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出典(authority):フリー百科事典『ウィキペディア（Wikipedia）』「2015/05/21 20:33:55」(JST)

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English Journal

Highly Enhanced Bisignate Circular Dichroism of Ferrocene-Bridged Zn(II) Bisporphyrin Tweezer with Extended Chiral Substrates due to Well-Matched Host-Guest System.

Brahma S1, Ikbal SA, Dhamija A, Rath SP.Author information 1Department of Chemistry, Indian Institute of Technology Kanpur , Kanpur-208016, India.AbstractFour new chiral tweezer-diamine complexes, consisting of an achiral ferrocene-bridged Zn(II)bisporhyrin host (1) and two small diamines (1R,2R)-1,2-diphenylethylene diamine {(1R,2R)-DPEA} and (1S,2S)-1,2-cyclohexane diamine {(1S,2S)-CHDA} and two extended diamines (1R,2R)-N,N'-bis-(isonicotinoyl)-1,2-diphenylethylene diamine {(1R,2R)-DPEApy} and (1S,2S)-N,N'-bis-(isonicotinoyl)-1,2-cyclohexane diamine {(1S,2S)-CHDApy} chiral guests, are reported. Additions of (1R,2R)-DPEA and (1S,2S)-CHDA separately to 1 in dichloromethane result in the formation of 1:1 sandwich complexes 1·DPEA(R,R) and 1·CHDA(S,S), respectively, at low guest concentration and 1:2 anti complexes 1·(DPEA(R,R))2 and 1·(CHDA(S,S))2, respectively, at higher guest concentration. In contrast, separate additions of (1R,2R)-DPEApy and (1S,2S)-CHDApy to 1 produce only 1:1 sandwich complexes of 1·DPEApy(R,R) and 1·CHDApy(S,S), respectively. The binding constants at 295 K between 1 and (1R,2R)-DPEA are observed to be (4.7 ± 0.2) × 104 M-1 and (4.3 ± 0.3) × 103 M-1 for 1:1 sandwich and 1:2 anti form, respectively, while the respective values with (1S,2S)-CHDA are (1.5 ± 0.2) × 105 M-1 and (5.9 ± 0.3) × 103 M-1. However, much larger values of (2.5 ± 0.3) × 105 M-1 and (1.3 ± 0.3) × 106 M-1 have been observed with DPEApy(R,R) and CHDApy(S,S), respectively, to produce the corresponding 1:1 sandwich complexes. 1·DPEApy(R,R) (Acal, -1759 cm-1 M-1) (Acal = Δε1 - Δε2, representing the total amplitude of the calculated circular dichroism (CD) couplets) shows ∼10-fold increase in CD amplitude compared to the values observed for 1·DPEA(R,R) (Acal, +187 cm-1 M-1), while 1·CHDApy(S,S) (Acal, +1886 cm-1 M-1) shows nearly 3-fold increase of the CD amplitude compared to the value observed for 1·CHDA(S,S) (Acal, -785 cm-1 M-1) at 295 K. The Acal values of -1759 cm-1 M-1 and +1886 cm-1 M-1 observed for the 1·DPEApy(R,R) and 1·CHDApy(S,S), respectively, are extremely high. To the best of our knowledge, these are some of the largest values reported for a chirality induction process involving bisporphyrin tweezer receptors. The large enhancement in the CD signal intensity is due to the well complementarity size between Zn(II)bisporphyrin host and the extended chiral diamines guest, which results large unidirectional twisting of two porphyrin units to accommodate the guests having preorganized binding sites with minimum host-guest steric interactions. It is interesting to note that 1·DPEA(R,R) and 1·DPEApy(R,R) show CD signal opposite in sign to each other, which happens to be the case between 1·CHDA(S,S) and 1·CHDApy(S,S) also.
Inorganic chemistry.Inorg Chem.2014 Feb 12. [Epub ahead of print]
Four new chiral tweezer-diamine complexes, consisting of an achiral ferrocene-bridged Zn(II)bisporhyrin host (1) and two small diamines (1R,2R)-1,2-diphenylethylene diamine {(1R,2R)-DPEA} and (1S,2S)-1,2-cyclohexane diamine {(1S,2S)-CHDA} and two extended diamines (1R,2R)-N,N'-bis-(isonicotinoyl)-1,
PMID 24520860

Phenylene-Coated Magnetic Nanoparticles that Boost Aqueous Asymmetric Transfer Hydrogenation Reactions.

