bluuebunny/crossref_metadata_2025 huggingface dataset:
ChemInform Abstract: Protodeboronation of Tertiary Boronic Esters: Asymmetric Synthesis of Tertiary Alkyl Stereogenic Centers.
Authors: Nave Stefan , Sonawane Ravindra P. , Elford Tim G. , Aggarwal Varinder K.
Published: April 2011

Tertiary boronic esters smoothly undergo protodeboronation in the presence of CsF or TBAF in aqueous solution.
ChemInform Abstract: Cooperative Catalysis in Highly Enantioselective Mannich‐Type Three‐Component Reaction of a Diazoacetophenone with an Alcohol and an Imine.
Authors: Xu Xinfang , Qian Yu , Yang Liping , Hu Wenhao
Published: April 2011

High diastereo‐ and enantioselectivities are observed in the three‐component Mannich‐type reaction of diazoacetophenone (I) with alcohol (III) and para‐ or meta‐substituted aromatic imines (II) using a Rh2(O‐Ac)4/BINOL‐derived chiral phosphoric acid catalyst combination.
ChemInform Abstract: Enantioselective Copper‐Catalyzed Intramolecular O—H Insertion: An Efficient Approach to Chiral 2‐Carboxy Cyclic Ethers.
Authors: Zhu Shou‐Fei , Song Xiao‐Guang , Li Yu , Cai Yan , Zhou Qi‐Lin
Published: April 2011

A highly enantioselective intramolecular carbene insertion into an X—H bond is developed.
ChemInform Abstract: Catalytic Activity of Gold Nanoclusters in Intramolecular Hydroamination of Alkenes and Alkynes with Toluenesulfonamide under Aerobic and Basic Conditions.
Authors: Kitahara Hiroaki , Sakurai Hidehiro
Published: April 2011

Under conditions A), 5‐ and 6‐aminoalkenes as well as 5‐aminoalkynes smoothly undergo cyclization to afford pyrrolidine and piperidine derivatives.
ChemInform Abstract: Broensted Acid Catalyzed Cyclization of Hydroxylated Enynes: A Concise Synthesis of Five‐Membered Heterocycles.
Authors: Ji Ke‐Gong , Chen Jin , Zhu Hai‐Tao , Yang Fang , Shaukat Ali , Liang Yong‐Min
Published: April 2011

A mild and direct route to five‐membered heterocyclic compounds from hydroxylated enynes is reported.
ChemInform Abstract: Facile Dearomatization of Nitrobenzene Derivatives and Other Nitroarenes with N‐Benzyl Azomethine Ylide.
Authors: Lee Sunyoung , Chataigner Isabelle , Piettre Serge R.
Published: April 2011

The TFA‐catalyzed reaction of nitroarenes or heterocycles featuring a less pronounced aromatic character affords a variety of pyrrolo‐fused polycycles in a highly regioselective manner.
ChemInform Abstract: Oxidation of Primary and Secondary Alkanols with the CeIII—LiBr—H2O2 System.
Authors: Kapustina N. I. , Sokova L. L. , Nikishin G. I.
Published: April 2011

In organic oxidations the system CeIII—LiBr—H2O2 is used for the first time.
ChemInform Abstract: Palladium‐Catalyzed Asymmetric Synthesis of Allylic Fluorides.
Authors: Katcher Matthew H. , Doyle Abigail G.
Published: April 2011

A new methodology for the enantioselective synthesis of allylic fluorides is developed.
ChemInform Abstract: Palladium‐Catalyzed Inter‐ and Intramolecular Hydroamination of Styrenes Coupled with Alcohol Oxidation Using N‐Fluorobenzenesulfonimide as the Oxidant.
Authors: Xu Tao , Qiu Shuifa , Liu Guosheng
Published: April 2011

It provides an effective method to prepare amines like (III) and (V) and pyrrolidines such as (VII) and (IX).
ChemInform Abstract: Direct Synthesis of Organic Azides from Primary Amines with 2‐Azido‐1,3‐dimethylimidazolinium Hexafluorophosphate.
Authors: Kitamura Mitsuru , Yano Masakazu , Tashiro Norifumi , Miyagawa Satoshi , Sando Mitsuyoshi , Okauchi Tatsuo
Published: April 2011

A stable, solid and easy to handle diazo‐transfer reagent is prepared.
ChemInform Abstract: Direct Arylations of Electron‐Deficient (Hetero)arenes with Aryl or Alkenyl Tosylates and Mesylates
Authors: Ackermann Lutz , Fenner Sabine
Published: April 2011

using a Pd/XPhos catalyst system (45 examples)
ChemInform Abstract: Ring‐Rearrangement Metathesis of Substituted Dihydropyrans and Dihydrofurans.
Authors: Donnard Morgan , Tschamber Theophile , Le Nouen Didier , Desrat Sandy , Hinsinger Karen , Eustache Jacques
Published: April 2011

Examples for functionalization of the substrates either prior to the metathesis reaction or following it are additionally given to demonstrate the value of this method for the preparation of nonclassical saccharides.
ChemInform Abstract: Copper‐Catalyzed Hydrocarboxylation of Alkynes Using Carbon Dioxide and Hydrosilanes.
Authors: Fujihara Tetsuaki , Xu Tinghua , Semba Kazuhiko , Terao Jun , Tsuji Yasushi
Published: April 2011

Copper complexes (I) bearing an N‐heterocyclic carbene ligand are efficient catalysts for the hydrocarboxylation of unsymmetrical or symmetrical alkynes using SiH(OEt)3 as reducing agent to give α,β‐unsaturated carboxylic acids as (E)‐isomers.
ChemInform Abstract: Highly Efficient Synthesis of Amides via Ritter Chemistry with Ionic Liquids.
Authors: Kalkhambkar Rajesh G. , Waters Sarah N. , Laali Kenneth K.
Published: April 2011

The Broensted‐acidic [bmimSO3H]OTf is found to be an efficient catalytic medium for the reaction of nitriles with tertiary alcohols.
ChemInform Abstract: New General Synthesis of α‐Alkoxyketones via α′‐Alkylation, α‐Alkylation and α,α′‐Dialkylation of α‐Alkoxyketimines.
Authors: Colpaert Filip , Mangelinckx Sven , Rocchetti Maria Teresa , De Kimpe Norbert
Published: April 2011

The α‐methoxyketones are prepared via deprotonation of the starting propylidene amine (I) with LDA, followed by reaction with alkyl halides and hydrolysis of the imino functionality.
ChemInform Abstract: The Grob—Eschenmoser Fragmentation of Cycloalkanones Bearing β‐Electron Withdrawing Groups: A General Strategy to Acyclic Synthetic Intermediates.
Authors: Hierold Judith , Hsia Tina , Lupton David W.
Published: April 2011

