORMATIONS OF IMINIUM M PHENYLHYDRAZONES. A NEW CONVENIENT SYNTHESIS OF IMIDAZO(1,2A)AZACYCLOALKANES
Authors: KANNER C. B. , PANDIT U. K.
Published: April 2016

Die β‐Aminoester (I) reagieren mit dem Diazoniumtetrafluoroborat (II) in Acetonitril bei 20°C zu den Salzen (III), die beim Erhitzen (in situ) mit Et3N unter Eliminierung von Anilin zu den Imidazoheterocyclen (IV) cyclisieren.
ChemInform Abstract: Some Reactions of 6‐Acetyl‐5‐oxo‐3‐aryl‐3‐cyclohexene‐1‐carboxylic Acids.
Authors: SOLIMAN E. A. , SALEM M. A.
Published: April 2016

Die Acetylcyclohexenoncarbonsäuren (I) lassen sich basenkatalysiert mit den Benzaldehyden (II) zu den Cinnamoylcyclohexenoncarbonsäuren (III) kondensieren.
ChemInform Abstract: THE PREPARATION OF OPTICALLY ACTIVE β‐OXO SULFOXIDES BY THE REACTION OF α‐LITHIOMETHYL‐P‐TOLYL SULFOXIDE WITH ETHYL CARBOXYLATES IN THE PRESENCE OF (‐)‐SPARTEINE
Authors: KUNIEDA N. , KINOSHITA M.
Published: April 2016

Die Enantioselektivität der Reaktion der Ester (III) mit 2 Äquivalenten racem· α‐Lithiomethyl‐p‐tolylsulfoxid (II), das aus (I) zugänglich ist, in Gegenwart von(‐)‐Spartein wird in Abhängigkeit vom Carbonsäurerest und der Konzentration des Induktionsmittels untersucht.
ChemInform Abstract: HETEROGENEOUS COBALT CARBONYL‐NITROARENE REACTIONS. A SIGNIFICANT DIFFERENCE FROM THE HOMOGENEOUS PROCESS
Authors: ALPER H. , GOPAL M.
Published: April 2016

Nitroaromaten (I) reagieren mit Dicobaltoctacarbonyl auf einem Tonerde‐Träger unter Reduktion zu den entsprechenden Aminen (II).
ChemInform Abstract: STUDIES ON THE METAL‐AMIDE BOND. X. AN EVALUATION OF MOLECULAR DISTORTIONS ENFORCED BY STERIC HINDRANCE IN THE CRYSTAL STRUCTURE OF (N,N′‐BIS(6′‐METHYLPYRIDINE‐2′‐CARBOXAMIDO)‐1,2‐BENZENE)COPPER(II)
Authors: CHAPMAN R. L. , STEPHENS F. S. , VAGG R. S.
Published: April 2016

Die Titelverbindung (I) kristallisiert mit Z=4 in der Raumgruppe P21/c. Durch axiale Bindungen zu den Amidsauerstoffatomen benachbarter Moleküle wird sechsfache Koordination unter Bildung von Ketten er‐ 15 reicht.
ChemInform Abstract: ALKYNES AND CUMULENES . PART 15. PHOTODIMERIZATION OF CONJUGATED ENYNES
Authors: EISENHUTH L. , SIEGEL H. , HOPF H.
Published: April 2016

Lichteinwirkung auf die Enine (I) in Gegenwart von Sensibilisatoren wie z.B. Benzophenon oder Michlers Keton mit einer Triplett‐Energie über 250 kJ/mol läßt die cyclischen Dimere (II) und (III) in Ausb. von 50‐85% entstehen, die im Fall (Ia) von einem weiteren Produkt (IVa) begleitet werden.
ChemInform Abstract: REDUCTIVE DEBROMINATION AND COUPLING REACTION IN THE THERMOLYSIS OF 5‐BROMOURACILS IN N,N‐DIALKYLAMIDES. CLEAVAGE OF THE C(5)‐BROMINE BOND BY AN INITIAL ELECTRON‐TRANSFER PROCESS
Authors: SAKO M. , SUZUKI M. , TANABE M. , MAKI Y.
Published: April 2016

Die Spaltung der C‐Br‐Bindung der Uracile (I) wird durch einen Elektronenübergang vom Lösungsmittel Dimethylacetamid auf das Bromuracil eingeleitet, wobei aus letzterem ein Radikalanion und aus dem Acetamid ein Radikalkation gebildet wird.
ChemInform Abstract: TOTAL SYNTHESIS OF METHYLENOMYCIN B
Authors: NEWTON R. F. , REYNOLDS D. P. , EYRE T.
Published: April 2016

Auf den beiden skizzierten Reaktionswegen kann die im Titel genannte antibakteriell wirksame Verbindung (VII) hergestellt werden.
ChemInform Abstract: METHYL β‐(2‐METHYL‐5‐OXOCYCLOPENTENYLPROPIONATE AND ETHYL 3‐METHYL‐6‐OXOHEPTA‐2,4‐DIENOATE
Authors: WENKERT E. , BAKUZIS M. L. F. , BUCKWALTER B. L. , WOODGATE P. D.
Published: April 2016

Umsetzung von Isopropenylacetat (I) mit der Diazoverbindung (II) unter Einwirkung von Cu‐Bronze liefert ein Gemisch der isomeren Cyclopropylketone (III).
ChemInform Abstract: A PALLADIUM‐CATALYZED CARBON‐CARBON BOND FORMATION OF CONJUGATED DIENONES. A MACROCYCLIC DIENONE LACTONE MODEL FOR THE CARBOMYCINS
Authors: ZIEGLER F. E. , CHAKRABORTY U. R. , WEISENFELD R. B.
Published: April 2016

