bluuebunny/crossref_metadata_2025 huggingface dataset:
Mechanistic Understanding of the Divergent Cyclizations of o‐Alkynylbenzaldehyde Acetals and Thioacetals Catalyzed by Metal Halides
Authors: Mi Yanhua , Zhou Tao , Wang Kung‐Pern , Lee Daesung , Xia Yuanzhi
Published: September 2015

The mechanisms of regiodivergent cyclizations of o‐alkynylbenzaldehyde acetals and thioacetals catalyzed by Pd and Pt halides are studied. DFT calculations found that both reactions are initiated by electrophilic activation of the acetylenic moiety instead of the previously proposed metal‐triggered CX (X=O, S) cleavage. Both the regioselective cyclization of the π‐alkyne complex and the chemoselective [1,2]‐migration in the carbenoid intermediate were determined as key steps to achieving the observed divergence. For acetal derivatives containing an internal alkyne, the 6‐endo‐dig cyclization is more favorable and leads to the carbenoid intermediate easily through further steps of CX fragmentation and carbocation cyclization. Then, from the carbenoid intermediate, the [1,2]‐migration of sulfur is easier than that of H, Me, and Ph; whereas, a reversed aptitude was predicted for the oxygen analogue, which is consistent with the greater ability of sulfur atoms to stabilize β‐carbocations. However, for precursors containing a terminal alkyne, the 5‐exo‐dig pathway is preferred and only the 1,2‐disubstituted indene product is seen, irrespective of the nature of the acetal; thus, a different product from that reported in the literature is predicted for benzaldehyde acetal with a terminal alkyne at the ortho position. This prediction led us to reconsider some of the reported results and hidden realities were uncovered with solid new experimental evidence.
Ruthenium(II)‐Catalyzed CH Functionalizations with Allenes: Versatile Allenylations and Allylations
Authors: Nakanowatari Sachiyo , Ackermann Lutz
Published: September 2015

Ruthenium(II)‐catalyzed direct CH functionalization of aromatic compounds with allenes was achieved under exceedingly mild reaction conditions to yield trisubstituted allenes. The reactions of N‐methoxybenzamides proceeded smoothly in an isohypsic fashion at ambient temperature with high chemo‐ and regioselectivity, thereby providing a versatile means of accessing trisubstituted allenes. Detailed mechanistic studies were suggestive of a kinetically relevant CH metalation step, which occurs by the assistance of a carboxylate moiety; this also set the stage for unprecedented CH allylations with removable directing groups in a step‐economical fashion.
ChemInform Abstract: Structural and Electronic Investigations of PbTa4O11 and BiTa7O19 Constructed from α‐U3O8 Types of Layers.
Authors: Boltersdorf Jonathan , Maggard Paul A.
Published: September 2015

PbTa4O11 (I) is prepared by flux‐mediated ion‐exchange by heating a 10:1 molar mixture of PbCl2 and Ag2Ta4O11 (evacuated silica tubes, 700 °C, 96 h) with the precursor Ag2Ta4O11 being prepared by solid state reaction of Ag2O and Ta2O5 (alumina crucible, 1000 °C, 24 h).
ChemInform Abstract: New Rhombohedral Pyrochlores Ca2Ln3Sb3O14 (Ln = Lanthanide and Y): Space Group Revised.
Authors: Fu W. T. , Ijdo D. J. W.
Published: September 2015

The structure of Ca2Ln3Sb3O14 (Ln: lanthanides, Y) is re‐examined by Rietveld refinements of either combined X‐ray and neutron diffraction or XRD data alone.
ChemInform Abstract: Al‐Doped Zinc Oxide Nanostructures as Transparent Conductive Window Layer for Photovoltaic Applications.
Authors: Mohite R. M. , Kothawale R. R.
Published: September 2015

ZnO:Al (5 wt.%) (AZO) nanorod thin films are deposited on glass plates from an aqueous solution of Zn(NO3)2, EDTA, en, and AlCl3 together with PEG as a morphology controlling surfactant (65 °C, 6 h) followed by staged annealing (200, 300, and 400 °C, 5 h each).
ChemInform Abstract: Phase Equilibria in BaB2O4—LiF System and β‐BaB2O4 Bulk Crystals Growth.
Authors: Simonova E. A. , Kokh A. E. , Kononova N. G. , Shevchenko V. S. , Kokh D. A.
Published: September 2015

Using BaCO3, H3BO3, and LiF as starting materials a phase diagram of the title system is established by solid state synthesis (Pt crucible, 700 °C, 3—5 d), differential thermal analysis, modified visual polythermal analysis, and XRD.
ChemInform Abstract: Organic—Inorganic Hybrid Materials Based on Basket‐Like {Ca@P6Mo18O73} Cages.
Authors: Zhang He , Yu Kai , Lv Jing‐hua , Gong Li‐hong , Wang Chun‐mei , Wang Chun‐xiao , Sun Di , Zhou Bai‐Bin
Published: September 2015

Compounds (IV), (VI), (VII), and (VIII) are hydrothermally synthesized and their structures are determined by single crystal XRD.
ChemInform Abstract: RFe2MgxAl8‐x (R: La—Nd and Sm; x ≈ 0.8): Flux Synthesis, Structure, Magnetic and Electrical Properties.
Authors: Ma Xiaowei , Chai Ping , Chen Banghao , Lochner Eric , Latturner Susan E.
Published: September 2015

Single crystals of Mg‐substituted CeFe2Al8‐type intermetallics LnFe2MgxAl8‐x (Ln: La—Nd, Sm; x ≤ 1) are grown by reaction of Fe and Ln in a 1:1 Mg/Al reactive flux (steel capsules in evacuated silica tubes, 950 °C, 5 h; controlled cooling).
ChemInform Abstract: Noncentrosymmetric Rare‐Earth Copper Gallium Chalcogenides RE3CuGaCh7 (RE: La—Nd; Ch: S, Se): An Unexpected Combination.
Authors: Iyer Abishek K. , Rudyk Brent W. , Lin Xinsong , Singh Harpreet , Sharma Arzoo Z. , Wiebe Christopher R. , Mar Arthur
Published: September 2015

Ln3CuGaS7 and Ln3CuGaSe7 (Ln: La—Nd) are prepared by heating stoichiometric amounts of the elements (evacuated silica tubes, 1050 °C (sulfides)/900 °C (selenides), 5 d).
ChemInform Abstract: Mild Arylboronic Acid Catalyzed Selective [4 + 3] Cycloadditions: Access to Cyclohepta[b]benzofurans and Cyclohepta[b]indoles.
Authors: Cao Kou‐Sen , Bian Hong‐Xu , Zheng Wen‐Hua
Published: September 2015