Introduction of a electron‐withdrawing group to cycloalkanones enables facile C—C bond fragmentation.
ChemInform Abstract: Phosphine‐Catalyzed Cascade [3 + 2] Cyclization—Allylic Alkylation, [2 + 2 + 1] Annulation, and [3 + 2] Cyclization Reactions Between Allylic Carbonates and Enones.
Authors: Zhou Rong , Wang Jianfang , Song Haibin , He Zhengjie
Published: April 2011

Depending on the nature of educts, the PBu3‐catalyzed reaction of allylic carbonates with enones allows efficient formation of cascade [3 + 2] cyclization—allylic alkylation, [3 + 2] cyclization, or [2 + 2 + 1] annulations products.
ChemInform Abstract: Competitive Pathways in the Reaction of Lithium Oxy‐ortho‐quinodimethanes and Fischer Alkoxy Alkynyl Carbene Complexes: Synthesis of Highly Functionalized Seven‐Membered Benzocarbocycles.
Authors: Garcia‐Garcia Patricia , Novillo Carlos , Fernandez‐Rodriguez Manuel A. , Aguilar Enrique
Published: April 2011

Reaction of in situ generated 1‐oxy‐ortho‐quinodimethanes with alkoxy alkynyl Fischer carbene complexes can provide four different cycloadducts depending on the substrate structure and on the reaction solvent used.
ChemInform Abstract: The First Example of Trimethylsilyl Methylenenitronate Reacting with Aldehydes under an Apparent Mukaiyama Nitro‐Aldol Reaction.
Authors: MacDonald Frank K. , Carneiro Karina M. M. , Pottie Ian R.
Published: April 2011

The reaction with (I) as the starting nitroalkane is presented.
ChemInform Abstract: Cu‐Catalyzed Carbon‐Heteroatom Coupling Reactions under Mild Conditions Promoted by Resin‐Bound Organic Ionic Bases.
Authors: Huang Yao‐Bing , Yang Chu‐Ting , Yi Jun , Deng Xiao‐Jian , Fu Yao , Liu Lei
Published: April 2011

The resin‐bound organic ionic bases promote efficiently Cu‐catalyzed carbon—heteroatom couplings as well as Ni‐catalyzed Suzuki and Pd‐catalyzed Heck reactions.
ChemInform Abstract: Hydrogen‐Bonding‐Promoted Oxidative Addition and Regioselective Arylation of Olefins with Aryl Chlorides.
Authors: Ruan Jiwu , Iggo Jonathan A. , Berry Neil G. , Xiao Jianliang
Published: April 2011

The general, and highly efficient catalytic system allows a wide range of activated and unactivated aryl chlorides to couple, α‐regioselectively, with electron‐rich olefins.
ChemInform Abstract: A Convenient Synthesis and Some Characteristic Reactions of Novel Propiolamidinium Salts.
Authors: Weingaertner Werner , Kantlehner Willi , Maas Gerhard
Published: April 2011

The reaction of alkynes such as (I) with hexaalkylguanidinium chlorides (II) provides novel orthoamide derivatives which are converted into propiolamidinium halides, triflates, and tetraphenylborates.
ChemInform Abstract: Palladium‐Catalyzed Cyanation of Aryl Bromides Using Phosphine‐Free Pyridyl‐Hydrazone Ligands.
Authors: Mino Takashi , Koizumi Tomoko , Shibuya Masanori , Hirai Kiminori , Sakamoto Masami , Fujita Tsutomu
Published: April 2011

The reaction affords poor results if electron‐deficient aryl bromides are used.
ChemInform Abstract: Palladium‐Catalyzed Conjugate Addition to Electron‐Deficient Alkynes with Benzenesulfinic Acid Derived from 1,2‐Bis(phenylsulfonyl)ethane: Selective Synthesis of (E)‐Vinyl Sulfones.
Authors: Song Ren‐Jie , Liu Yu , Liu Yan‐Yun , Li Jin‐Heng
Published: April 2011

In most cases, high regio‐ and stereoselectivity is observed.
ChemInform Abstract: Zinc‐Mediated Allylation of Aldoxime Esters.
Authors: Wolan Andrzej , Joachimczak Alicja , Budny Marcin , Kozakiewicz Anna
Published: April 2011

The title reaction proceeds under Barbier conditions to afford the corresponding homoallylic hydroxylamine esters.
ChemInform Abstract: A Highly para‐Selective Copper(II)‐Catalyzed Direct Arylation of Aniline and Phenol Derivatives.
Authors: Ciana Claire‐Lise , Phipps Robert J. , Brandt Jochen R. , Meyer Falco‐Magnus , Gaunt Matthew J.
Published: April 2011

A complex polyaryl (XXII) is prepared by iterative arylation of aniline (XVa) at the para‐, ortho‐ and meta‐position.
ChemInform Abstract: Pd(OAc)2‐Catalyzed Oxidative C—H/C—H Cross‐Coupling of Electron‐Deficient Polyfluoroarenes with Simple Arenes.
Authors: Wei Ye , Su Weiping
Published: April 2011

An efficient and straightforward method for the coupling of diverse electron‐deficient polyfluoroarenes with benzene and substituted benzenes is developed.
ChemInform Abstract: Pd‐Catalyzed Decarboxylative Suzuki Reactions and Orthogonal Cu‐Based O‐Arylation of Aromatic Carboxylic Acids.
Authors: Dai Jian‐Jun , Liu Jing‐Hui , Luo Dong‐Fen , Liu Lei
Published: April 2011

The reaction of carboxylic acids with boronic acids in the presence of cupric triflate as catalyst gives rise to esters (III) as sole products, whilst the use of palladous trifluoroacetate as catalyst leads to biaryls (IV) and (VII) as a result of a decarboxylative Suzuki reaction.
ChemInform Abstract: Enantioselective Synthesis of Biphenols from 1,4‐Diketones by Traceless Central‐to‐Axial Chirality Exchange.
Authors: Guo Fenghai , Konkol Leah C. , Thomson Regan J.
Published: April 2011

Key step in the new method is the highly selective transfer of central to axial chirality by double aromatization provided by BF3·OEt2.
ChemInform Abstract: Synthesis of Polysubstituted Olefins by Pd‐Catalyzed Cross‐Coupling Reaction of Tosylhydrazones and Aryl Nonaflates.
Authors: Barluenga Jose , Florentino Lucia , Aznar Fernando , Valdes Carlos
Published: April 2011