Die Umsetzung der Iodalkene (I) mit Methylvinylketon (II) unter PdCl2(CH3CN)2 ‐Katalyse liefert die Dienone (III) unter milden Bedingungen.
ChemInform Abstract: EQUILIBRIUM AND STRUCTURAL STUDIES OF SILICON(IV) AND ALUMINUM(III) IN AQUEOUS SOLUTION. 3. POTENTIOMETRIC STUDY OF ALUMINUM(III) HYDROLYSIS AND ALUMINUM(III) HYDROXO CARBONATES IN 0.6 M SODIUM CHLORIDE
Authors: OEHMAN L.‐O. + , FORSLING W.
Published: April 2016

Die Gleichgewichte zwischen A1(III), CO2 und OH′ werden in einem 0.6 M Na(Cl)‐Medium bei 25°C mit Hilfe von EMK‐ Titrationen (Glaselektrode) in den Bereichen 1.5 ‐log[H+] 4.3, 0.0025 M [A13 ] 0.02 Mund 9.5 kPa pCOQ 101 kPa untersucht.
ChemInform Abstract: THERMAL DECOMPOSITION OF ARENEDIAZONIUM TETRAFLUOROBORATES IN NITROMETHANE
Authors: HASHIDA Y. , TAKEDA Y. , MATSUI K.
Published: April 2016

Die thermische Zersetzung der p‐substituierten Benzoldiazoniumtetrafluoroborate (I) in Nitromethan (II) liefert neben den erwarteten p‐substituierten Fluorbenzolen (III) die Phenole (IV) und die Benzoxazole (V).
ChemInform Abstract: EPIMERIZATION AT C‐2 OF 2‐SUBSTITUTED THIAZOLIDINE‐4‐CARBOXYLIC ACIDS
Authors: NAGASAWA H. T. , GOON D. J. W. , SHIROTA F. N.
Published: April 2016

Aus den stereoisomeren Penicillaminen (I) und Aldehyden (II) entstehen verschiedene isomere Thiazolidin‐4‐carbonsäuren (III).
ChemInform Abstract: A Facile Synthesis of 1‐Alkylpyridino 2‐Acylamides and Their Catalytic Action.
Authors: INOKUMA S. , KAMEYAMA E. , KUWAMURA T.
Published: April 2016

Aminopyridin (I) liefert nach Quaternierung mit den Alkylhalogeniden (II) zu den Salzen (III) aus diesen mit Carbonsäurechloriden (IV) die Acyliminopyridine (V).
ChemInform Abstract: 1,2,3‐TRIAZINE
Authors: OHSAWA A. , ARAI H. , OHNISHI H. , IGETA H.
Published: April 2016

Die N‐Amino‐pyrazole (I) ergeben bei der Oxidation mit Nickelperoxid die 1,2,3‐Triazine (II).
ChemInform Abstract: ROLE OF THE 4β‐METHYL IN THE FORMATION OF STEROIDAL OXETANONES. CASE OF THE B RING
Authors: HANNA R. , KODEIH M. , CHERRY A.
Published: April 2016

Die Steroid‐ketole (I), deren Herstellung z.Tl. beschrieben ist, werden mit Triphenylmethylammoniumbromid in die isomeren Bromide (II) und (III) übergeführt.
ChemInform Abstract: STRUCTURAL STUDY OF THE SPIN‐CROSSOVER TRANSITION IN THE CLUSTER COMPOUNDS NIOBIUM IODIDE (NB6I11) AND HYDROGEN NIOBIUM IODIDE (HNB6I11)
Authors: IMOTO H. , SIMON A.
Published: April 2016

Die Kristallstrukturen der Titelverbindungen werden im Temp.‐Bereich l10‐350 K untersucht.
ChemInform Abstract: CYCLOHEPTATRIENES AND NORCARADIENES. 9. RELATION BETWEEN HINDRANCE OF ROTATION ABOUT THE C‐7‐C‐8 BOND AND STRUCTURE
Authors: BAUER W. , DAUB J. , MAAS G. , MICHNA M. , RAPP K. M. , STEZOWSKI J. J.
Published: April 2016

C‐8‐Bindung und Struktur.
ChemInform Abstract: BIBICYCLO(3.2.0)HEPTADIENYL DICATIONS. SYNTHESIS OF THE PRECURSORS AND CHEMICAL BEHAVIOR
Authors: HOGEVEEN H. , VAN KRUCHTEN E. M. G. A.
Published: April 2016

Die bicyclischen Ketone (I) werden nach Umwandlung in die Li‐Verbindung mit Kupfer(II)‐chlorid zu den Dimeren (II) umgesetzt.
ChemInform Abstract: INCORPORATION OF UNSATURATED HYDROCARBONS INTO A BORANE CAGE. A MODEL FOR THE IRREVERSIBLE ADSORPTION OF ALKYNES
Authors: DEKOCK R. L. , FEHLNER T. P. , HOUSECROFT C. E. , LUBBEN T. V. , WADE K.
Published: April 2016

MO‐ und Bindungsenergie‐Berechnungen werden zur Diskussion der Änderungen verwandt, die erfolgen, wenn B4H10 mit Ethylen oder Acetylen zu den closo‐Carboranen 1,2‐ und 1,6‐C,B4 H6 über arachno‐ und nido‐Vorläufer reagiert.
ChemInform Abstract: On the Use of Dynamical Diffraction Theory to Refine Crystal Structure from Electron Diffraction Data: Application to KLa5O5(VO4)2, a Material with Promising Luminescent Properties.
Authors: Colmont Marie , Palatinus Lukas , Huve Marielle , Kabbour Houria , Saitzek Sebastien , Djelal Nora , Roussel Pascal
Published: April 2016

Polycrystalline KLa5O5(VO4)2 is prepared by firing stoichiometric amounts of La(OH)3, V2O5, and K2CO3 in air (Al2O3 crucible, 1.
ChemInform Abstract: Phase Transitions in the Ruddlesden—Popper Phase Li2CaTa2O7: X‐Ray and Neutron Powder Thermodiffraction, TEM, Raman, and SHG Experiments.
Authors: Galven Cyrille , Mounier Denis , Bouchevreau Boris , Suard Emmanuelle , Bulou Alain , Crosnier‐Lopez Marie‐Pierre , Le Berre Francoise
Published: April 2016

