Silver(I) and Copper(I) Coordination Polymers Based on Thiaoxa-Macrocycles

Kim, Hyun Jee,Song, Mi Ryoung,Lee, So Young,Lee, Jai Young,Lee, Shim Sung WILEY-VCH Verlag 2008 European journal of inorganic chemistry Vol.2008 No.22

<P>Two S<SUB>2</SUB>O<SUB>2</SUB>-macrocycles with different ring size (L<SUP>1</SUP>: 17- and L<SUP>2</SUP>: 18-membered) were synthesised and structurally characterised by X-ray analysis. Reactions of L<SUP>1</SUP> and L<SUP>2</SUP> with silver(I) salts (ClO<SUB>4</SUB><SUP>–</SUP> and NO<SUB>3</SUB><SUP>–</SUP>) afforded respective ligand- and/or anion-directed complexes 1–4 with different topologies; single-stranded 1D coordination polymer [AgL<SUP>1</SUP>(ClO<SUB>4</SUB>)(DMSO)]<SUB>n</SUB> (1), double-stranded 1D coordination polymer {[Ag<SUB>2</SUB>(L<SUP>1</SUP>)<SUB>2</SUB>(NO<SUB>3</SUB>)<SUB>2</SUB>]·DMSO}<SUB>n</SUB> (2), cyclic dimer [Ag<SUB>2</SUB>(L<SUP>2</SUP>)<SUB>2</SUB>(ClO<SUB>4</SUB>)<SUB>2</SUB>]·CH<SUB>2</SUB>Cl<SUB>2</SUB>·CH<SUB>3</SUB>OH (3) and 2D polymeric sheet [Ag(L<SUP>2</SUP>)NO<SUB>3</SUB>]<SUB>n</SUB> (4). Meanwhile, reactions of these two ligands with copper(I) iodide afforded 1D (5) and 2D (6a) coordination polymers linked with a rhomboid-type Cu–I<SUB>2</SUB>–Cu unit, respectively. The formation of such discrete and continuous supramolecular complexes is discussed in terms of discrimination of the anion effect, ligand flexibility as well as interligand π-π stacking interaction. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)</P> <B>Graphic Abstract</B> <P>Two analogous dithiamacrocycles (17- and 18-membered) are synthesised. Five coordination polymers and one metallo-cyclic dimer were obtained from the reactions of the macrocycles with the silver(I) and copper(I) salts. The versatility of results is discussed in relation to macrocyclic ring flexibility, anions and π-π stacking. <img src='wiley_img/14341948-2008-2008-22-EJIC200800284-fig000.gif' alt='wiley_img/14341948-2008-2008-22-EJIC200800284-fig000'> </P>

Rhodium-Catalyzed Tandem Transformations with Organoboron Reagents: Sequential Multiple C–C Bond Formations

WILEY-VCH Verlag 2009 EUROPEAN JOURNAL OF ORGANIC CHEMISTRY Vol.2009 No.16

<P>Tandem transformations represent one of the most efficient methods for the synthesis of complex molecules from readily available starting materials, as evidenced by the intense research activity and the plethora of literature published in this area. This review highlights recent developments of rhodium(I)-catalyzed tandem transformations with organoboron compounds involving the formation of multiple carbon–carbon bonds. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)</P> <B>Graphic Abstract</B> <P>This review provides an overview of recent developments of rhodium(I)-catalyzed tandem transformations with organoborons involving the formation of multiple carbon–carbon bonds. These processes are powerful and straightforward methods for the synthesis of complex molecules including both acyclic and cyclic compounds. <img src='wiley_img/1434193X-2009-2009-16-EJOC200900001-fig000.gif' alt='wiley_img/1434193X-2009-2009-16-EJOC200900001-fig000'> </P>

Ratiometric Fluorescence Sensing of Fluoride Ions by an Asymmetric Bidentate Receptor Containing a Boronic Acid and Imidazolium Group