A variety of di‐, tri‐ and tetrasubstituted alkenes is prepared with high selectivity.
ChemInform Abstract: Nuclease p1: A New Biocatalyst for Direct Asymmetric Aldol Reaction under Solvent‐Free Conditions.
Authors: Li Hai‐Hong , He Yan‐Hong , Yuan Yi , Guan Zhi
Published: April 2011

A mild biocatalytic reaction is presented.
ChemInform Abstract: Glycerine and CeCl3·7H2O: An Efficient and Recyclable Reaction Medium for Ring Opening of Epoxides with Thioamides and Amines.
Authors: Narsaiah A. Venkat , Wadavrao Sachin B. , Reddy A. Ramesh , Yadav J. S.
Published: April 2011

A simple, mild and efficient green protocol for the synthesis of the compounds (III) and (V) is presented.
ChemInform Abstract: Organic Photovoltaics Incorporating Fulleroisoquinolinones as n‐Type Materials
Authors: Chen Chih‐Ping , Luo Charlene , Ting Ching , Chuang Shih‐Ching
Published: April 2011

Pd‐catalyzed synthesis of fulleroisoquinolinones and fulleroindolines and evaluation of their performance when incorporated with the conjugated polymer P3HT in a device
ChemInform Abstract: Synthesis of Aziridine‐ and Oxirane‐2‐phosphonates Spiro‐Fused with Oxindoles.
Authors: Gasperi Tecla , Loreto M. Antonietta , Migliorini Antonella , Ventura Claudia
Published: April 2011

Cyclization of phosphorylmethyleneoxindoles (III) with nosyloxy carbamate (IV) provides access towards new spirocyclic aziridinephosphonates (V) as single trans‐diastereomers, while the epoxidation with hydrogen peroxide proceeds with moderate trans‐selectivity [cf.
ChemInform Abstract: TfOH‐Catalyzed Tandem Cyclopropane Ring Enlargement/C—C Formation/Etherification of Alkynylcyclopropanes and 1,3‐Diketones to Cyclobutane‐Fused Dihydrofurans.
Authors: Ye Siyu , Yu Zhi‐Xiang
Published: April 2011

A series of cyclobutane‐fused dihydrofurans (III) is obtained by a novel reaction between alkynylcyclopropanes (I) and diketones (II) in the presence of TfOH as catalyst.
ChemInform Abstract: Samarium Diiodide Mediated Intramolecular Cyclization of Mixed Enone—Enoate Systems: A Simple Preparation of Spirocyclic Ethers.
Authors: Meng Junxiu , Light Mark E. , Kilburn Jeremy D. , Dixon Sally
Published: April 2011

The cyclization of substrates with different ring size and length of the tether is achieved with 2 equiv.
ChemInform Abstract: An Efficient and Selective Synthesis of 2,5‐Substituted Pyrroles by Gold‐Catalyzed Ring Expansion of Alkynyl Aziridines.
Authors: Davies Paul W. , Martin Nicolas
Published: April 2011

In the case of silylated alkynes like (V), desilylation takes place giving 2‐substituted pyrroles such as (VI).
ChemInform Abstract: Iron‐Catalyzed Synthesis of Polysubstituted Pyrroles via [4C + 1N] Cyclization of 4‐Acetylenic Ketones with Primary Amines.
Authors: Wang Yeming , Bi Xihe , Li Dehua , Liao Peiqiu , Wang Yidong , Yang Jin , Zhang Qian , Liu Qun
Published: April 2011

A convenient procedure is elaborated for the synthesis of tetra‐ and pentasubstituted pyrroles (III) using an iron‐catalyzed cyclization of acetylenic ketones (I) with amines (II) (31 examples).
ChemInform Abstract: One‐Pot Synthesis of 2,4,5‐Triaryl‐1H‐imidazoles from Arylaldehydes, Benzyl Alcohols, or Benzyl Halides with Hexamethyldisilazane in Molten Tetrabutylammonium Bromide.
Authors: Salehi Javad , Khodaei Mohammad M. , Khosropour Ahmad R.
Published: April 2011

Simple and efficient methods for the synthesis of the title compounds (II), by using available and inexpensive reagents, is developed in the ionic liquid Bu4NBr as a green solvent.
ChemInform Abstract: Diastereoselective Cyclization Reactions of Chiral Proline Auxiliary‐Substituted N‐Benzoyl‐α‐dehydro(1‐naphthyl)alaninamide Derivatives via Photoinduced Electron Transfer.
Authors: Sato Yuhki , Haruyama Yuhta , Igarashi Tetsutaro , Sakurai Tadamitsu
Published: April 2011

The effects of the substituent in the chiral auxiliary of naphthylalaninamide derivatives (I) and solvent on the extent to which either diastereomer is formed in excess are examined with the aim of elucidating a detailed mechanism for the observed asymmetric photoinduction.
ChemInform Abstract: Highly Enantioselective Nitrone Cycloadditions with 2‐Alkenoyl Pyridine N‐Oxides Catalyzed by Cu(II)—BOX Complexes.
Authors: Barroso Santiago , Blay Gonzalo , Munoz M. Carmen , Pedro Jose R.
Published: April 2011

The reaction is catalyzed best by the chiral BOX catalyst and the addition of 4Å molecular sieves is crucial.
ChemInform Abstract: Synthesis and in vitro Antitumor Activity of New Oxadiazole Thioglycosides.
Authors: Abu‐Zaied M. A. , El‐Telbani E. M. , Elgemeie G. H. , Nawwar G. A. M.
Published: April 2011

Key step in the synthesis of novel oxadiazole‐2‐thiol aglycon (IV) and (VIII), respectively is the formation of pyrazole‐4‐carbaldehyde (III) via Vilsmeier—Haack reaction.
ChemInform Abstract: Total Asymmetric Syntheses of β‐Hydroxy‐δ‐lactones via Umpolung with Sulfur Dioxide.
Authors: Exner Claudia J. , Laclef Sylvain , Poli Florent , Turks Maris , Vogel Pierre
Published: April 2011

A number of title compounds like (V) and (VIII) and analogously (XII) and (XIII) is prepared.
ChemInform Abstract: Efficient Transformation of Flav‐3‐Enes Using Reductive Elimination of Flav‐4‐Triflate.
Authors: Kohari Yoshihito , Hoshino Yukio , Matsuyama Haruo , Nakano Hiroto
Published: April 2011

A mild and efficient synthetic methodology for obtaining the compounds (IV), which are useful intermediates for the synthesis of flavonoids, is developed.
ChemInform Abstract: Identification of Dihydropyridines that Reduce Cellular Tau Levels.
Authors: Evans Christopher G. , Jinwal Umesh K. , Makley Leah N. , Dickey Chad A. , Gestwicki Jason E.
Published: April 2011