3,5‐Bis(trifluoromethyl)benzeneboronic acid proves to be an efficient catalyst for the cycloaddition of allylic cations with various dienes under mild reaction conditions.
ChemInform Abstract: Catalytic Intramolecular Aminofluorination, Oxyfluorination, and Carbofluorination with a Stable and Versatile Hypervalent Fluoroiodine Reagent.
Authors: Yuan Weiming , Szabo Kalman J.
Published: September 2015

For the first time, three types of fluorocyclization reactions are accomplished by using the same fluorination reagent (HFR).
ChemInform Abstract: Accessing Nitrosocarbonyl Compounds with Temporal and Spatial Control via the Photoredox Oxidation of N‐Substituted Hydroxylamines.
Authors: Frazier Charles P. , Palmer Leoni I. , Samoshin Andrey V. , Read de Alaniz Javier
Published: September 2015

Highly reactive acylnitroso species are generated from hydroxamic acids (I) via photoredox catalysis.
ChemInform Abstract: Safe and Convenient Nitroxyl Radical and Imide Dual Catalyzed NaOCl Oxidation of Alcohols to Aldehydes/Ketones.
Authors: Fukuda Naohiro , Izumi Minoru , Ikemoto Tomomi
Published: September 2015

A combination of cyanuric acid, NaOCl, K2CO3, and TEMPO or 2‐azaadamantane N‐oxyl is described as an efficient system for the oxidation of primary alcohols to carboxylic acids and secondary alcohols to ketones.
ChemInform Abstract: Enantioselective Fluorination of β‐Ketoesters Catalyzed by Complexes of New Mono‐Oxazoline Ligands.
Authors: Niu Teng , Han Xiping , Huang Danfeng , Wang Ke‐Hu , Su Yingpeng , Hu Yulai , Fu Ying
Published: September 2015

A new kind of mono‐oxazoline ligand (OXP) is prepared and used as catalyst for the enantioselective fluorination of β‐ketoesters by NFSI.
ChemInform Abstract: Reductions of Aryl Bromides in Water at Room Temperature.
Authors: Fennewald James C. , Landstrom Evan B. , Lipshutz Bruce H.
Published: September 2015

Surfactant (NOK) generates nanoreactors in water in which the reduction of aryl bromides with NaBH4 proceeds efficiently.
ChemInform Abstract: Enantioselective 1,4‐Addition of Cyclopropylboronic Acid Catalyzed by Rhodium/Chiral Diene Complexes.
Authors: Takechi Ryosuke , Nishimura Takahiro
Published: September 2015

Regioselective cyclopropylation of alkenylsulfones (I) and (IV), enones (VI), enoates (VIII) and nitroalkenes (X) proceeds in good to high yields and with high enantioselectivities.
ChemInform Abstract: Copper‐Free Arylation of 3,3‐Disubstituted Allylic Halides with Triazene‐Softened Aryl Grignard Reagents.
Authors: Xu Lijun , Liu Zhubo , Dong Weipeng , Song Jinyu , Miao Maozhong , Xu Jianfeng , Ren Hongjun
Published: September 2015

The α‐ vs.
ChemInform Abstract: Rhodium‐Catalyzed Hydroformylation of 1,1‐Disubstituted Allenes Employing the Self‐Assembling 6‐DPPon System.
Authors: Koepfer Alexander , Breit Bernhard
Published: September 2015

Disubstituted 3‐butenals are formed (Z)‐selectively by hydroformylation of allenes in the presence of the rhodium catalyst.
ChemInform Abstract: One‐Pot Dehydrations Using Phenyl Isothiocyanate.
Authors: Majetich George , Irvin Thomas C. , Thompson Stephen B.
Published: September 2015

Alcohols, e.g. (I), (III), (V) and (VII), undergo dehydration after conversion into the corresponding sodium carbonimidothioate salts followed by pyrolysis.
ChemInform Abstract: Synthesis of Thioacetal via AgOTf‐Catalyzed Reaction of 2‐Alkynylbenzaldehyde with Thiol.
Authors: Wu Ran , Gao Shang , Yang Guanghui , Pan Lingling , Liu Ming , Hu Keyong , Zhong Weihui , Yu Chuanming
Published: September 2015

The title reaction affords 2‐alkynylbenzaldehyde thioacetals (III) in good to excellent yields at room temperature in short reaction times.
ChemInform Abstract: Synthesis of α‐Trifluoroethoxy‐Substituted Ketones.
Authors: Wang Yuguang , You Yi , Weng Zhiqiang
Published: September 2015

The nucleophilic substitution of α‐haloketones with 2,2,2‐trifluoroethanol is readily accomplished in the presence of Cs2CO3 as the base to give α‐(2,2,2‐trifluoroethoxy)ketones under mild reaction conditions.
ChemInform Abstract: Difluoroallylation Using a 2‐Bromomethyl‐1,1‐difluoroalk‐1‐ene.
Authors: Mears Paul R. , Thomas Eric J.
Published: September 2015

A variety of aromatic and aliphatic aldehydes are difluoroallylated by the title difluoroalkene (I) leading to fluorinated methylenealkanols (III) in good to excellent yields.
ChemInform Abstract: A Convenient Synthesis of Dialkyl 2‐(2‐Haloethylidene)malonates, Cyanoacetates and Halocrotonates by One Carbon Extension
Authors: Sathishkumar S. , Mahasampathgowri S. , Balasubramanian K. K. , Saiganesh R.
Published: September 2015

using dimethylsulfoxonium methylide
ChemInform Abstract: A Novel Method for Synthesis of α‐Keto Esters with Phenyliodine(III) Diacetate.
Authors: Xie Yuanyuan , Liu Jiwei , Huang Yingyi , Yao Lixia
Published: September 2015

This method gives also access to α‐keto amides.
ChemInform Abstract: Ruthenium‐Catalyzed Rearrangement of Propargyl Sulfoxides: Formation of α,β‐Unsaturated Thioesters.
Authors: Zheng Renhua , Wang Youliang , Zhang Liming
Published: September 2015

A Ru catalyzed transformation of propargyl sulfoxides (I) into synthetically useful α,β‐unsaturated thioesters (II) is developed.
ChemInform Abstract: Rhodium‐Catalyzed Addition—Spirocyclization of Arylboronic Esters Containing β‐Aryl α,β‐Unsaturated Ester Moiety.
Authors: Matsuda Takanori , Yasuoka Satoshi , Watanuki Shoichi , Fukuhara Keisuke
Published: September 2015