Xu, Zhaochao,Kim, Sook Kyung,Han, Su Jung,Lee, Chongmok,Kociok-Kohn, Gabriele,James, Tony D.,Yoon, Juyoung WILEY-VCH Verlag 2009 EUROPEAN JOURNAL OF ORGANIC CHEMISTRY Vol.2009 No.18

<P>The synthesis of the first examples of anion receptors that utilize boron–fluoride interactions and (C–H)<SUP>+</SUP>···F<SUP>–</SUP>-type ionic hydrogen-bond interactions in the binding of F ions is reported herein. o-, m-, and p-Phenylboronic acids were linked to naphthoimidazolium through a methylene group. On the basis of fluorescence and <SUP>19</SUP>F NMR studies, we have confirmed that the addition of fluoride to a boron center occurs prior to the formation of (C–H)<SUP>+</SUP>···F<SUP>–</SUP>-type ionic hydrogen bond with the imidazolium moiety. More importantly, these investigations have demonstrated that only the receptor bearing the ortho-directed boron and imidazolium exhibits enhanced fluoride binding. The increased binding ability of the asymmetric bidentate receptor of ortho-boronic acid and imidazolium towards F<SUP>–</SUP> enables it to sense fluoride ions in a 95:5 CH<SUB>3</SUB>CN/HEPES aqueous solution. The fluorescence responses to different anions were also explored; the ortho-boron-imidazolium receptor displayed ratiometric fluorescence changes and a high selectivity towards fluoride ions over other anions (Cl<SUP>–</SUP>, Br<SUP>–</SUP>, CH<SUB>3</SUB>CO<SUB>2</SUB><SUP>–</SUP>, HSO<SUB>4</SUB><SUP>–</SUP>, and H<SUB>2</SUB>PO<SUB>4</SUB><SUP>–</SUP>).(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)</P> <B>Graphic Abstract</B> <P>An asymmetric bidentate receptor containing boronic acid and an imidazolium group can recognize F<SUP>–</SUP>, as evidenced by ratiometric fluorescence responses in aqueous solution. <img src='wiley_img/1434193X-2009-2009-18-EJOC200900120-fig000.gif' alt='wiley_img/1434193X-2009-2009-18-EJOC200900120-fig000'> </P>

TMSOTf-Promoted Addition of Alkynes to Aldehydes: A Novel Synthesis of Chroman-4-ones

Park, Ji Yeon,Ullapu, Punna Reddy,Choo, Hyunah,Lee, Jae Kyun,Min, Sun-Joon,Pae, Ae Nim,Kim, Youseung,Baek, Du-Jong,Cho, Yong Seo WILEY-VCH Verlag 2008 EUROPEAN JOURNAL OF ORGANIC CHEMISTRY Vol.2008 No.32

<P>A novel synthetic method to prepare chalcones 2 and chroman-4-ones 3 by TMSOTf-promoted addition of alkynes 1 to various aldehydes has been developed. The ratios of chalcones 2, chroman-4-ones 3 and hydrated products 4 varied depending upon the substituents R (nBu, phenyl, H and TMS) on the alkynes 1. We also describe the transformation of the chalcones 2 to the corresponding chroman-4-ones 3 under basic conditions. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)</P> <B>Graphic Abstract</B> <P>A novel synthetic method to prepare chalcones and chroman-4-ones by TMSOTf-promoted addition of alkynes to various aldehydes has been developed. The ratios of chalcones, chroman-4-ones and hydratedproducts vary depending upon the substituents on the alkynes. We also describe the transformation of the chalcones to the corresponding chroman-4-ones under basic conditions. <img src='wiley_img/1434193X-2008-2008-32-EJOC200800782-fig000.gif' alt='wiley_img/1434193X-2008-2008-32-EJOC200800782-fig000'> </P>

Ring-Closing Metathesis Dimerizations of Enynes and Deprotections of Propargyl Ethers Mediated by Carbene Ruthenium Complexes