Hantzsch synthesis and SAR of a series of dihydropyridines (39 examples) with an effect on the accumulation of tau are presented.
ChemInform Abstract: Regiocontrolled Gold(I)‐Catalyzed Cyclization Reactions of N‐(3‐Iodoprop‐2‐ynyl)‐N‐tosylanilines.
Authors: Moran‐Poladura Pablo , Suarez‐Pantiga Samuel , Piedrafita Maria , Rubio Eduardo , Gonzalez Jose M.
Published: April 2011

Depending on the gold catalyst and the nature of the aryl substituents, selective formation of 3‐ or 4‐iodinated 1,2‐dihydroquinolines takes place.
ChemInform Abstract: Efficient One‐Pot Synthesis of Substituted 4,7‐Phenanthroline, Pyrano[3,2‐f]quinoline and Pyrano[3,2‐g]quinoline Derivatives by Aza‐Diels—Alder Reaction.
Authors: Majumdar K. C. , Ponra Sudipta , Ghosh Debankan , Taher Abu
Published: April 2011

A novel and mild procedure allows the synthesis of title compounds via in situ formation of an imine intermediate which undergoes aza‐Diels—Alder reaction with phenylacetylene.
ChemInform Abstract: Cu(II) Catalyzed Oxidation‐[3 + 2] Cycloaddition‐Aromatization Cascade: Efficient Synthesis of Pyrrolo[2,1‐a]isoquinolines.
Authors: Yu Chenguang , Zhang Yianan , Zhang Shilei , Li Hao , Wang Wei
Published: April 2011

An efficient methodology for the one‐pot synthesis of biologically important pyrrolo[2.1‐a]isoquinolines, relying on a novel oxidation‐dipolar cycloaddition—aromatization cascade, is developed.
ChemInform Abstract: Spirocyclization of an N‐Acyliminium Ion with Substituted Pyridine: Stereoselective Synthesis of Tetracyclic Spirolactams Possessing the Pyridone Nucleus.
Authors: Abe Hideki , Takaya Kei‐ichi , Watanabe Kazuhiro , Aoyagi Sakae , Kibayashi Chihiro , Katoh Tadashi
Published: April 2011

An efficient method for the stereoselective synthesis of tetracyclic spirolactams is presented.
ChemInform Abstract: Simple and Efficient One Pot Synthetic Protocol to Construct Morpholin‐2‐ones.
Authors: Yellol Gorakh S. , Mohapatra Debendra K. , Gurjar Mukund K. , Sun Chung‐Ming
Published: April 2011

A wide range of 3‐substituted N‐benzyl‐morpholine‐2‐ones are synthesized based on the condensation of amino acids with 1,2‐Dibromoethane.
ChemInform Abstract: Synthesis and Anticancer Evaluation of New Derivatives of 3‐Phenyl‐1,5‐dimethyl‐1H‐[1,2,4]triazolo[4′,3′:1,2′]pyrimido[4,5‐e] [1,3,4]oxadiazine.
Authors: Bakavoli Mehdi , Rahimizadeh Mohammad , Shiri Ali , Akbarzadeh Marzieh , Mousavi Seyed‐Hadi , Atapour‐Mashhad Hoda , Tayarani‐Najaran Zahra
Published: April 2011

The compound (IXd) is tested on the cancer cell lines MCF‐7 and HepG2 and decreases viability of the cells in a concentration‐dependent manner.
ChemInform Abstract: New Sulfur Bridged Neutral Annulenes. Structure, Physical Properties and Applications in Organic Field‐Effect Transistors.
Authors: Singh Kamaljit , Sharma Amit , Zhang Jing , Xu Wei , Zhu Daoben
Published: April 2011

Title compounds (V), synthesized starting from bis(thienyl)methanes (I) are found to display p‐type semiconductor behavior.
ChemInform Abstract: An Unusual Reaction of 2‐Ethoxyethenylphosphonic Dichloride with Resorcinol and Its Derivatives: Synthesis of Bicyclic Phosphonates with Endocyclic P—C Bond.
Authors: Sadykova Yulia M. , Knyazeva Irina R. , Burilov Alexander R. , Pudovik Michael A. , Dobrynin Alexey B. , Litvinov Igor A. , Sinyashin Oleg G.
Published: April 2011

Product structures are proved by X‐ray analysis.
ChemInform Abstract: Solid—Liquid Two‐Phase Alkylation of Tetraethyl Methylenebisphosphonate Under Microwave Irradiation.
Authors: Greiner Istvan , Gruen Alajos , Ludanyi Krisztina , Keglevich Gyoergy
Published: April 2011

Optimum conditions for the two‐phase alkylation of tetraethyl methylenebisphosphonate (I) depend on the nature of the alkyl halide.
ChemInform Abstract: Isomerization of Diethyl 1‐Alkynylphosphonates to 1,3‐Dienylphosphonates Followed by Diels—Alder Reaction with Dead, Maleic Anhydride and Maleimide.
Authors: Azab Abdullatif , Quntar Abed Al Aziz , Antebi Tamar , Srebnik Morris
Published: April 2011

The two‐step synthesis starting from the compounds (I) to the compounds (IV), (VI), or (VII) can also be accomplished in an one‐pot reaction with comparable yields.
ChemInform Abstract: Efficient Ring Opening of Protected and Unprotected Aziridines Promoted by Stable Zinc Selenolate in Ionic Liquid.
Authors: Salman Syed M. , Schwab Ricardo S. , Alberto Eduardo E. , Vargas Josimar , Dornelles Luciano , Rodrigues Oscar E. D. , Braga Antonio L.
Published: April 2011

An efficient method is presented for the synthesis of chiral β‐seleno amines via ring‐opening reaction of aziridines (I) using zinc selenoate (II) as nucleophile.
ChemInform Abstract: Asymmetric Syntheses of Highly Functionalized Bicyclo[2.2.2]octene Derivatives.
Authors: Iwatsu Masafumi , Urabe Daisuke , Inoue Masayuki
Published: April 2011

Bicyclooctene derivatives bearing two quaternary carbon centers are synthesized in an asymmetric fashion.
ChemInform Abstract: Antiproliferative and Apoptotic Sesquiterpene Lactones from Carpesium faberi.
Authors: Li Xu‐Wen , Weng Liang , Gao Xue , Zhao Yun , Pang Fei , Liu Jian‐Hui , Zhang Hong‐Feng , Hu Jin‐Feng
Published: April 2011

Four new (I)—(IV) and 13 known sesquiterpene lactones along with two known diterpenes are isolated from the whole plant mentioned in title.
ChemInform Abstract: A Synthetic Approach to Anhydroketopyranoses Having a 6,8‐Dioxabicyclo[3.2.1]octane Structure from Ketopyranoses.
Authors: Yamanoi Takashi , Matsumura Kazuhide , Matsuda Sho , Oda Yoshiki
Published: April 2011