Spirocyclic 1‐indanones are synthesized by rhodium‐catalyzed spirocyclization involving sequential transmetalation, intramolecular addition to a C=C bond, and β‐oxygen elimination.
ChemInform Abstract: An Alkyne Hydrosilylation—Hiyama Coupling Approach to Highly Functionalized 1,3‐Dienes.
Authors: McAdam Catherine A. , McLaughlin Mark G. , Cook Matthew J.
Published: September 2015

Both hydrosilylation and Hiyama coupling give E isomers exclusively.
ChemInform Abstract: Convenient N‐Acetylation of Amines in N,N‐Dimethylacetamide with N,N‐Carbonyldiimidazole.
Authors: Chikkulapalli Anil , Aavula Sanjeev Kumar , Rifahath Mona N. P. , Karthikeyan C. , Vinodh Kumar C. H. , Manjunatha Sulfur G. , Shanmugam Sumathi
Published: September 2015

The acetylation agent (I) also acts as solvent.
ChemInform Abstract: Ru(II)‐Catalyzed Site‐Selective Hydroxylation of Flavone and Chromone Derivatives: The Importance of the 5‐Hydroxyl Motif for the Inhibition of Aurora Kinases.
Authors: Kim Kiho , Choe Hyeonjeong , Jeong Yujeong , Lee Jun Hee , Hong Sungwoo
Published: September 2015

The title reaction allows a rapid and site‐selective installation of the hydroxyl group.
ChemInform Abstract: Enantioselective Synthesis of Tertiary Propargylic Alcohols under N‐Heterocyclic Carbene Catalysis.
Authors: Sanchez‐Diez Eduardo , Fernandez Maitane , Uria Uxue , Reyes Efraim , Carrillo Luisa , Vicario Jose L.
Published: September 2015

An enantioselective unprecedented NHC‐catalyzed benzoin reaction of aromatic and aliphatic aldehydes with alkyl alkynyl ketones including trifluoromethyl ketones is developed.
ChemInform Abstract: Selective Access to All Four Diastereomers of a 1,3‐Amino Alcohol by Combination of a Keto Reductase‐ and an Amine Transaminase‐Catalyzed Reaction.
Authors: Kohls Hannes , Anderson Mattias , Dickerhoff Jonathan , Weisz Klaus , Cordova Armando , Berglund Per , Brundiek Henrike , Bornscheuer Uwe T. , Hoehne Matthias
Published: September 2015

The synthetic pathway to obtain the (2R,4R)‐enantiomer (III) is outlined.
ChemInform Abstract: Selective Oxidative Deoximation with Anhydrous Ce(IV) Sulfate.
Authors: Asutay Oktay , Hamarat Niluefer , Uludag Nesimi , Coskun Necdet
Published: September 2015

The title method allows the cleavage of oximes to their parent aldehydes and ketones in good yields.
ChemInform Abstract: Palladium‐Catalyzed Asymmetric Arylation of C(sp3)—H Bonds of Aliphatic Amides: Controlling Enantioselectivity Using Chiral Phosphoric Amides/Acids.
Authors: Yan Shao‐Bai , Zhang Song , Duan Wei‐Liang
Published: September 2015

Among various chiral ligands tested, BPA is found to be the most efficient one.
ChemInform Abstract: [2,3]‐Sigmatropic Rearrangement of Propargylic Sulfinates by a Pale Cu1‐USY Zeolite and Copper Salts.
Authors: Hampton Carissa S. , Harmata Michael
Published: September 2015

Copper ions are found to catalyze the [2,3]‐sigmatropic rearrangement of propargylic sulfinates (I), (III), and (V) to allenic sulfones (II), (IV), and (VI), respectively.
ChemInform Abstract: Organocatalyzed Benzannulation for the Construction of Diverse Anthraquinones and Tetracenediones.
Authors: Somai Magar Krishna Bahadur , Xia Likai , Lee Yong Rok
Published: September 2015

The reaction of α,β‐unsaturated aldehydes with quinone derivatives gives the annulated title compounds in high yields with remarkable regioselectivities.
ChemInform Abstract: AgNO2‐Mediated Cleavage of the N—N Bond of Sulfonylhydrazones and Oxygen Transfer: Access to Fulleroisoxazolines via Radical Cyclization with [60]Fullerene.
Authors: Liu Tong‐Xin , Ma Jinliang , Chao Di , Zhang Pengling , Liu Qingfeng , Shi Lei , Zhang Zhiguo , Zhang Guisheng
Published: September 2015

An unprecedented AgNO2‐mediated novel transformation of sulfonylhydrazones with [60]fullerene to various fulleroisoxazolines is presented.
ChemInform Abstract: Light‐Driven Nitrile Imine‐Mediated Tetrazole—Ene Cycloaddition as a Versatile Platform for Fullerene Conjugation.
Authors: Sugawara Yuuki , Jasinski Nils , Kaupp Michael , Welle Alexander , Zydziak Nicolas , Blasco Eva , Barner‐Kowollik Christopher
Published: September 2015

An efficient methodology for modular fullerene functionalization via photo‐induced nitrile imine‐mediated tetrazole—ene cycloaddition (NITEC) is introduced.
ChemInform Abstract: Use of the Thiophenesulfonyl Protecting Group in the Catalytic, Asymmetric Synthesis of Unprotected β‐Lactams.
Authors: Wang Yazhong , Calter Michael A.
Published: September 2015

The thiophenesulfonyl group is found to be compatible with the catalytic, enantioselective synthesis of β‐lactams (III) from acid chlorides (II) and sulfonyl imines (I).
ChemInform Abstract: Iodine‐Catalyzed Radical Oxidative Annulation for the Construction of Dihydrofurans and Indolizines.
Authors: Tang Shan , Liu Kun , Long Yue , Gao Xinlong , Gao Meng , Lei Aiwen
Published: September 2015

The iodine‐catalytic system can be scaled up to 20 mmol with an excellent efficiency.
ChemInform Abstract: Copper‐Catalyzed [4 + 1] Annulation Between α‐Hydroxy Ketones and Nitriles: An Approach to Highly Substituted 3(2H)‐Furanones.
Authors: He Haitao , Qi Chaorong , Hu Xiaohan , Ouyang Lu , Xiong Wenfang , Jiang Huanfeng
Published: September 2015