Li2CaTa2O7 is prepared by solid state reaction of stoichiometric amounts of CaCO3, Ta2O5, and a 10% excess of Li2CO3 (Al2O3 crucible, 1150 °C, 28 h).
ChemInform Abstract: Tailoring Magnetic Behavior in the Tb‐Au‐Si Quasicrystal Approximant System.
Authors: Gebresenbut Girma H. , Andersson Mikael S. , Nordblad Per , Sahlberg Martin , Pay Gomez Cesar
Published: April 2016

“Arc‐melting‐self‐flux” as a new preparative method isemployed to prepare five Tsai‐type 1/1 approximant crystals in the Tb—Au—Si system.
ChemInform Abstract: Na‐α′‐GeGaON Solid Solution Analogous to α′‐SiAlON: Synthesis, Crystal Structure, and Potentiality as a Photocatalyst.
Authors: Suehiro Takayuki , Tansho Masataka , Shimizu Tadashi
Published: April 2016

The polycrystalline Na‐α′‐GeGaON (NamGe12‐ (m+n)Gam+nOnN16‐n) solid solution is prepared as a single phase by gas reduction—nitridation of mixtures of Na2CO3, GeO2, and Ga2O3 in the solubility range of m ≈0.8—1.7 with n ≈0.2—0.3 (Al2O3 crucible, 875 °C, 4 h; NH3/1.5 vol% methane stream).
ChemInform Abstract: New Series of Polar and Nonpolar Platinum Iodates A2Pt(IO3)6 (A: H3O, Na, K, Rb, Cs).
Authors: Yang Bing‐Ping , Hu Chun‐Li , Xu Xiang , Mao Jiang‐Gao
Published: April 2016

α‐(H3O)2Pt(IO3)6 (I), β‐(H3O)2Pt(IO3)6 (II), and M2Pt(IO3)6 with M: Na, K, Rb, and Cs (III)—(VI) are prepared by hydrothermal reaction of PtO2, alkali carbonates, and H5IO6 (for (I) and (II)) or I2O5 for (III)—(VI) (autoclave, 200—220 °C, 4 d; cooling to 25 °C at a rate of 6 °C/h; 85% yield for (I) and 50—60% for (II)—(VI)).
ChemInform Abstract: DMSO and Iodine Mediated Reaction of 4‐Hydroxycoumarins and Aldehydes/Aryl Methyl Ketones: Synthesis of Furo[3,2‐c]coumarins.
Authors: Kolita Sinki , Borah Pallabi , Naidu P. Seetham , Bhuyan Pulak J.
Published: April 2016

The transformation follows an initial iodine‐catalyzed reaction of 4‐hydroxycoumarins with carbonyl compounds to biscoumarins followed by lactone ring opening, cyclization, and oxidative aromatization.
ChemInform Abstract: AIBN/NaBr‐Promoted Aerobic Oxidation of Benzylic Alcohols via a Radical Process.
Authors: Liu Chengkou , Fang Zheng , Yang Zhao , Li Qingwen , Guo Shiyu , Guo Kai
Published: April 2016

A green and economic aerobic oxidation of benzylic, (hetero)aryl, and allyl alcohols is developed.
ChemInform Abstract: A Novel Protocol for the One‐Pot Borylation/Suzuki Reaction Provides Easy Access to Hinge‐Binding Groups for Kinase Inhibitors.
Authors: Hooper A. , Zambon A. , Springer C. J.
Published: April 2016

An one‐pot sequence of borylation and Suzuki reaction is used for the preparation of 20 bi‐ and polyarenes, e.g. vemurafenib precursor (IIId) and analogues (V) of kinase inhibitor GDC‐0879.
ChemInform Abstract: C—C Activation by Retro‐Aldol Reaction of Two β‐Hydroxy Carbonyl Compounds: Synergy with Pd‐Catalyzed Cross‐Coupling to Access Mono‐α‐Arylated Ketones and Esters.
Authors: Zhang Song‐Lin , Yu Ze‐Long
Published: April 2016

The cross‐coupling reaction of aryl halides with aldol‐type ketones and esters produces selectively mono‐α‐arylated ketones and esters.
ChemInform Abstract: DMF‐Mediated Deprotection of Bulky Silyl Esters under Neutral and Fluoride‐Free Conditions.
Authors: Chen Bo , Sun Hui‐Xia , Qin Jian‐Feng , Wang Bing
Published: April 2016

This simple protocol allows the cleavage of a wide range of bulky silyl esters and tolerates various acid and base labile functional groups.
ChemInform Abstract: Synthesis of 2,5‐Epoxy‐1,4‐benzoxazepines via Rhodium(II)‐Catalyzed Reaction of 1‐Tosyl‐1,2,3‐triazoles and Salicylaldehydes.
Authors: Meng Jiang , Ding Xiangfeng , Yu Xingxin , Deng Wei‐Ping
Published: April 2016

The title synthesis probably follows an α‐Imino carbene formation/[3 + 2]‐cycloaddition/ring opening/ring closing sequence.
ChemInform Abstract: One Pot Oxidative N—S Bond Formation to Access 2‐Sulfenylimine Chromenes.
Authors: Kale Ashok , Chennapuram Madhu , Bingi Chiranjeevi , Nanubolu Jagadeesh Babu , Atmakur Krishnaiah
Published: April 2016

The simple, efficient and one‐pot, catalyst‐free protocol leads to the synthesis of new 2‐sulfenylimine chromene compounds.
ChemInform Abstract: Asymmetric α,γ‐Regioselective [3 + 3] Formal Cycloadditions of α,β‐Unsaturated Aldehydes via Cascade Dienamine—Dienamine Catalysis.
Authors: Xiao Wei , Yin Xiang , Zhou Zhi , Du Wei , Chen Ying‐Chun
Published: April 2016