The compounds (III) and (VIII) are quantitatively converted to the corresponding compounds (IV) and (IX) by using NaOMe in MeOH.
ChemInform Abstract: Total Synthesis of Rutaecarpine and Analogues by Tandem Azido Reductive Cyclization Assisted by Microwave Irradiation.
Authors: Kamal Ahmed , Reddy M. Kashi , Reddy T. Srinivasa , Santos Leonardo Silva , Shankaraiah Nagula
Published: April 2011

A convenient three‐step synthesis is presented for rutaecarpine (Va) and analogues such as euxylophoricine A (Vb) and C (Vc) involving a microwave‐assisted nickel boride reduction in the final cyclization step.
ChemInform Abstract: Studies on the Biosynthesis of the Stephacidins and Notoamides. Total Synthesis of Notoamide S.
Authors: McAfoos Timothy J. , Li Shengying , Tsukamoto Sachiko , Sherman David H. , Williams Robert M.
Published: April 2011

The synthesis of notoamide S (V) is accomplished in seven steps from indole (I) in 19% overall yield.
ChemInform Abstract: Enantioselective Total Synthesis and Confirmation of the Absolute and Relative Stereochemistry of Streptorubin B.
Authors: Hu Dennis X. , Clift Michael D. , Lazarski Kiel E. , Thomson Regan J.
Published: April 2011

The synthetic studies confirm the (7′S) stereochemistry of the anti atropdiastereomer as the absotute configuration of the natural product.
ChemInform Abstract: Synthesis of 8,1′‐etheno and 8,2′‐ethano Bridged Guanosine Derivatives Using Radical Cyclization.
Authors: Strohmeier Julian , Nadler Andre , Heinrich Daniel , Fitzner Ansgar , Diederichsen Ulf
Published: April 2011

Conformationally constrained nucleosides are generated by radical cyclization reactions.
ChemInform Abstract: Stereoselective Synthesis of Caribbean Ciguatoxin M‐Ring Using [2 + 2] Photocyclization.
Authors: Yamashita Shuji , Iijima Naoya , Shida Takahiro , Hirama Masahiro
Published: April 2011

A secure and stereocontrolled route to the seven‐membered M‐ring moiety of Caribbean ciguatoxin C‐CTX‐1 is developed featuring i) the photoinduced [2 + 2]cyclization to construct the cyclobutene structure (III), ii) the enzymatic desymmetrization of bis‐acetate (III), and iii) the stereoselective reduction of diketone (VII).
ChemInform Abstract: Highly Selective c‐Jun N‐Terminal Kinase (JNK) 2 and 3 Inhibitors with in vitro CNS‐Like Pharmacokinetic Properties Prevent Neurodegeneration.
Authors: Probst Gary D. , et al. et al.
Published: April 2011

The discovery of selective JNK2 and JNK3 inhibitors, such as (Ia), that routinely exhibit <10‐fold selectivity over JNK1 and <1000‐fold selectivity over related MAPKs, p38α and ERK2 is reported.
ChemInform Abstract: Molecular Iron Clusters, Wheels and Cages: Syntheses, Structural Aesthetics and Magnetic Properties
Authors: Dutta Anup Kumar , Ghosh Rajarshi
Published: April 2011

Review: 56 refs.
ChemInform Abstract: Synthesis of Anisotropic Noble Metal Nanoparticles
Authors: Aherne Damian , Ledwith Deirdre M. , Kelly John M.
Published: April 2011

Review: 135 refs.
ChemInform Abstract: Sol‐Gel Synthesis of Nano‐Scaled Metal Fluorides — Mechanism and Properties
Authors: Kemnitz Erhard , Scholz Gudrun , Ruediger Stephan
Published: April 2011

Review: 68 refs.
ChemInform Abstract: Structural Chemistry of Zeolites
Authors: Wright Paul A. , Pearce Gordon M.
Published: April 2011

Review: 82 refs.
ChemInform Abstract: In situ Monitoring of the Formation of Crystalline Solids
Authors: Pienack Nicole , Bensch Wolfgang
Published: April 2011

Review: ca. 150 refs.
ChemInform Abstract: Nitrogen‐Rich Azoles as Lignad Spacers in Coordination Polymers
Authors: Bai Shi‐Qiang , Young David J. , Hor T. S. Andy
Published: April 2011

Review: about 100 refs.
ChemInform Abstract: Coordination Chemistry of 2,4,6‐Tri(pyridyl)‐1,3,5‐triazine Ligands
Authors: Therrien Bruno
Published: April 2011

Review: about 100 refs.
ChemInform Abstract: New Trends Towards Well‐Defined Low‐Valent Iron Catalysts
Authors: Garcia Mancheno Olga
Published: April 2011

Review: 35 refs.
ChemInform Abstract: Organometallic Complexes of Aminopyridines
Authors: Sadimenko Alexander P.
Published: April 2011

Review: ca. 300 refs.
ChemInform Abstract: Nitrogen‐Centered Radical Scavengers
Authors: Hoefling Sarah B. , Heinrich Markus R.
Published: April 2011

Review: 83 refs.
ChemInform Abstract: Reactions between Grignard Reagents and Heterocyclic N‐Oxides: Stereoselective Synthesis of Substituted Pyridines, Piperidines, and Piperazines
Authors: Andersson Hans , Olsson Roger , Almqvist Fredrik
Published: April 2011

Review: 31 refs.
ChemInform Abstract: Molecular Clips and Tweezers Hosting Neutral Guests
Authors: Hardouin‐Lerouge Marie , Hudhomme Pietrick , Salle Marc
Published: April 2011

Review: 72 refs.
ChemInform Abstract: Main‐Chain Supramolecular Block Copolymers
Authors: Yang Si Kyung , Ambade Ashootosh V. , Weck Marcus
Published: April 2011

Review: 47 refs.
ChemInform Abstract: Asymmetric Cu(II) Catalyses for Cycloaddition Reactions Based on π‐Cation or n‐Cation Interactions
Authors: Sakakura Akira , Ishihara Kazuaki
Published: April 2011

Review: 62 refs.
ChemInform Abstract: Water‐Soluble, Self‐Assembling Container Molecules: An Update
Authors: Laughrey Zachary , Gibb Bruce C.
Published: April 2011

Review: 177 refs.
ChemInform Abstract: Stimuli‐Responsive Gels as Reaction Vessels and Reusable Catalysts
Authors: Diaz Diaz David , Kuehbeck Dennis , Koopmans Rudy J.
Published: April 2011