The facile and highly efficient method allows the approach to a broad spectrum of the required biologically interesting furanone structures.
ChemInform Abstract: Regioselective Synthesis of Multisubstituted Furans via Copper‐Mediated Coupling Between Ketones and β‐Nitrostyrenes.
Authors: Ghosh Monoranjan , Mishra Subhajit , Hajra Alakananda
Published: September 2015

A broad spectrum of di‐ and trisubstituted furans is available in a completely regioselective manner following conditions A).
ChemInform Abstract: Synthesis and Characterization of Tetraarylporphyrins in the Presence of Nano‐TiCl4·SiO2.
Authors: Zamani Leila , Mirjalili Bi Bi Fatemeh
Published: September 2015

Synthesis of tetraarylporphyrins by the coupling of an aromatic aldehyde and pyrrole using nano‐TiCl4·SiO2 as a mild, inexpensive, and highly efficient catalyst is studied.
ChemInform Abstract: Palladium‐Catalyzed Asymmetric Allylic Amination of Racemic Butadiene Monoxide with Isatin Derivatives.
Authors: Li Gen , Feng Xiangqing , Du Haifeng
Published: September 2015

A palladium‐catalyzed asymmetric allylic amination of racemic butadiene monoxide with isatins and their derivatives as nucleophiles under mild reaction conditions is successfully realized using a chiral P/terminal‐olefin ligand.
ChemInform Abstract: Iodine‐Mediated C—H Functionalization of sp, sp2, and sp3 Carbon: A Unified Multisubstrate Domino Approach for Isatin Synthesis.
Authors: Satish Gandhesiri , Polu Ashok , Ramar Thangeswaran , Ilangovan Andivelu
Published: September 2015

The approach to the desired isatins is possible starting from 2′‐aminophenylacetylenes, 2′‐aminostyrenes and 2′‐amino‐β‐ketoesters via oxidative amidation in the presence of specified amounts of iodine.
ChemInform Abstract: Efficient Synthesis of Chiral Indolines Using an Imine Reductase from Paenibacillus lactis.
Authors: Li Hao , Luan Zheng‐Jiao , Zheng Gao‐Wei , Xu Jian‐He
Published: September 2015

2‐Phenyl‐3,3‐dimethyl‐3H‐indole and 2′‐Methylspiro[cyclohexane‐1,3′‐(3′H)‐indole] don′t yield the desired products using the presented reaction conditions.
ChemInform Abstract: Stereocontrolled Intramolecular Iron‐Mediated Tandem [6 + 2]‐Ene‐Type Diene/Dienol Ether Double Cyclization Reactions.
Authors: Pearson Anthony J. , Zhang Sheng
Published: September 2015

The photothermally induced title reaction is catalyzed by a pendant iron carbonyl moiety and provides diastereomerically pure spirotricyclic products in high yields.
ChemInform Abstract: A New Type of Lewis Acid‐Base Bifunctional M(salphen) (M: Zn, Cu and Ni) Catalysts for CO2 Fixation.
Authors: Ren Yanwei , Chen Jungui , Qi Chaorong , Jiang Huanfeng
Published: September 2015

The catalyst can be easily recycled and reused at least 5 times.
ChemInform Abstract: An Efficient Synthesis of gem‐Diiodoolefins and (E)‐Iodoalkenes from Propargylic Amides with a Cu(I)/Cu(III) Cycle.
Authors: Zhang Shuo , Chen Ying , Wang Jianwu , Pan Yue , Xu Zhenghu , Tung Chen‐Ho
Published: September 2015

The resulting mono‐ and diiodoalkenes can be used in Suzuki, Heck and Sonogashira coupling reactions furnishing the corresponding tri‐ and tetrasubstituted alkenes.
ChemInform Abstract: A Convenient Strategy to 2,4,5‐Triaryl and 2‐Alkyl‐4,5‐diaryl Oxazole Derivatives Through Silver‐Mediated Oxidative C—O Cross Coupling/Cyclization.
Authors: Sarkar Rajib , Mukhopadhyay Chhanda
Published: September 2015

A simple protocol is developed for the synthesis of oxazoles from 1,2‐diketones and primary amines via Ag(I)‐mediated Cα(sp3)—H activation of the amines followed by oxidative C—O cross coupling and cyclization.
ChemInform Abstract: Facile Synthesis of 2,5‐Disubstituted Thiazoles from Terminal Alkynes, Sulfonyl Azides, and Thionoesters.
Authors: Miura Tomoya , Funakoshi Yuuta , Fujimoto Yoshikazu , Nakahashi Junki , Murakami Masahiro
Published: September 2015

Procedures are evaluated for the preparation of various thiazole structures either from triazole precursors (prepared from terminal alkynes and sulfonyl azides) or directly starting with their formation in a one‐pot approach.
ChemInform Abstract: Access to Substituted Dihydrothiopyrano[2,3‐b]indoles via Sequential Rearrangements During S‐Alkylation and Au‐Catalyzed Hydroarylation on Indoline‐2‐thiones.
Authors: Jha Mukund , Shelke Ganesh M. , Cameron T. Stanley , Kumar Anil
Published: September 2015

Various cyclization precursors are prepared from indoline‐2‐thiones and selected unsaturated alcohols.
ChemInform Abstract: Synthesis of Cinnolin‐3(2H)‐one Derivatives from Rh‐Catalyzed Reaction of Azobenzenes with Diazotized Meldrum′s Acid.
Authors: Son Jeong‐Yu , Kim Sunghwa , Jeon Woo Hyung , Lee Phil Ho
Published: September 2015

Both symmetrical and unsymmetrical azobenzenes can be used in the title synthesis.
ChemInform Abstract: Efficient Synthesis of Pyrrolo[2,3‐d]pyrimidines via a Cu(I)/6‐Methylpicolinic Acid Catalyzed Coupling Reaction
Authors: Jiang Xi , Sun Dequn , Jiang Yongwen , Ma Dawei
Published: September 2015

of 4‐amino‐5‐bromopyrimidines with alkynes
ChemInform Abstract: Rearrangement of Oxazolo[3,2‐a]pyridines as an Approach of Synthesizing Aza[3.3.2]cyclazines.
Authors: Babaev Eugene V. , Nevskaya Aleksandra A. , Dlynnikh Ilya V.
Published: September 2015

Dihydropyridine derivative (I) is used as starting material for oxazolopyridinium perchlorate (V) and indolizine derivatives (VII), (IX), and (XI).
ChemInform Abstract: Nitrosation of 5H‐Thiazolo[3,2‐a]pyrimidin‐3(2H)‐ones.
Authors: Lashmanova Evgenia A. , Shiryaev Andrey K.
Published: September 2015