The title reaction between α,β‐unsaturated aldehydes and 2‐nitroallylic acetates followed by base‐mediated epimerization provides multifunctionalized cyclohexene derivatives in moderate yields and with excellent enantioselectivities as trans‐diastereomers, and cis‐diastereomers may be isolated upon omitting epimerization.
ChemInform Abstract: A Protocol for Amide Bond Formation with Electron Deficient Amines and Sterically Hindered Substrates.
Authors: Due‐Hansen Maria E. , Pandey Sunil K. , Christiansen Elisabeth , Andersen Rikke , Hansen Steffen V. F. , Ulven Trond
Published: April 2016

A method for efficient in situ coupling of sterically hindered carboxylic acids with hindered or electron deficient amines and oxazolidinones is developed.
ChemInform Abstract: Selective Direct N‐Alkylation of Amines with Alcohols Using Iron(III) Phthalocyanine Chloride under Solvent‐Free Conditions.
Authors: Minakawa Maki , Okubo Masataka , Kawatsura Motoi
Published: April 2016

N‐alkyl amines are prepared with excellent selectivity by mono‐alkylation of various primary aromatic amines with benzyl alcohols using microwave irradiation.
ChemInform Abstract: Regioselective Rhodium‐Catalyzed Addition of 1,3‐Dicarbonyl Compounds to Terminal Alkynes.
Authors: Beck Thorsten M. , Breit Bernhard
Published: April 2016

The title reaction has a broad substrate scope and provides valuable branched α‐allylated 1,3‐dicarbonyl compounds in often very high yields.
ChemInform Abstract: Rh(III)‐Catalyzed ortho‐Alkylation of N‐Benzyltriflamides with Diazo Compounds
Authors: Han Sang Hoon , Mishra Neeraj Kumar , Kim In Su
Published: April 2016

in the absence of external oxidants
ChemInform Abstract: Unprecedented Reaction of Ninhydrin with Ethyl Cyanoacetate and Diethyl Malonate on Ultrasonic Irradiation.
Authors: Saini Yeshwinder , Khajuria Rajni , Rana Love Karan , Hundal Geeta , Gupta Vivek K. , Kant Rajni , Kapoor Kamal K.
Published: April 2016

In addition to the title reactions, ninhydrin is also transformed with ethyl acetonate, ethyl nitroacetate, and dimedone.
ChemInform Abstract: Facile Synthesis of Functionalized 6‐Cyano‐2‐oxa‐7‐azabicyclo[4.1.0]hept‐3‐en‐1‐yl Acetates: A Catalyst Free Approach to Access the Pyran Fused 2‐Acetoxy‐NH‐aziridines.
Authors: Mukherjee Prasun , Das Asish R.
Published: April 2016

The highly functionalized products are obtained following a one‐step reaction of 4H‐pyrans or spiropyrans with iodobenzene diacetate without aid of any other reagent or catalyst.
ChemInform Abstract: A Fortuitously Straightforward Synthesis of 4‐Acetoxy‐2‐propyltetrahydrothiophene.
Authors: Ma Bianbian , Yang Shaoxiang , Tao Feiyan , Sun Baoguo , Liu Yongguo , Tian Hongyu
Published: April 2016

The title tetrahydrothiophene is synthesized by a three‐step procedure involving a known epoxidation step of 1‐hepten‐4‐ol and subsequent mesylation and acetoxylation‐ring closing reactions.
ChemInform Abstract: Palladium‐Catalyzed Propargylative and Allenylative Dearomatization of 2‐(Chloromethyl)thiophenes: Remarkable Effect of Solvents.
Authors: Ullah Aziz , Zhang Sheng , Bao Ming , Yamamoto Yoshinori , Almansour Abdulrahman I. , Arumugam Natarajan , Kumar Raju Suresh
Published: April 2016

The title reaction affords only propargylic compounds in coordinating solvent MeCN, but gives allenic compounds as major products in uncoordinating solvent CH2Cl2.
ChemInform Abstract: An Efficient Route to Regioselective Functionalization of Benzo[b]thiophenes via Palladium‐Catalyzed Decarboxylative Heck Coupling Reactions: Insights from Experiment and Computation.
Authors: Yang Daoshan , Liu Yuxia , Sun Pengfei , Zhang Ning , Wei Wei , Sun Mingyang , Chen Guang , Bi Siwei , Wang Hua
Published: April 2016

The decarboxylative Heck coupling reaction of 3‐chlorobenzo[b]thiophene‐2‐carboxylic acids (I) with styrenes leads to desired (E)‐3‐chloro‐2‐styrylbenzo[b]thiophenes (III) in good to high yields, while the reactions with 1‐pentene and methyl acrylate fail.
ChemInform Abstract: One‐Pot Synthesis of 14‐Aryl‐14 H‐Dibenzo[a,j]xanthene Derivatives Catalyzed by Nano‐Alumina Sulfuric Acid Through Solvent‐Free Conditions.
Authors: Davod Fereshteh , Kiasat Ali R. , Enjilzadeh Marzieh , Cheraghchi Mina
Published: April 2016

An environmentally friendly method for preparation of the title xanthenes by multicomponent condensation of naphthol and aromatic benzaldehydes in short times and high yield is developed.
ChemInform Abstract: Regioselective α‐Arylation of Coumarins and 2‐Pyridones with Phenylhydrazines under Transition‐Metal‐Free Conditions.
Authors: Chauhan Parul , Ravi Makthala , Singh Shikha , Prajapati Prashant , Yadav Prem P.
Published: April 2016

In addition to coumarins and N‐methyl or N‐unprotected 2‐pyridones the reaction is also applied to aza‐coumarins.
ChemInform Abstract: Cobalt‐Catalyzed Carbonylative Cyclization of Pyridinyl Diazoacetates for the Synthesis of Pyridoisoquinolinones.
Authors: Baek Yonghyeon , Kim Sunghwa , Jeon Bongkeun , Lee Phil Ho
Published: April 2016

The title reaction is extended to a semi‐one‐pot transformation of ethylpyridinyl aryl acetates into pyridoisoquinolinones.
ChemInform Abstract: Catalytic Enantioselective Synthesis of N—C Axially Chiral Phenanthridin‐6‐one Derivatives.
Authors: Hirata Tomoaki , Takahashi Isao , Suzuki Yuya , Yoshida Hiroaki , Hasegawa Hiroshi , Kitagawa Osamu
Published: April 2016