Hahn, Dong-Woo,Byun, Dong-Min,Tae, Jinsung WILEY-VCH Verlag 2005 European journal of organic chemistry Vol.2005 No.1

<P>The ring-forming dimerizations of enynes were catalyzed by the first-generation carbene ruthenium complex, and the effects of the catalysts and ethylene gas were studied. The deprotection of propargyl ethers by the carbene ruthenium complexes is the first to be reported. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)</P> <B>Graphic Abstract</B> <P> <img src='wiley_img/1434193X-2005-2005-1-EJOC200400630-fig000.gif' alt='wiley_img/1434193X-2005-2005-1-EJOC200400630-fig000'> </P>

Unprecedented N-Inserted Disulfide Ligand Stabilized by Coordination to the Electropositive Co^III Center

Yoo, Houng Sik,Yoon, Jung Hee,Kim, Jae Il,Koh, Eui Kwan,Hong, Chang Seop WILEY-VCH Verlag 2008 European journal of inorganic chemistry Vol.2008 No.20

<P>The reaction of Co<SUP>II</SUP> and 2,2′-dipyridyldisulfide (PySSPy) in the presence of azide produced a peculiar monomeric complex [Co<SUP>III</SUP>(PyS)(PyS-N-SPy)(N<SUB>3</SUB>)] (1). In this reaction, redox chemistry takes place, which is associated mainly with the oxidation of Co<SUP>II</SUP> to Co<SUP>III</SUP> and the reduction of PySSPy. During the reaction, the azide ion decomposes and donates a nitrogen atom to PySSPy. The crystal structure of 1 provides evidence that the unusual, N-inserted ligand PyS-N-SPy can be stabilized through coordination to the electropositive Co<SUP>III</SUP> ion. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)</P> <B>Graphic Abstract</B> <P>The reaction of Co<SUP>II</SUP> and 2,2′-dipyridyldisulfide (PySSPy) in the presence of azide produced a monomeric complex [Co<SUP>III</SUP>(PyS)(PyS-N-SPy)(N<SUB>3</SUB>)] (1), which was characterized by means of UV/Vis, X-ray crystallography, XPS, and cyclic voltammetry. The unusual, N-inserted ligand PyS-N-SPy can be stabilized through coordination to the electropositive Co<SUP>III</SUP> ion. <img src='wiley_img/14341948-2008-2008-20-EJIC200800439-fig000.gif' alt='wiley_img/14341948-2008-2008-20-EJIC200800439-fig000'> </P>

[Cu^II₄] Clusters From the Self-Assembly of Two Imidazolidinyl 2-Phenolate-Bridged [Cu^II₂] Units: The Role of the Chloride Bridge

Paital, Alok Ranjan,Hong, Chang Seop,Kim, Hyoung Chan,Ray, Debashis WILEY-VCH Verlag 2007 European journal of inorganic chemistry Vol.2007 No.12

<P>A new family of tetracopper clusters [Cu<SUB>4</SUB>(μ<SUB>4</SUB>-X)L<SUB>2</SUB>]ClO<SUB>4</SUB>·nH<SUB>2</SUB>O (1a–c) [X = Cl, Br, I; n = 12, 2, 2; H<SUB>3</SUB>L = 2-(2′-hydroxyphenyl)-1,3-bis[4-(2-hydroxyphenyl)-3-azabut-3-enyl]-1,3-imidazolidine] have been synthesised and characterised. The X-ray crystal structure of 1a reveals that the template action of the spherical Cl<SUP>–</SUP> anion (μ<SUB>4</SUB>-Cl<SUP>–</SUP>), which features a unique rectangular planar bridging mode, is responsible for the self-assembly of two [Cu<SUB>2</SUB>L]<SUP>+</SUP> units in complex 1a. In this family of complexes the spherical halides serve as templates to assemble the dimeric unit into tetrameric complexes, which gives an insight into the role of the halide bridge in tetranuclear complex formation. The capacity of this bridge to mediate magnetic coupling has been examined by bulk magnetic measurements for complex 1a. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)</P> <B>Graphic Abstract</B> <P> <img src='wiley_img/14341948-2007-2007-12-EJIC200600917-fig000.gif' alt='wiley_img/14341948-2007-2007-12-EJIC200600917-fig000'> </P>