Review: 152 refs.
ChemInform Abstract: Transformations of Peroxide Products of Olefins Ozonolysis
Authors: Ishmuratov G. Yu. , Legostaeva Yu. V. , Botsman L. P. , Tolstikov G. A.
Published: April 2011

Review: 120 refs.
ChemInform Abstract: Catalysis and Mechanistic Insights into Sirtuin Activation
Authors: Dittenhafer‐Reed Kristin E. , Feldman Jessica L. , Denu John M.
Published: April 2011

Review: about 70 refs.
ChemInform Abstract: Use of Carbon Dioxide in Chemical Syntheses via a Lactone Intermediate
Authors: Behr A. , Henze G.
Published: April 2011

Review: polymerization, hydrosilylation, hydroamination etc.; 63 refs.
ChemInform Abstract: Direct Nucleophilic SN1‐Type Reactions of Alcohols
Authors: Emer Enrico , Sinisi Riccardo , Guiteras Capdevila Montse , Petruzziello Diego , De Vincentiis Francesco , Cozzi Pier Giorgio
Published: April 2011

Review: new approaches for a green chemistry; 148 refs.
ChemInform Abstract: Bifunctional Acid—Base Cooperativity in Heterogeneous Catalytic Reactions: Advances in Silica Supported Organic Functional Groups
Authors: Shylesh Sankaranarayanapillai , Thiel Werner R.
Published: April 2011

Review: ca. 60 refs.
ChemInform Abstract: X/π‐Interactions in Aromatic Heterocycles: Basic Principles and Recent Advances
Authors: Hayashi Naoto , Higuchi Hiroyuki , Ninomiya Keiko
Published: April 2011

Review: 101 refs.
ChemInform Abstract: KAT(ching) Metabolism by the Tail: Insight into the Links Between Lysine Acetyltransferases and Metabolism
Authors: Albaugh Brittany N. , Arnold Kevin M. , Denu John M.
Published: April 2011

Review: ca. 80 refs.
ChemInform Abstract: A Modified Epigenetics Toolbox to Study Histone Modifications on the Nucleosome Core
Authors: Frederiks Floor , Stulemeijer Iris J. E. , Ovaa Huib , van Leeuven Fred
Published: April 2011

Review: 75 refs.
ChemInform Abstract: Excited States and Optical Absorption of Small Semiconducting Clusters: Dopants, Defects and Charging
Authors: Fischer Sean A. , Isborn Christine M. , Prezhdo Oleg V.
Published: April 2011

Review: ab initio electronic structure calculations; 79 refs.
Antioxidant Enzymes Response in Vetiver Grass: A Greenhouse Study for Chelant‐Assisted Phytoremediation of Lead‐Contaminated Residential Soils
Authors: Andra Syam S. , Datta Rupali , Reddy Ramana , Saminathan Sumathi K. M. , Sarkar Dibyendu
Published: April 2011

In a previous study we have demonstrated the suitability of using vetiver grass (Vetiveria zizanioides L.) for the phytostabilization of lead‐based paint contaminated residential soils. Vetiver did not show any growth retardation or toxicity symptoms despite high soil Pb levels. Antioxidant enzymes like superoxide dismutase (SOD), catalase (CAT), and glutathione peroxidase (GPx) reportedly allow plants to combat metal stress. Thus, we hypothesized that in vetiver, these antioxidant enzymes can play an important role in combating Pb induced stress, and that chelant‐bound Pb is less toxic to vetiver compared to free Pb in soil. The response of antioxidant enzymes was studied in vetiver grass grown in Pb paint‐contaminated residential soils collected from San Antonio, Texas and Baltimore, Maryland. Chelating agents such as ethylenediaminetetraacetic acid (EDTA) and ethylenediaminedisuccinic acid (EDDS) were used to mobilize Pb from bound fractions to the labile pool, facilitating Pb uptake by vetiver. Although the Pb concentration in vetiver from these treatments was significantly higher than those grown in the absence of a chelant, the antioxidant enzymes activities were lower compared to the latter. Antioxidant enzymes activity of vetiver plants grown in the presence of chelants is lower compared to those in without chelant treatment, while they tended to increase with dose in treatments with varying chelant concentrations. Data obtained support the proposed hypothesis.
Response Surface Analysis and Statistical Modeling of Sulfide Generation from Municipal Wastewater
Authors: Zinatizadeh Ali Akbar , Bonakdari H. , Pirsaheb M. , Gharacheh E.
Published: April 2011

In this study, the interactive effects of four independent variables (initial chemical oxygen demand (COD) concentration, rotational velocity, temperature, and retention time) on the sulfide generation process in municipal wastewater were investigated. The process was modeled and analyzed with the variables in a series batch experiments. Experiments were conducted based on a central composite face‐centered design and analyzed using response surface methodology. The region of exploration for the process was taken as the area enclosed by COD (250 and 650 mg/L), rotational velocity (40 and 200 rpm), temperature (16 and 28°C), and retention time (2 and 40 h) boundaries. Eleven dependent parameters were either directly measured or calculated as response. The most influential variable on H2S (g) production was found to be retention time. The results showed that simultaneous increase in temperature and rotational velocity caused an increasing trend in the amount of H2S (g) emitted. Total sulfide was decreased by increasing rotational velocity due to more H2S (g) secretion resulting from increased mixing rate. The present study provides valuable information about interrelations of quality and process parameters at different values of the studied variables.
Prediagnostic smoking history, alcohol consumption, and colorectal cancer survival
Authors: Phipps Amanda I. , Baron John , Newcomb Polly A.
Published: April 2011

BACKGROUND:

Smoking and alcohol consumption are associated with an increased risk of developing colorectal cancer. However, it is unclear whether these exposures are associated with survival after colorectal cancer diagnosis.

METHODS:

Men and women diagnosed with incident colorectal cancer between 1998 and 2007 in 13 counties in western Washington State were identified by using the Surveillance, Epidemiology, and End Results cancer registry. Information on smoking history and alcohol consumption was collected by telephone interview. Follow‐up for mortality was completed through linkage to the National Death Index. Cox proportional hazards regression was used to estimate hazard ratios (HR) and 95% confidence intervals (CI) for associations among smoking, alcohol consumption, and mortality after colorectal cancer diagnosis. Stratified analyses were conducted by sex, age at diagnosis (<50 years, ≥50 years), tumor site (proximal, distal, rectal), stage (I‐II, III‐IV), and microsatellite instability status (stable/low, high).