Phenanthridinone derivatives bearing ortho‐substituted phenyl groups on the nitrogen atom are enantioselectively obtained by a palladium/Segphos‐catalyzed intramolecular Buchwald—Hartwig amination.
ChemInform Abstract: Silica—ZnCl2: An Efficient and Reusable Solid Catalyst for One Pot Synthesis of 5‐Methyl Mercaptothiocarbonyl‐4‐aryl‐3‐dihydropyrimidin‐2(1H)‐ones under Solvent‐Free Conditions.
Authors: Devi Laishram Ronibala , Chanu Leimajam Vartima , Choi Hojune , Lee Dahyun , Singh Okram Mukherjee , Lee Sang‐Gyeong
Published: April 2016

An eco‐friendly method is developed for preparation of the title compounds by one‐pot three‐component reaction of β‐oxodithiocarboxylates, benzaldehydes, and urea.
ChemInform Abstract: Reaction of Elemental Phosphorus with α‐Methylstyrenes: One‐Pot Synthesis of Secondary and Tertiary Phosphines, Prospective Bulky Ligands for Pd(II) Catalysts.
Authors: Trofimov Boris A. , et al.
Published: April 2016

Depending on the reaction conditions, the one‐pot transformation of α‐methylstyrenes with red phosphorus gives secondary and tertiary phosphines or phosphinic acids.
ChemInform Abstract: Copper‐Catalyzed One‐Pot Tandem Synthesis of Unsymmetrical Diaryl Chalcogenides from Two Different Aryl Iodides.
Authors: Zhang Shaozhong , Koe Adam , Heintz Christina , Senior Aunajay , Jin Jin
Published: April 2016

Coupling of aryl iodides with elemental selenium or tellurium affords symmetrical diaryl dichalcogenide intermediates which are further converted to unsymmetrical diaryl chalcogenides through the reaction with different aryl iodides.
ChemInform Abstract: Synthesis of D‐Desosamine and Analogues by Rapid Assembly of 3‐Amino Sugars.
Authors: Zhang Ziyang , Fukuzaki Takehiro , Myers Andrew G.
Published: April 2016

Key step in the synthesis of D‐desosamine and analogs (V) is the chromatography‐free procedure for the coupling of chiral nitrobutanols (I) with glyoxal to give pure 3‐nitro sugars by crystallization.
ChemInform Abstract: A New Xanthone from the Pericarp of Garcinia mangostana.
Authors: Xu Tao , Deng Yunxia , Zhao Shengyin , Shao Zhiyu
Published: April 2016

A new prenylated xanthone, named mangostanate (I), is isolated from the pericarp of Garcinia mangostana.
ChemInform Abstract: Structure Revision of Pilidiostigmin from the Leaves of Pilidiostigma glabrum.
Authors: Carroll Anthony R.
Published: April 2016

The structure of natural pilidiostigmin is revised to structure (I) based on reinterpretation of the spectroscopic data.
ChemInform Abstract: Total Synthesis of (‐)‐Hymenosetin.
Authors: Kauhl Ulrich , Andernach Lars , Weck Stefan , Sandjo Louis P. , Jacob Stefan , Thines Eckhard , Opatz Till
Published: April 2016

Hymenosetin (I) and its N‐methyl analogue are prepared in 11 and 8 steps, respectively, from citronellal employing an intramolecular Diels‐Alder reaction as the key step.
ChemInform Abstract: Recent Advances in Transition Metal Phosphide Nanomaterials: Synthesis and Applications in Hydrogen Evolution Reaction
Authors: Shi Yanmei , Zhang Bin
Published: April 2016

Review: 50 refs.
ChemInform Abstract: Activation of Gold on Metal Carbides and the Discovery of Novel Catalysts for DeSOx and HDS Reactions
Authors: Rodriguez J. A. , Liu P. , Nakamura K. , Illas F.
Published: April 2016

Review: 53 refs.
ChemInform Abstract: New Developments in the Synthesis, Structure, and Applications of Borophosphates and Metalloborophosphates
Authors: Li Min , Verena‐Mudring Anja
Published: April 2016

Review: 178 refs.
ChemInform Abstract: Filling the Gap Between the Quantum and Classical Worlds of Nanoscale Magnetism: Giant Molecular Aggregates Based on Paramagnetic 3d Metal Ions
Authors: Papatriantafyllopoulou Constantina , Moushi Eleni E. , Christou George , Tasiopoulos Anastasios J.
Published: April 2016

Review: [syntheses, structures and magnetic properties of giant molecular 3d and 3d/4f paramagnetic metal clusters; 79 refs.
ChemInform Abstract: Lanthanide‐Based Luminescence Biolabeling
Authors: Sy Mohamadou , Nonat Aline , Hildebrandt Niko , Charbonniere Loic J.
Published: April 2016

Review: [182 refs.
ChemInform Abstract: Nitroolefins as Starting Materials for 5‐Membered N‐Heterocycles
Authors: Mierina Inese , Jure Mara
Published: April 2016

Review: 22 refs.
ChemInform Abstract: The Diaza[5.5.6.6]fenestrane Skeleton — Synthesis of Leuconoxine Alkaloids
Authors: Pfaffenbach Magnus , Gaich Tanja
Published: April 2016

Review: [36 refs.
ChemInform Abstract: Carbonylmetallates — A Special Family of Nucleophiles in Aromatic and Vinylic Substitution Reactions
Authors: Sazonov Petr K. , Beletskaya Irina P.
Published: April 2016

Review: [32 refs.
ChemInform Abstract: Strain‐Induced Helical Chirality in Polyaromatic Systems
Authors: Rickhaus Michel , Mayor Marcel , Juricek Michal
Published: April 2016

Review: 50 refs.
ChemInform Abstract: Organic Catalysts for Photocontrolled Polymerizations
Authors: Trotta Jacob T. , Fors Brett P.
Published: April 2016