The title nitrosation reaction enables the formation of 2‐(hydroxyimino)thiazolo[3,2‐a]pyrimidinones (II) in moderate yields.
ChemInform Abstract: Ligand‐Free Copper‐Catalyzed Coupling of α‐Amino Acids with N‐Boc‐2‐iodoanilines for the Synthesis of Enantiopure 3‐Substituted Dihydroquinoxalinones.
Authors: Luo Sheng , De Brabander Jef K.
Published: September 2015

The initially obtained N‐arylated α‐amino acids (III) are subsequently transformed into enantiomerically pure 3‐substituted dihydroquinoxalinones (IV) via Boc‐deprotection/condensation.
ChemInform Abstract: Synthesis and Biological Activity of Fluorinated 7‐Benzylamino‐2‐phenyl‐1,2,4‐triazolo[1,5‐a][1,3,5]triazin‐5‐amines.
Authors: Dolzhenko Anna V. , Tan Bee Jen , Chiu Gigi Ngar Chee , Chui Wai Keung , Dolzhenko Anton V.
Published: September 2015

5‐Azapurine derivatives (V) having fluorinated benzyl groups are developed and tested for anticancer and antiangiogenic properties.
ChemInform Abstract: The Chemistry of Redox‐Flow Batteries
Authors: Noack Jens , Roznyatovskaya Nataliya , Herr Tatjana , Fischer Peter
Published: September 2015

Review: introduction of a systematic classification of electrolyte systems; 339 refs.
ChemInform Abstract: Recent Advances in the Construction of Lanthanide‐Copper Heterometallic Metal‐Organic Frameworks
Authors: Zhang Shaowei , Cheng Peng
Published: September 2015

Review: 137 refs.
ChemInform Abstract: Isatin Derivatives in Reactions with Phosphorus(III—V) Compounds
Authors: Musin Lenar I. , Bogdanov Andrei V. , Mironov Vladimir F.
Published: September 2015

Review: 148 refs.
ChemInform Abstract: Benign Approaches for the Microwave‐Assisted Synthesis of Five‐Membered 1,2‐N,N‐Heterocycles
Authors: Kaur Navjeet
Published: September 2015

Review: 122 refs.
ChemInform Abstract: 1,4‐Dioxo‐1,4‐dihydronaphthalene‐2,3‐dicarbonitrile and 1,1,2,2‐Tetracyanoethene in Heterocyclization
Authors: Aly Ashraf A.
Published: September 2015

Review: 93 refs.
ChemInform Abstract: Asymmetric Synthesis of Pyrazoles and Pyrazolones Employing the Reactivity of Pyrazolin‐5‐one Derivatives
Authors: Chauhan Pankaj , Mahajan Suruchi , Enders Dieter
Published: September 2015

Review: [64 refs.
ChemInform Abstract: Artificial Diiron Enzymes with a de novo Designed Four‐Helix Bundle Structure
Authors: Chino Marco , Maglio Ornella , Nastri Flavia , Pavone Vincenzo , DeGrado William F. , Lombardi Angela
Published: September 2015

Review: 174 refs.
ChemInform Abstract: Redox‐State Dependent Ligand Exchange in Manganese‐Based Oxidation Catalysis
Authors: Abdolahzadeh Shaghayegh , de Boer Johannes W. , Browne Wesley R.
Published: September 2015

Review: 188 refs.
ChemInform Abstract: 1,3‐Dipolar Cycloadditions of Azomethine Imines
Authors: Najera Carmen , Sansano Jose M. , Yus Miguel
Published: September 2015

Review: [162 refs.
ChemInform Abstract: Deactivation of Solid Catalysts in Liquid Media: The Case of Leaching of Active Sites in Biomass Conversion Reactions
Authors: Sadaba Irantzu , Lopez Granados Manuel , Riisager Anders , Taarning Esben
Published: September 2015

Review: 121 refs.
ChemInform Abstract: Gold‐Catalyzed Reactions via Cyclopropyl Gold Carbene‐Like Intermediates
Authors: Dorel Ruth , Echavarren Antonio M.
Published: September 2015

Review: 119 refs.
ChemInform Abstract: Multifunctional Nanoparticles: Recent Progress in Cancer Therapeutics
Authors: Raju G. Seeta Rama , Benton Leah , Pavitra E. , Yu Jae Su
Published: September 2015

Review: 102 refs.
ChemInform Abstract: The Potential of Microwave in Organophosphorus Syntheses
Authors: Keglevich Gyorgy , Kiss Nora Zsuzsa , Jablonkai Erzsebet , Balint Erika , Mucsi Zoltan
Published: September 2015

Review: 27 refs.
ChemInform Abstract: Wittig Reactions of Trialkylphosphine‐Derived Ylides: New Directions and Applications in Organic Synthesis
Authors: McNulty James , McLeod David , Das Priyabrata , Zepeda‐Velazquez Carlos
Published: September 2015

Review: 48 refs.
ChemInform Abstract: P‐Chirogenic Secondary Phosphine Oxides: New Stereoselective Synthesis and Applications
Authors: Dutartre Mathieu , Bayardon Jerome , Eymin Marie‐Joelle , Juge Sylvain
Published: September 2015

Review: 8 refs.
ChemInform Abstract: Synthesis of Quinazolines and Quinazolinones via Palladium‐Mediated Approach
Authors: Abdou Ibrahim M. , Al‐Neyadi Shaikha S.
Published: September 2015

Review: 59 refs.
ChemInform Abstract: Annulated 3‐Amino‐4‐imino‐pyrimidines: Their Utility as Useful Precursors for the Synthesis of Fused Heterocycles
Authors: Ahmad Sami A. S. Shawali
Published: September 2015

Review: 76 refs.
ChemInform Abstract: Organic and Inorganic Azides in Fullerene Chemistry: Achievements and Trends
Authors: Tuktarov Airat R. , Akhmetov Arslan R. , Dzhemilev Usein M.
Published: September 2015

Review: 118 refs.
ChemInform Abstract: Uranium‐Mediated Oxidative Addition and Reductive Elimination
Authors: Lu Erli , Liddle Stephen T.
Published: September 2015

Review: 115 refs.
ChemInform Abstract: EPR Spectroscopy as a Tool in Homogeneous Catalysis Research
Authors: Goswami Monalisa , Chirila Andrei , Rebreyend Christophe , de Bruin Bas
Published: September 2015