A Terephthalato-Bridged Ni^II Complex Capped with a Nonchelating Ligand Displays a Three-Dimensional Supramolecular Network Constructed by Coordination and Multi-Intermolecular Forces

Seop Hong, Chang,Hee Yoon, Jung,Hak Lim, Jeong,Hee Ko, Hyun WILEY-VCH Verlag 2005 European journal of inorganic chemistry Vol.2005 No.23

<P>A new tp-bridged complex [Ni(pyrazole)<SUB>4</SUB>(tp)]<SUB>n</SUB> (1; tp = terephthalate) coordinated with a nonchelating pyrazole ligand has been synthesized and characterized using X-ray structure determination and magnetic studies. The crystal structure reveals that the capping ligand functions as a source of hydrogen bonding and intermolecular contacts, such as π–π and CH–π interactions, that result in a three-dimensional supramolecular assembly. Weak antiferromagnetic couplings are transmitted between Ni<SUP>II</SUP> centers through the tp linkage. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)</P> <B>Graphic Abstract</B> <P> <img src='wiley_img/14341948-2005-2005-23-EJIC200500526-fig000.gif' alt='wiley_img/14341948-2005-2005-23-EJIC200500526-fig000'> </P>

A Versatile Synthesis of Cyclic Diphenyl Ether-Type Diarylheptanoids: Acerogenins, (±)-Galeon, and (±)-Pterocarine

Jeong, Byeong-Seon,Wang, Qian,Son, Jong-Keun,Jahng, Yurngdong WILEY-VCH Verlag 2007 EUROPEAN JOURNAL OF ORGANIC CHEMISTRY Vol.2007 No.8

<P>A versatile method for the total synthesis of cyclic diphenyl ether-type diarylheptanoids, acerogenin C, acerogenin L, (±)-galeon, and (±)-pterocarine was described. The Ullmann reaction of suitably substituted linear diphenylheptanoids was employed for the intramolecular formation of the key ether intermediates as the final step. The prerequisite diarylheptanoids were prepared by a series of cross-aldol condensation reactions from readily available starting benzaldehydes.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)</P> <B>Graphic Abstract</B> <P> <img src='wiley_img/1434193X-2007-2007-8-EJOC200600938-fig000.gif' alt='wiley_img/1434193X-2007-2007-8-EJOC200600938-fig000'> </P>

Synthesis of the Tetraketide Lactones from the Pikromycin Biosynthetic Pathway

Oh, Hong-Se,Yun, Ji-Suk,Nah, Ki-Hyun,Kang, Han-Young,Sherman, David H. WILEY-VCH Verlag 2007 European journal of organic chemistry Vol.2007 No.20

<P>Synthesis of tetraketide lactones 2 and 3, which are likely to be produced by a model pikromycin polyketide synthase (PKS), has been investigated. The tetraketide lactones with six-membered rings, 2a and 2b, were synthesized successfully by the asymmetric aldol reaction, allylation, and the Reformatsky reaction. The attempted synthesis of tetraketide lactones with eight-membered rings, 3a and 3b, led to the formation of the compounds 2a and 2b. The synthesis of another tetraketide lactone compounds 35 was attempted with the hope that introducing an additional methyl group would lead to a change in thermodynamic stability. However, it produced the corresponding tetraketide lactone 34 with a six-membered ring. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)</P> <B>Graphic Abstract</B> <P> <img src='wiley_img/1434193X-2007-2007-20-EJOC200700254-fig000.gif' alt='wiley_img/1434193X-2007-2007-20-EJOC200700254-fig000'> </P>