Review: [43 refs.
ChemInform Abstract: Advanced Solid‐State NMR Techniques for the Study of Molecular Sieves
Authors: Mafra Luis , Klinowski Jacek
Published: April 2016

Review: 238 refs.
ChemInform Abstract: Molecular‐Level Understanding of Structural Changes of Organic Crystals Induced by Macroscopic Mechanical Stimulation
Authors: Seki Tomohiro , Ito Hajime
Published: April 2016

Review: [18 refs.
ChemInform Abstract: Smart Polymeric Nanoparticles as Emerging Tools for Imaging — The Parallel Evolution of Materials
Authors: Papadimitriou Sofia A. , Salinas Yolanda , Resmini Marina
Published: April 2016

Review: [62 refs.
ChemInform Abstract: Computational Studies on the Regioselectivity of Metal‐Catalyzed Synthesis of 1,2,3 Triazoles via Click Reaction: A Review
Authors: Hosseinnejad Tayebeh , Fattahi Bahareh , Heravi Majid M.
Published: April 2016

Review: 174 refs.
ChemInform Abstract: Computational Characterization and Prediction of Metal‐Organic Framework Properties
Authors: Coudert Francois‐Xavier , Fuchs Alain H.
Published: April 2016

Review: 335 refs.
Microtubule and microtubule associated protein anomalies in psychiatric disease
Authors: Marchisella Francesca , Coffey Eleanor T. , Hollos Patrik
Published: April 2016

Anomalies in neuronal cell architecture, in particular dendritic complexity and synaptic density changes, are widely observed in the brains of subjects with schizophrenia or mood disorders. The concept that a disturbed microtubule cytoskeleton underlies these abnormalities and disrupts synaptic connectivity is supported by evidence from clinical studies and animal models. Prominent changes in tubulin expression levels are commonly found in disease specific regions such as the hippocampus and prefrontal cortex of psychiatric patients. Genetic linkage studies associate tubulin‐binding proteins such as the dihydropyrimidinase family with an increased risk to develop schizophrenia and bipolar disorder. For many years, altered immunoreactivity of microtubule associated protein‐2 has been a hallmark found in the brains of individuals with schizophrenia. In this review, we present a growing body of evidence that connects a dysfunctional microtubule cytoskeleton with neuropsychiatric illnesses. Findings from animal models are discussed together with clinical data with a particular focus on tubulin post‐translational modifications and on microtubule‐binding proteins. © 2016 Wiley Periodicals, Inc.
Solution‐Based Chemical Process for Synthesis of Highly Active Li2S/Carbon Nanocomposite for Lithium‐Sulfur Batteries
Authors: Strubel Patrick , Althues Holger , Kaskel Stefan
Published: April 2016

A novel method for the preparation of Li2S integrated into porous carbon black as host material by using a facile solution‐based chemical process is described. Li2S was synthesized by disproportionation of a Li2S6 polysulfide solution. The combination of a homogeneous Li2S distribution with small Li2S particle size and good contact with the carbon surface leads to ideal properties for the application in high‐energy‐density long‐cycle‐life lithium‐sulfur batteries. An initial discharge capacity of 1259 mA h g−1sulfur with good cycle stability as well as low polarization are achieved, rendering the novel method particularly suitable for application in full cells with silicon‐ or carbon‐based anodes, which are used to overcome the main limitations observed using metallic lithium as anode in lithium‐sulfur batteries.
Conversion of Xylose to Furfuryl Alcohol and 2‐Methylfuran in a Continuous Fixed‐Bed Reactor
Authors: Cui Jinglei , Tan Jingjing , Cui Xiaojing , Zhu Yulei , Deng Tiansheng , Ding Guoqiang , Li Yongwang
Published: April 2016

An efficient process was designed for the synthesis of furfuryl alcohol and 2‐methylfuran from xylose using a continuous fixed‐bed reactor over a catalyst combining Hβ zeolite and Cu/ZnO/Al2O3 in γ‐butyrolactone (GBL)/water as solvent. The cooperative effect of Hβ zeolite and GBL facilitated the dehydration of xylose and enhanced largely the furfural yield. The production of furfuryl alcohol and 2‐methylfuran can be simply tuned by changing the hydrogenation temperature for furfural over the Cu/ZnO/Al2O3 catalyst. The yield for furfuryl alcohol reached 87.2 % at 150 °C whereas a yield of 86.8 % was achieved for 2‐methylfuran at 190 °C.
The Energy‐Autocorrelation Function in Magnetized and Unmagnetized Strongly Coupled Plasmas
Authors: Ott T. , Donkó Z. , Bonitz M.
Published: April 2016

The energy‐autocorrelation function is calculated for a screened Coulomb system in equilibrium and the contributions of different energy transport channels to the total heat conductivity are explored for magnetized and unmagnetized systems. A special focus is on the time scales of the energy‐autocorrelation function which contribute to the field‐parallel enhancement of heat conduction in strongly coupled plasmas. The investigation is based on first‐principle molecular dynamics simulations. (© 2016 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Equation of State of Nickel in WDM Region
Authors: Lomonosov I.V. , Gryaznov V.K.
Published: April 2016

Results of theoretical calculations and experimental measurements of the equation of state (EOS) in the region of warm dense matter (WDM) are discussed and applied to nickel. The thermodynamic properties of nickel and its phase diagram are calculated with the use of multi‐phase EOS model. Theoretical calculations of thermodynamic properties of the solid, liquid, and plasma phases, and of the critical point, are compared with results of experiments. The analysis deals with thermodynamic properties of solid nickel at T = 0 and 298 K from different band–structure theories, static compression experiments in diamond anvil cells, and the information obtained in shock‐wave experiments. Thermodynamic data in the liquid and plasma states, resulting from traditional thermophysical measurements, ”exploding wire” experiments, and evaluations of the critical point are presented. Numerous shock‐wave experiments for nickel have been done to measure shock adiabats of crystal and porous samples and release isentropes. These data are analyzed in a self‐consistent manner together with all other available data at high pressure. (© 2016 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
A native plant competitor mediates the impact of above‐ and belowground damage on an invasive tree
Authors: Carrillo Juli , Siemann Evan
Published: April 2016