RESULTS:

Disease‐specific and all‐cause mortality were significantly higher for smokers (HR, 1.30; 95% CI, 1.09‐1.74) compared with never‐smokers (HR, 1.51; 95% CI, 1.24‐1.83). However, this association was most prominent in those with tumors exhibiting high microsatellite instability (HR, 3.83; 95% CI, 1.32‐11.11) and did not extend to those with rectal cancer (HR, 1.08; 95% CI, 0.72‐1.61) or those diagnosed before age 50 years (HR, 0.99; 95% CI, 0.67‐1.48). Alcohol consumption was not associated with disease‐specific or all‐cause mortality, regardless of patient or tumor characteristics.

CONCLUSIONS:

In addition to an association with disease risk, smoking is associated with increased mortality after colorectal cancer diagnosis. This association is especially pronounced for colorectal cancer with high microsatellite instability. Cancer 2011;. © 2011 American Cancer Society.
Genetic amplification of the vascular endothelial growth factor (VEGF) pathway genes, including VEGFA, in human osteosarcoma
Authors: Yang Jilong , Yang Da , Sun Yan , Sun Baocun , Wang Guowen , Trent Jonathan C. , Araujo Dejka M. , Chen Kexin , Zhang Wei
Published: April 2011

BACKGROUND:

Osteosarcoma is the most common primary tumor of bone. It is a highly vascular and extremely destructive malignancy that mainly affects children and young adults. The authors conducted microarray‐based comparative genomic hybridization (aCGH) and pathway analyses to gain a systemic view of pathway alterations in the genetically altered genes.

METHODS:

Recurrent amplified and deleted genes that were detected by aCGH were subjected to an analysis based on the Kyoto Encyclopedia of Genes and Genomes to identify the altered pathways. Among the enriched pathways, vascular endothelial growth factor (VEGF) pathway genes collectively were amplified, and alterations of this pathway were validated by fluorescence in situ hybridization (FISH) and immunohistochemistry analyses in 58 formalin‐fixed, paraffin‐embedded osteosarcoma archival tissues that had clinical follow‐up information.

RESULTS:

The pathway enrichment analyses of the aCGH data revealed that VEGF pathway genes, including the VEGFA gene itself, were amplified significantly in osteosarcoma. Genetic amplification of the VEGFA gene, both focally and in larger fragment, was validated by FISH analysis. It is noteworthy that amplification of the VEGFA gene and elevated expression of the VEGFA protein were associated significantly with microvascular density and adverse tumor‐free survival in patients with osteosarcoma.

CONCLUSIONS:

The authors report for the first time that VEGF pathway genes, including the VEGFA gene, are amplified in osteosarcoma. Amplification of the VEGFA gene is not only an important mechanism for elevated VEGFA protein expression but also is a poor prognostic factor for tumor‐free survival. Combined classification of VEGFA gene amplification and positive VEGFA protein expression may provide a more accurate stratification method of selecting anti‐VEGF therapy for patients with osteosarcoma. Cancer 2011;. © 2011 American Cancer Society.
Clinical results and risk factors of proton and carbon ion therapy for hepatocellular carcinoma
Authors: Komatsu Shohei , Fukumoto Takumi , Demizu Yusuke , Miyawaki Daisuke , Terashima Kazuki , Sasaki Ryohei , Hori Yuichi , Hishikawa Yoshio , Ku Yonson , Murakami Masao
Published: April 2011

BACKGROUND:

The objective of this study was to evaluate the clinical outcome of proton and carbon ion therapy for hepatocellular carcinoma (HCC).

METHODS:

In total, 343 consecutive patients with 386 tumors, including 242 patients (with 278 tumors) who received proton therapy and 101 patients (with 108 tumors) who received carbon ion therapy, were treated on 8 different protocols of proton therapy (52.8‐84.0 gray equivalents [GyE] in 4‐38 fractions) and on 4 different protocols of carbon ion therapy (52.8‐76.0 GyE in 4‐20 fractions).

RESULTS:

The 5‐year local control and overall survival rates for all patients were 90.8% and 38.2%, respectively. Regarding proton and carbon ion therapy, the 5‐year local control rates were 90.2% and 93%, respectively, and the 5‐year overall survival rates were 38% and 36.3%, respectively. These rates did not differ significantly between the 2 therapies. Univariate analysis identified tumor size as an independent risk factor for local recurrence in proton therapy, carbon ion therapy, and in all patients. Multivariate analysis identified tumor size as the only independent risk factor for local recurrence in proton therapy and in all patients. Child‐Pugh classification was the only independent risk factor for overall survival in proton therapy, in carbon ion therapy, and in all patients according to both univariate and multivariate analyses. No patients died of treatment‐related toxicities.

CONCLUSIONS:

Proton and carbon ion therapies for HCC were comparable in terms of local control and overall survival rates. These therapies may represent innovative alternatives to conventional local therapies for HCC. Cancer 2011;. © 2011 American Cancer Society.
Sisters Peer Counseling in Reproductive Issues After Treatment (SPIRIT)
Authors: Schover Leslie R. , Rhodes Michelle M. , Baum George , Adams Jennifer Harned , Jenkins Rosell , Lewis Pamela , Jackson Karen Eubanks
Published: April 2011

BACKGROUND:

African American breast cancer survivors may be at high risk for reproductive health problems, including menopause symptoms, sexual dysfunction, and distress about cancer‐related infertility. The authors partnered with Sisters Network Inc. to create the Sisters Peer Counseling in Reproductive Issues After Treatment (SPIRIT) program, a culturally sensitive intervention program that combined a written workbook and peer counseling.

METHODS:

Three hundred women were randomized to receive either the workbook plus 3 in‐person sessions with a trained peer counselor or the workbook plus ≤30 minutes of telephone counseling to be initiated by the participant. Questionnaires at baseline, post‐treatment, and at 6‐month and 12‐month follow‐up assessed emotional distress, sexual function, relationship satisfaction, spirituality, menopause symptoms, and knowledge. Satisfaction with the program and the use of medical care also were assessed.

RESULTS:

Both groups of women improved significantly in knowledge, decreased in distress, and had decreased hot flashes. Sexually active women had improved sexual function at 6‐month follow‐up but not at 1 year. However, peer counseling had little incremental benefit over the telephone counseling.