Review: 104 refs.
ChemInform Abstract: Mechanistic Insights for the Development of Li—O2 Battery Materials: Addressing Li2O2 Conductivity Limitations and Electrolyte and Cathode Instabilities
Authors: McCloskey Bryan D. , Burke Colin M. , Nichols Jessica E. , Renfrew Sara E.
Published: September 2015

Review: 139 refs.
ChemInform Abstract: Modeling Free Radical Polymerization Using Dissipative Particle Dynamics
Authors: Yong Xin , Kuksenok Olga , Balazs Anna C.
Published: September 2015

Review: 46 refs.
Glycerol dehydration to acrolein: Selectivity control over CsPW/Nb2O5 catalyst
Authors: Liu Chang , Liu Rong , Wang Tiefeng
Published: September 2015

The catalytic dehydration of glycerol to acrolein is a very attractive alternative to the propylene‐based process, due to the future exhaustion of fossil feedstocks and the increasing production of biomass‐based glycerol. This work aimed to study the selectivity control over Cs2.5H0.5PW12O40/Nb2O5 (CsPW‐Nb). The Brønsted and Lewis acid sites were characterized by FTIR to understand the catalytic mechanism. The effects of reaction temperature (260−360 °C), oxygen co‐feed ratio (0−0.175), and glycerol concentration (0.2−0.5 g/g) were studied to determine the optimum conditions for the production of acrolein. The loading of CsPW on Nb2O5 increased the Brønsted acidity and enhanced the acrolein dehydration route. Co‐feeding oxygen at an appropriate ratio significantly enhanced the selectivity of the acrolein dehydration route and slightly enhanced the selectivity of the acetol dehydration route by suppressing the glycerol oligomerization reaction. The selectivity to acrolein significantly decreased when the glycerol concentration increased from 0.2 to 0.5 g/g due to increased glycerol oligomerization reactions. The acrolein selectivity in dehydration of glycerol was affected by reaction temperature, oxygen co‐feeding, and glycerol concentration. The highest acrolein selectivity (76.5 %) was obtained at 320 °C, O2/N2/glycerol molar ratio of 1/5/0.16 (mol/mol), and glycerol concentration of 0.2 g/g.
Influence of Structural Parameters on the Self‐Association Properties of Anti‐HIV Catanionic Dendrimers
Authors: Perez‐Anes Alexandra , Rodrigues Fernanda , Caminade Anne‐Marie , Stefaniu Cristina , Tiersch Brigitte , Turrin Cédric‐Olivier , Blanzat Muriel
Published: September 2015

The self‐association properties of anti‐HIV catanionic dendrimers as multivalent galactosylceramide (GalCer)‐derived inhibitors are presented. The study was designed to elucidate the origin of the relatively high cytotoxicity values of these anti‐HIV catanionic dendrimers, which have previously been found to exhibit in vitro anti‐HIV activity in the submicromolar range. The physicochemical properties of these catanionic dendrimers were studied to tentatively correlate the structural parameters with self‐association and biological properties. We can conclude from this study that the absence of correlation between the hydrophobicity and the cytotoxicity of the catanionic systems could be explained by the partial segregation of the different partners of the catanionic entities.
Role of endocannabinoids in the progression of diabetic retinopathy
Authors: Behl Tapan , Kaur Ishneet , Kotwani Anita
Published: September 2015

In the past decades, the role of numerous factors in the pathophysiology of diabetic retinopathy has been explored, following which marked progress has been made in developing several novel therapeutic options, such as anti‐vascular endothelial growth factor, anti‐tumor necrosis factor‐alpha and various other anti‐inflammatory and anti‐angiogenic agents, for the treatment of diabetic retinopathy. However, the involvement of endocannabinoid system in its pathogenesis has not been much explored. This review aims at unveiling every aspect of association of the endocannabinoid system and its interactions with various physiological and pathological pathways to induce disease progression. The various alterations induced by endocannabinoids, such as anandamide and 2‐arachidonylglycerol, in retina during hyperglycaemia clearly demonstrate and verify their involvement in aggravating the pathological conditions, hence leading to the progression of diabetic retinopathy. Exploring this involvement furthermore, in greater depths, might be beneficial in acknowledging and understanding the hidden aspects of the pathogenesis of this complication even better and might provide a therapeutically beneficial alternative target to combat and restrict its progression amongst diabetic patients. Copyright © 2015 John Wiley & Sons, Ltd.
Inadequate hepcidin serum concentrations predict incident type 2 diabetes mellitus
Authors: Pechlaner Raimund , Weiss Günter , Bansal Sukhvinder , Mayr Manuel , Santer Peter , Pallhuber Barbara , Notdurfter Marlene , Bonora Enzo , Willeit Johann , Kiechl Stefan
Published: September 2015

Background

Type 2 diabetes mellitus (T2DM) is closely associated with elevated body iron stores. The hormone hepcidin is the key regulator of iron homeostasis. Inadequately low hepcidin levels were recently reported in subjects with manifest T2DM. We investigated whether alterations of hepcidin levels precede the manifestation of T2DM and predict T2DM development independently of established risk conditions.

Methods

This prospective population‐based study included 675 subjects aged 50–89 years, 51.9% of whom were female. Hepcidin levels were measured by gold standard tandem mass spectrometry. Diabetes was diagnosed according to American Diabetes Association criteria, and incident diabetes was recorded between baseline in 2000 and 2010.

Results

The baseline hepcidin‐to‐ferritin ratio in subjects that subsequently developed diabetes during follow‐up was reduced on average by 29.8% as compared with subjects with normal glucose tolerance (95% confidence interval, −50.7% to −0.2%; p = 0.049). After adjustment for age, sex, and serum ferritin, higher hepcidin levels were associated with reduced risk of incident diabetes (hazard ratio per 1‐unit higher log2 hepcidin, 0.80; 95% confidence interval, 0.64–0.98; p = 0.035; 33 events). Additional adjustment for established diabetes risk factors and determinants of hepcidin concentration did not appreciably change these results (HR, 0.81; 95% CI, 0.66–0.99). Likewise, inadequately low hepcidin levels were also detected in subjects with prevalent T2DM (n = 76).