Plant competition may mediate the impacts of herbivory on invasive plant species through effects on plant growth and defense. This may predictably depend on whether herbivory occurs above or below ground and on relative plant competitive ability. We simulated the potential impact of above‐ or belowground damage by biocontrol agents on the growth of a woody invader (Chinese tallow tree, Triadica sebifera) through artificial herbivory, with or without competition with a native grass, little bluestem (Schizachyrium scoparium). We measured two defense responses of Triadica through quantifying constitutive and induced extrafloral nectar production and tolerance of above‐ and belowground damage (root and shoot biomass regrowth). We examined genetic variation in plant growth and defense across native (China) and invasive (United States) Triadica populations. Without competition, aboveground damage had a greater impact than belowground damage on Triadica performance, whereas with competition and above‐ and belowground damage impacted Triadica similarly. Whole plant tolerance to damage below ground was negatively associated with tolerance to grass competitors indicating tradeoffs in the ability to tolerate herbivory vs. compete. Competition reduced investment in defensive extrafloral nectar (EFN) production. Aboveground damage inhibited rather than induced EFN production while belowground plant damage did not impact aboveground nectar production. We found some support for the evolution of increased competitive ability hypothesis for invasive plants as United States plants were larger than native China plants and were more plastic in their response to biotic stressors than China plants (they altered their root to shoot ratios dependent on herbivory and competition treatments). Our results indicate that habitat type and the presence of competitors may be a larger determinant of herbivory impact than feeding mode and suggest that integrated pest management strategies including competitive dynamics of recipient communities should be incorporated into biological control agent evaluation at earlier stages.
Landscape‐scale ecohydrological mapping demonstrating how flood inundation water quality types relate to floodplain vegetation communities
Authors: Keizer F. M. , Schot P. P. , Okruszko T. , Wassen M. J.
Published: April 2016

Landscape‐scale ecohydrological mapping is commonly restrained to one‐dimensional ecohydrological transect studies or two‐dimensional vegetation distributions lacking adequate spatial coverage of explanatory hydrological data. The objective of this paper is to construct a two‐dimensional (semi‐3D) landscape‐scale ecohydrological map based on vegetation distribution maps and detailed spatial, multi‐year, floodplain inundation water quality data. The dataset comes from the near‐natural Biebrza floodplain mire in Poland encompassing 658 inundation water quality analyses over the period 2002–2012, covering 17 different vegetation communities of freshwater marshes and rich fens. The data represent the main hydrological gradients from valley edge to river encompassing groundwater seepage, local stagnant precipitation influences and river flooding and drainage. We used chi‐squared Haberman residuals analysis to correlate communities to inundation water quality types, resembling river water and three different types of groundwater. Out of 17 communities, six showed a preference for river water, three showed a preference for clean groundwater, four for diluted groundwater and one for polluted groundwater. For three communities, no significant preference was found. Spatial patterns in vegetation and attributed water quality preference can be linked to three dominant hydrological processes at the landscape scale, i.e. discharge of clean and polluted groundwater near the valley edges, dilution of exfiltrated groundwater with local snowmelt and precipitation water and flooding with river water along the river. The ecohydrological relations are depicted in two‐dimensional maps and a semi‐3D diagram with typical cross sections. Copyright © 2016 John Wiley & Sons, Ltd.
Plasma calcidiol, calcitriol, and parathyroid hormone and risk of new onset heart failure in a population‐based cohort study
Authors: Meems Laura M. G. , Brouwers Frank P. , Joosten Michel M. , Lambers Heerspink Hiddo J. , de Zeeuw Dick , Bakker Stephan J. L. , Gansevoort Ron T. , van Gilst Wiek H. , van der Harst Pim , de Boer Rudolf A.
Published: April 2016

Background

Heart failure (HF) is a major problem in the Western world, with increasing prevalence and incidence. Because HF cannot be cured, prevention of HF is of utter importance. Calcidiol, calcitriol, and parathyroid hormone (PTH) have been identified as risk factors for cardiovascular disease. However, their association with new onset HF remains to be established. We investigated whether calcidiol, calcitriol, and PTH could be used to identify those subjects at risk for new onset HF, and if they had additive predictive value over established risk predictors like N‐terminal‐pro Brain‐type natriuretic peptide and highly sensitive Troponin‐T.

Methods and results

We examined 7470 HF‐free participants in Prevention of Renal and Vascular End‐stage Disease, a community‐based cohort study in Groningen, the Netherlands (latitude 53°N, mean age: 49 years, 48% male). During follow‐up time of 12.6 years (interquartile range: 12.3–12.9), 281 participants (4%) developed HF: 181 (66%) HF with reduced and 94 (34%) HF with preserved ejection fraction (HFrEF [left ventricular ejection fraction ≤ 40%], and HFpEF [left ventricular ejection fraction ≥ 50%], respectively). Mean (±SD) of calcidiol was 58 (±24) nmol/L, mean calcitriol 145 (±48) pmol/L, and median (interquartile range) PTH was 3.7 (3.0–4.6) pmol/L. Calcidiol levels were univariately associated with new onset HF [hazard ratio (HR) 0.82 (95% CI 0.69–0.96)], but calcitriol levels were not [HR 0.85 (95% CI 0.71–1.03)]. PTH levels kept their predictive value after adjustment for age, sex, and day of blood withdrawal (HR 1.26 [95% CI 1.04–1.53]). However, in our full model this association was lost [HR 1.10 (95% CI 0.92–1.32)]. Calcidiol, calcitriol, and PTH could not differentiate between new onset HFrEF or HFpEF.