CONCLUSIONS:

The SPIRIT program was rated very useful by 66% of women. Outcomes justify continued use of the workbook and further research to optimize the impact of peer counseling. Cancer 2011;. © 2011 American Cancer Society.
Decentralization of CD4 testing in resource‐limited settings: 7 years of experience in six African countries
Authors: Marinucci F. , Medina‐Moreno S. , Paterniti A. D. , Wattleworth M. , Redfield R. R.
Published: April 2011

Improving access to CD4 testing in resource‐limited settings can be achieved through both centralized and decentralized testing networks. Decentralized testing models are more suitable for countries where the HIV epidemic affects a large portion of rural populations. Timely access to accurate CD4 results is crucial at the primary level of the health system. For the past 7 years, the Institute of Human Virology of the University of Maryland School of Medicine has implemented a flexible and sustainable three‐phase model: (1) site assessment and improvement, (2) appropriate technology selection with capacity building through practical training and laboratory mentoring, and (3) quality management system strengthening and monitoring, to support accessibility to reliable CD4 counting at the point of service. CD4 testing capacity was established in 122 of 229 (53%) laboratories supported in Nigeria, Uganda, Kenya, Zambia, Tanzania, and Rwanda. Among those in rural settings, 46% (69/151) had CD4 testing available at site level, with a functioning flow cytometer installed at 28% (8/29) and 50% (61/122) of level 1 and level 2 sites, respectively. To strengthen local capacity, a total of 1,152 laboratory technicians were trained through 188 training sessions provided both on‐site and at central locations. The overall quality of CD4 total testing procedure was assessed at 76% (92/121) of the laboratories, with 25% (23/92), 34% (31/92), and 33% (30/92) of them reporting excellent, good, and satisfactory performance. Balancing country‐specific factors with the location of the clinic, number of patients, and the expected workload, was crucial in adapting this flexible model for decentralizing CD4 testing. The close collaboration with local governments and private vendors was key to successfully expanding access to CD4 testing within the framework of HIV care and treatment programs and for the sustainability of medical laboratories in resource‐limited settings. © 2011 International Society for Advancement of Cytometry
Design and synthesis of novel NO‐donor‐ferulic acid hybrids as potential antiatherosclerotic drug candidatesa
Authors: Li Nian‐Guang , Wang Rong , Shi Zhi‐Hao , Tang Yu‐Ping , Li Bao‐Quan , Wang Zhen‐Jiang , Song Shu‐Lin , Qian Li‐Hua , Wei Li , Yang Jian‐Ping , Yao Li‐Juan , Xi Jun‐Zuan , Xu Jia , Feng Feng , Qian Da‐Wei , Duan Jin‐Ao
Published: April 2011

Novel NO‐donor‐ferulic acid hybrids were designed and synthesized through a symbiotic approach using ferulic acid and three different NO‐donating groups, such as nitric ester, 4‐hydroxyl‐3‐phenylfuroxan, and 4‐hydroxymethyl‐3‐phenylsulfonylfuroxan. Antioxidant, nitric oxide release, and vasodilator properties studies showed that the target phenylsulfonylfuroxan 14, especially 14c, while keeping the antioxidant activity, showed more NO release activity and vasodilating activity than isosorbide dinitrate (ISDN). Thus, 14c may be considered a novel potent anti‐atherosclerosis drug candidate. Drug Dev Res 72: 405–415, 2011. © 2011 Wiley‐Liss, Inc.
Tips for success: Getting more done in less time
Authors: Kiefer Julie C.
Published: April 2011

Whether a student or full professor, it seems there is never enough time in the day to get everything done. Yet as a scientist rises through the ranks, somehow she is expected to do even more. Excellent time management skills enable one to work more effectively, and to accomplish more in less time. Therefore, the ability to manage time well is paramount to success. Here, three busy full professors, David Kimelman, Ph.D., Thomas Rando, Ph.D., and Monica Vetter, Ph.D. share tips on how they organize and prioritize their time, and cope with unexpected demands. Developmental Dynamics 240:1635–1637, 2011. © 2011 Wiley‐Liss, Inc.
The Relationship between the Electrochemical and Chemical Oxidation of Ferrocene‐Containing Carbonyl‐Phosphane‐β‐Diketonato‐Rhodium(I) Complexes – Cytotoxicity of [Rh(FcCOCHCOPh)(CO)(PPh3)]
Authors: Conradie Jeanet , Swarts Jannie C.
Published: April 2011

Ferrocene‐containing rhodium(I) complexes of the type [Rh(FcCOCHCOR)(CO)(PPh3)] with R = Fc (ferrocenyl),1, Ph (phenyl),2, CH3,3, and CF3,4, have been studied by cyclic voltammetry (CV) and bulk electrolysis techniques in CH3CN. Two isomers for complexes2–4were detected. Results are consistent with RhIbeing oxidised first in an electrochemically irreversible two‐electron transfer process, followed by the electrochemical reversible oxidation of each ferrocenyl group in a one‐electron transfer process at slightly larger potentials. Only theEpa(Rh) CV peaks resolved into two separate waves, each one being associated with an isomer. Slow isomerisation kinetics allowed the detection of two isomers of2–4.Epa(Rh) and other compound physical parameters relates to the second‐order rate constant for the oxidative addition of CH3I to complexes1–4in acetone. Rhodium(III) reduction of oxidised1,2,3and4was observed at large negative potentials, while for [Rh(FcCOCHCOCF3)(CH3)(I)(CO)(PPh3)] (9) it was observed at –1.492 V vs. Fc/Fc+. Complex2was slightly more cytotoxic than the free FcCOCH2COPh ligand but less cytotoxic than cisplatin.
On the Reduction of NC Chelated Organoantimony(III) Chlorides
Authors: Dostál Libor , Jambor Roman , Růžička Aleš , Šimon Petr
Published: April 2011

The conversion of organolithium compound LLi, for which L = [o‐C6H4(CH=NC6H3iPr2‐2,6)]–, with antimony chloride gave the molecular chlorides LSbCl2 (1) and L2SbCl (2) depending on the molar ratio used (either 1:1 or 2:1). Bothcompounds were characterized by using 1H and 13C NMR spectroscopy, elemental analysis and single‐crystal X‐ray diffraction. The reaction of 1 with two molar equivalents of K[B(sBu)3H] led to smooth formation of compound L4Sb4 (3) as a result of hydrogen elimination from the unstable hydrido compound. On the contrary, a similar reaction between 2 and K[B(sBu)3H] (1:1) did not result in hydrogen elimination and the formation of expected distibine L2SbSbL2, but an addition of an in situ generated L2Sb–H bond across the C=N functionality in the pendant arm of one of the ligands was observed. The reduction of compound 2 with an excess amount of magnesium was strongly dependent on the reaction time. The distibine L2SbSbL2 (5) could be isolated after 4–5 h from this reaction mixture. Elongation of the reaction time to 1 d (and more) gave a more complicated reaction mixture, in which three products, distibine 5, compound 3 and organomagnesium compound L2Mg(THF) (6), were characterized by single‐crystal X‐ray diffraction in addition to other unidentified products. These results can be rationalized by a migration of the ligand L from the antimony atom to the magnesium, thus explaining formation of both L4Sb4 (3) compound and L2Mg(THF) (6).