Conclusions

Hepcidin levels that are inadequately low in relation to body iron stores are an independent predictor for incident T2DM and may contribute to diabetes‐related tissue iron overload. Copyright © 2015 John Wiley & Sons, Ltd.
The more pieces, the better the puzzle: sperm concentration increases gametic compatibility
Authors: Sherman Craig D. H. , Ab Rahim Emi S. , Olsson Mats , Careau Vincent
Published: September 2015

The genetic benefits individuals receive from mate choice have been the focus of numerous studies, with several showing support for both intrinsic genetic benefits and compatibility effects on fertilization success and offspring viability. However, the robustness of these effects have rarely been tested across an ecologically relevant environmental gradient. In particular, sperm environment is a crucial factor determining fertilization success in many species, especially those with external fertilization. Here, we test the importance of sperm environment in mediating compatibility‐based selection on fertilization using a factorial breeding design. We detected a significant intrinsic male effect on fertilization success at only one of four sperm concentrations. Compatibility effects were significant at the two highest sperm concentrations and, interestingly, the magnitude of the compatibility effect consistently increased with sperm concentration. This suggests that females are able to modify the probability of sperm–egg fusion as the amount of sperm available increases.
The transduction pattern of IL‐12‐encoding lentiviral vectors shapes the immunological outcome
Authors: Goyvaerts Cleo , Broos Katrijn , Escors David , Heirman Carlo , Raes Geert , De Baetselier Patrick , Thielemans Kris , Breckpot Karine
Published: September 2015

In situ modification of antigen‐presenting cells garnered interest in cancer immunotherapy. Therefore, we developed APC‐targeted lentiviral vectors (LVs). Unexpectedly, these LVs were inferior vaccines to broad tropism LVs. Since IL‐12 is a potent mediator of antitumor immunity, we evaluated whether this proinflammatory cytokine could enhance antitumor immunity of an APC‐targeted LV‐based vaccine. Therefore, we compared subcutaneous administration of broad tropism LVs (VSV‐G‐LV) with APC‐targeted LVs (DC2.1‐LV)‐encoding enhanced GFP and ovalbumin, or IL‐12 and ovalbumin in mice. We show that codelivery of IL‐12 by VSV‐G‐LVs or DC2.1‐LVs augments CD4+ or CD8+ T‐cell proliferation, respectively. Furthermore, we demonstrate that codelivery of IL‐12 enhances the CD4+ TH1 profile irrespective of its delivery mode, while an increase in cytotoxic and therapeutic CD8+ T cells was only induced upon VSV‐G‐LV injection. While codelivery of IL‐12 by DC2.1‐LVs did not enhance CD8+ T‐cell performance, it increased expression of inhibitory checkpoint markers Lag3, Tim3, and PD‐1. Finally, the discrepancy between CD4+ T‐cell stimulation with and without functional CD8+ T‐cell stimulation by VSV‐G‐ and DC2.1‐LVs is partly explained by the observation that IL‐12 relieves CD8+ T cells from CD4+ T‐cell help, implying that a TH1 profile is of minor importance for antitumor immunotherapy if IL‐12 is exogenously delivered.
5‐Nitriminotetrazole 1‐Oxide: An Exciting Oxygen‐ and Nitrogen‐Rich Heterocycle
Authors: Fischer Dennis , Klapötke Thomas M. , Stierstorfer Jörg
Published: September 2015

5‐Nitriminotetrazole 1‐oxide (CH2N6O3) and selected salts (e.g., dipotassium, diammonium, dihydroxylammonium) were prepared and characterized for the first time. The neutral molecule can be obtained by nitration of an O‐protected 5‐aminotetrazole 1‐oxide. The new compounds were characterized by using low‐temperature X‐ray diffraction as well as IR, Raman, and multinuclear NMR spectroscopy and elemental analysis. Differential scanning calorimetry measurements showed a large range for the decomposition temperatures. The highest value of 320 °C was observed for the dipotassium salt. The energetic performances (detonation velocities up to 9842 m s–1) were calculated with the EXPLO5 code by using calculated (CBS‐4M) heats of formation and experimentally obtained X‐ray densities. Calculated performance data support the highly energetic character of these new compounds. The sensitivities toward impact, friction, and electrostatic discharge were also determined.
Seismic design and testing of buckling‐restrained braces with a thin profile
Authors: Lin Pao‐Chun , Tsai Keh‐Chyuan , Chang Chieh‐An , Hsiao Yu‐Yun , Wu An‐Chien
Published: September 2015

A thin‐profile buckling‐restrained brace (thin‐BRB) consists of a rectangular steel casing and a flat steel core that is parallel to a gusset plate. A thin configuration reduces the width of the restraining member and thus saves usable space in buildings. However, deformable debonding layers, which cover the steel core plate in order to mitigate the difference between the peak tensile and compressive axial forces, provide a space for the steel core to form high mode buckling waves when the thin‐BRB is under compression. The wave crests squeeze the debonding layers and produce outward forces on the inner surface of the restraining member. If the restraining member is too weak in sustaining the outward forces, local bulging failure occurs and the thin‐BRB loses its compression capacity immediately. In order to investigate local bulging behavior, a total of 22 thin‐BRB specimens with a ratio of steel core plate to restraining steel tube depth ranging from 0.3 to 0.7 and axial yield force capacities ranging from 421 kN to 3036 kN were tested by applying either cyclically increasing, decreasing, or constant axial strains. The restraining steel tube widths of all the specimens were smaller than 200 mm and were infilled with mortar with a compressive strength of 97 MPa or 55 MPa. Thirteen of the 22 thin‐BRB specimens' restraining members bulged out when the compressive core strains exceeded 0.03. A seismic design method of the thin‐BRB in preventing local bulging failure is proposed in this study. Test and finite element model (FEM) analysis results suggest that the outward forces can be estimated according to the BRB compressive strength, steel core high mode buckling wavelength, and the debonding layer thickness. In addition, the capacity of the restraining member in resisting the outward forces can be estimated by using the upper bound theory in plastic analysis. Both the FEM analysis and test results indicate that the proposed method is effective in predicting the possibility of local bulging failure. Test results indicate that the proposed design method is conservative for thin‐BRB specimens with a large steel core plate to restraining steel tube depth ratio. This paper concludes with design recommendations for thin‐BRBs for severe seismic services. Copyright © 2015 John Wiley & Sons, Ltd.
Suicidal Ideation and Behaviours Among Adolescents Receiving Bariatric Surgery: A Case–Control Study
Authors: McPhee Jeanne , Khlyavich Freidl Eve , Eicher Julia , Zitsman Jeffrey L. , Devlin Michael J. , Hildebrandt Tom , Sysko Robyn
Published: September 2015

Objective

This study examined the prevalence and correlates of suicidal ideation and behaviour (SI/B) among adolescents receiving bariatric surgery.