Conclusions

After adjustment for confounding factors, a single measurement of plasma calcidiol, calcitriol, or PTH was not associated with risk of developing HF. Screening for these markers to identify subjects at risk for new onset HF cannot be advocated.
Expansion of a Discrete [3 × 3] Mn9 Metallogrid to a µ‐Carboxylato‐Bridged Polymeric {Mn11}n Assembly
Authors: Lakma Avinash , Hossain Sayed Muktar , Pradhan Rabindra Nath , Topwal Dinesh , Cornia Andrea , Singh Akhilesh Kumar
Published: April 2016

Compounds based on the [3 × 3] nonamanganese(II) square grid motif and featuring additional manganese(II) ions linked to the grid core were isolated through a strict self‐assembly approach. Extended tritopic picolinic dihydrazide ligands were used, which contain terminal ester groups and differ in the R substituent on the para position of the central pyridine ring (H2L1, R = OCH3; H2L2, R = H). Upon reaction with Mn(OAc)2·4H2O, the ligand H2L1 undergoes hydrolysis and spontaneous self‐assembly to afford [Mn10(L1′)6(H2O)5][Mn(H2O)6]2·11H2O, where a pentaaquomanganese(II) unit is connected to one of the terminal carboxylate functions of the grid through a Mn–O bond. The same reaction carried out with H2L2 affords an unprecedented 2D polymeric structure [Mn11(L2′)6(H2O)8][Mn(H2O)6]·24H2O, in which each nonamanganese grid is connected to its four neighbors through tetraaquomanganese(II) centers, again linked to the carboxylate functions. The two compounds also contain [Mn(H2O)6]2+ complexes in the lattice. These metallogrid‐based compounds, for which DC magnetic data were collected and analysed in detail, emphasize the rich binding affinity and bridging versatility of the used ligands, which provide access to both discrete complexes and extended polymeric assemblies.
Highly DNA‐Photoreactive Ruthenium 1,4,5,8‐Tetraazaphenanthrene Complex Conjugated to the TAT Peptide: Efficient Vectorization inside HeLa Cells without Phototoxicity – The Importance of Cellular Distribution
Authors: Marcélis Lionel , Kajouj Sofia , Ghesquière Jonathan , Fettweis Gregory , Coupienne Isabelle , Lartia Rémy , Surin Mathieu , Defrancq Eric , Piette Jacques , Moucheron Cécile , Kirsch‐De Mesmaeker Andrée
Published: April 2016

The photoreactive [Ru(TAP)2(phen)]2+ (TAP = 1,4,5,8‐tetraazaphenanthrene; phen = 1,10‐phenanthroline) complex tethered to the cell‐penetrating peptide (CPP) TAT was studied in vitro and in cellulo. The tethering of the complex does not affect its behavior under blue‐light irradiation in the presence of guanine‐containing oligodeoxyribonucleotides (ODNG). Thus, the luminescence is quenched in the presence of ODNG, and gel electrophoresis experiments showed the appearance of products corresponding to the irreversible attachment of the conjugate to ODNG upon illumination. The cellular uptake of the conjugate was examined by flow cytometry, inductively coupled plasma mass spectrometry (ICP‐MS), and confocal imaging microscopy. These experiments showed that the [Ru(TAP)2(phen‐TAT)] conjugate is readily taken up by HeLa cells and, despite these favorable factors, the cellular survival was 100 %, as measured by a 3‐(4,5‐dimethylthiazol‐2‐yl)‐2,5‐diphenyltetrazolium bromide (MTT) assay. A possible origin of the inactivity of [Ru(TAP)2(phen‐TAT)] under irradiation is proposed on the basis of the fluorescence‐activated cell sorting (FACS), ICP‐MS, and confocal microscopy results.
Zinc‐Catalyzed Multicomponent Reactions: Easy Access to Furyl‐Substituted Cyclopropane and 1,2‐Dioxolane Derivatives
Authors: Mata Sergio , González Jesús , Vicente Rubén , López Luis A.
Published: April 2016

A convenient synthesis of cyclopropyl‐substituted furan derivatives by a zinc‐catalyzed three‐component coupling of 1,3‐dicarbonylic compounds, 2‐alkynals and alkenes is reported. A sequence consisting of an initial Knoevenagel condensation, cyclization, and a final cyclopropanation reaction would account for the formation of the final products. In most cases, this multicomponent process proceeds in good yield under mild reaction conditions and in the presence of a low catalyst loading. The efficient formation of 1,2‐dioxolane derivatives by the zinc‐promoted aerobic oxidation of some cyclopropane derivatives is also reported. The 1,2‐dioxolane derivatives are also available by a four‐component reaction.
Quantitation of low molecular weight sugars by chemical derivatization‐liquid chromatography/multiple reaction monitoring/mass spectrometry
Authors: Han Jun , Lin Karen , Sequria Carita , Yang Juncong , Borchers Christoph H.
Published: April 2016

A new method for the separation and quantitation of 13 mono‐ and disaccharides has been developed by chemical derivatization/ultra‐HPLC/negative‐ion ESI‐multiple‐reaction monitoring MS. 3‐Nitrophenylhydrazine (at 50°C for 60 min) was shown to be able to quantitatively derivatize low‐molecular weight (LMW) reducing sugars. The nonreducing sugar, sucrose, was not derivatized. A pentafluorophenyl‐bonded phase column was used for the chromatographic separation of the derivatized sugars. This method exhibits femtomole‐level sensitivity, high precision (CVs of ≤ 4.6%) and high accuracy for the quantitation of LMW sugars in wine. Excellent linearity (R2 ≥ 0.9993) and linear ranges of ∼500‐fold for disaccharides and ∼1000–4000‐fold for monosaccharides were achieved. With internal calibration (13C‐labeled internal standards), recoveries were between 93.6% ± 1.6% (xylose) and 104.8% ± 5.2% (glucose). With external calibration, recoveries ranged from 82.5% ± 0.8% (ribulose) to 105.2% ± 2.1% (xylulose). Quantitation of sugars in two red wines and two white wines was performed using this method; quantitation of the central carbon metabolism‐related carboxylic acids and tartaric acid was carried out using a previously established derivatization procedure with 3‐nitrophenylhydrazine as well. The results showed that these two classes of compounds—both of which have important organoleptic properties—had different compositions in red and white wines.