Method

Charts of 206 adolescents receiving bariatric surgery were reviewed. Cases with SI/B (current/lifetime reported at baseline or event occurring in the programme n = 31, 15%) were case matched on gender, age and surgery type to 31 adolescents reporting current or past psychiatric treatment and 31 adolescents denying lifetime SI/B or psychiatric treatment.

Results

Before surgery, adolescents with SI/B reported significantly lower total levels of health‐related quality of life (p = 0.01) and greater depressive symptoms (p = 0.004) in comparison with candidates who never received psychiatric treatment. No significant differences were found between groups for the change in depressive symptoms or body mass index following surgery.

Conclusions

As in studies of adults, a notable subset of adolescents receiving bariatric surgery indicated pre‐operative or post‐operative SI/B. It is critical that clinicians evaluate and monitor adolescent patients undergoing bariatric surgery for risk of SI/B. Copyright © 2015 John Wiley & Sons, Ltd and Eating Disorders Association.
Effect of activated carbon or biochars on toxicity of different soils contaminated by mixture of native polycyclic aromatic hydrocarbons and heavy metals
Authors: Kołtowski Michał , Oleszczuk Patryk
Published: September 2015

Activated carbon (AC), biochar from wheat straw (BCS), and biochar from willow (BCW) were added to the soils sampled from areas of strong anthropogenic influence at doses of 0.5%, 1%, 2.5%, or 5% (w/w) and incubated for 2 mo. At the end of this period, the toxicity of the soils was measured. The effect of AC and biochars on the toxicity of the soils varied based on soil, type of amendment, dose, and test organism. For most of the parameters tested, the highest effectiveness of AC in terms of reduction of toxicity was observed in soil POPI (from bitumen processing plant area). In the case of the remaining soils, after the addition of AC varied results were observed, in which a reduction or an increase of toxicity, relative to the control soil, occurred. As in the case of AC, biochars also caused a significant reduction of phytotoxicity of soil POPI. In soils KB (from coking plant area, industrial waste deposit) and KOK (from coking plant area, coking battery), the reduction or increase of toxicity depended on biochar dose. Compared with the biochars, the effectiveness of AC in the reduction of toxicity depended also on soil, type of amendment, dose, and test organism. Generally, the AC was more effective than biochars in relation to mortality and reproduction of Folsomia candida (in all soils) and for reduction of luminescence inhibition of Vibrio fischeri (in POPI soil). Environ Toxicol Chem 2016;35:1321–1328. © 2015 SETAC
Proximate, mineral, and antinutrient compositions of indigenous Okra (Abelmoschus esculentus) pod accessions: implications for mineral bioavailability
Authors: Gemede Habtamu Fekadu , Haki Gulelat Desse , Beyene Fekadu , Woldegiorgis Ashagrie Z. , Rakshit Sudip Kumar
Published: September 2015

The promotion and consumption of indigenous vegetables could help to mitigate food insecurity and alleviate malnutrition in developing countries. Nutrient and antinutrient compositions of eight accessions of Okra Pods were investigated. Molar ratios and mineral bioavailability of Okra pod accessions were also calculated and compared to the critical values to predict the implications for mineral bioavailability. Proximate and mineral composition of Okra pod accessions were determined using standard methods of Association of Official Analytical Chemists. The result of the study revealed that the proximate composition (g/100 g) in dry weight basis was significantly (P < 0.05) varied and ranged: moisture/dry matter 9.69–13.33, crude protein 10.25–26.16, crude fat 0.56–2.49, crude fiber 11.97–29.93, crude ash 5.37–11.30, utilizable carbohydrate 36.66–50.97, and gross energy 197.26–245.55 kcal/100 g. The mineral concentrations (mg/100 g) were also significantly (P < 0.05) varied and ranged: calcium (111.11–311.95), Iron (18.30–36.68), potassium (122.59–318.20), zinc (3.83–6.31), phosphorus (25.62–59.72), and sodium (3.33–8.31) on dry weight bases. The Okra Pods of “OPA#6” accession contained significantly higher amounts of crude protein, total ash, crude fat, calcium, iron, and zinc than all other accessions evaluated in this study. The results of antinutrients analysis showed that, except phytate, tannin, and oxalate contents of all the accessions were significantly (P < 0.05) varied. The range of phytate, tannin, and oxalate contents (mg/100 g) for Okra pod accessions studied were as follows: 0.83–0.87, 4.93–9.90, and 0.04–0.53, respectively. The calculated molar ratios of phytate: calcium, phytate: iron, phytate: zinc, oxalate: calcium and [Phytate][Calcium]/[Zinc] were below the critical value and this indicate that the bioavailability of calcium, iron, and zinc in these accessions could be high. The results of the study revealed that Okra pod contain appreciable amount of vital nutrients like protein, fiber, calcium, iron, and zinc and low in antinutrient contents with high mineral bioavailability. Therefore, increase in the production and consumption of these nutrient‐rich indigenous Okra pods will help to supplement/formulate the diets and alleviate the problems associated with malnutrition in the country.
Loss of IL‐4Rα–mediated PI3K signaling accelerates the progression of IgE/mast cell–mediated reactions
Authors: Sledd Jane , Wu David , Ahrens Richard , Lee Jeebong , Waggoner Lisa , Tsai Ying Ting , Wang Yui‐Hsi , Hogan Simon P.
Published: September 2015

Clinical and experimental evidence indicate that polymorphisms within the interleukin 4 (IL‐4) receptor (IL‐4R) chain are sufficient for altered strength of IL‐4/IL‐13 signaling, leading to an exaggerated allergic inflammatory response and increase susceptibility to allergic phenotypes. In the present study, we show that ablation of IL‐4Rα–induced phosphatidylinositol 3‐kinase (PI3K) activating signal by germline point mutation within the IL‐4Rα motif (Y500F) did not alter susceptibility to IgE‐mediated, food‐induced experimental anaphylaxis. Moreover, diarrhea occurrence, antigen‐specific IgE and intestinal mastocytosis were comparable between WT and IL‐4RαY500F mice. However, mice unable to stimulate IL‐4Rα–mediated PI3K signaling had accelerated disease progression. Notably, the accelerated anaphylactic response was associated with more rapid histamine‐induced hypovolemia. Mechanistic in vitro and in vivo analyses revealed that endothelial IL‐4Rα PI3K signaling negatively regulates the histamine‐induced endothelial leak response. These results define an unanticipated role for IL‐4Rα–mediated PI3K signaling in negative regulation of IgE‐mediated anaphylactic reactions.