Gao X1, Liu R, Zhang D, Wu M, Cheng T, Liu G.Author information 1Key Laboratory of Resource Chemistry of Ministry of Education, Shanghai Key Laboratory of Rare Earth Functional Materials, Shanghai Normal University, Shanghai 200234 (P. R. China).AbstractPhenylene-coated organorhodium-functionalized magnetic nanoparticles are developed through co-condensation of chiral 4-(trimethoxysilyl)ethyl)phenylsulfonyl-1,2-diphenylethylene-diamine and 1,4-bis(triethyoxysilyl)benzene onto Fe3 O4 followed complexation with [{Cp*RhCl2 }2 ]. This magnetic catalyst exhibits excellent catalytic activity and high enantioselectivity in asymmetric transfer hydrogenation in aqueous medium. Such activity is attributed to the high hydrophobicity and the confined nature of the chiral organorhodium catalyst. The magnetic catalyst can be easily recovered by using a small external magnet and it can be reused for at least 10 times without loss of its catalytic activity. This characteristic makes it an attractive catalyst for environmentally friendly organic syntheses.
Chemistry (Weinheim an der Bergstrasse, Germany).Chemistry.2014 Feb 3;20(6):1515-9. doi: 10.1002/chem.201302797. Epub 2014 Jan 8.
Phenylene-coated organorhodium-functionalized magnetic nanoparticles are developed through co-condensation of chiral 4-(trimethoxysilyl)ethyl)phenylsulfonyl-1,2-diphenylethylene-diamine and 1,4-bis(triethyoxysilyl)benzene onto Fe3 O4 followed complexation with [{Cp*RhCl2 }2 ]. This magnetic catalyst
PMID 24403274

Complexation, thermal and catalytic studies of N-substituted piperazine, morpholine and thiomorpholine with some metal ions.

Kacan M1, Turkyilmaz M, Karabulut F, Altun O, Baran Y.Author information 1Trakya University, Science Faculty, Department of Chemistry, Edirne, Turkey.AbstractSeveral Cu(II), Pt(II) and Ni(II) complexes of N-substituted, piperazine (NN donor), morpholine (NO donor) and thiomorpholine (NS donor) derivatives were synthesized and their thermal behavior and catalytic activity in epoxidation reaction of cis-diphenylethylene were studied using oxygen sources NaOCl. The coordination compounds of Cu(II), Pt(II) and Ni(II) having general formula [MLCl]Cl, [ML2l]Cl2 or [ML]Cl2 with tetra coordinated geometry around metal ions have been isolated as solid. All the ligands and complexes were identified by spectroscopic methods and elemental analysis, magnetic measurements, electrical conductance and thermal analysis. A square planer structures have been proposed for all complexes. The thermal stability of the complexes discussed in terms of ligands donor atoms, geometry and central metal ions. The complexes have a similar thermal behavior for the selected metal ions. The thermogravimetric analyses suggest high thermal stability for most complexes followed by thermal decomposition in different steps. The decomposition processes were observed as water elimination, chloride anion removal and degradation of the organic ligands. Catalytic ability of the complexes were examined and found that all the complexes can effectively catalyze the epoxidation of cis-stilbene with NaOCl.
Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy.Spectrochim Acta A Mol Biomol Spectrosc.2014 Jan 24;118:572-7. doi: 10.1016/j.saa.2013.09.031. Epub 2013 Sep 16.
Several Cu(II), Pt(II) and Ni(II) complexes of N-substituted, piperazine (NN donor), morpholine (NO donor) and thiomorpholine (NS donor) derivatives were synthesized and their thermal behavior and catalytic activity in epoxidation reaction of cis-diphenylethylene were studied using oxygen sources Na
PMID 24091345

Japanese Journal

触媒的不斉[3+2]環化付加反応 : 多置換ピロリジン化合物の新立体化学制御

有機合成化学協会誌 71(7), 672-682, 2013-07-01
NAID 10031185763

Optical Resolution of 1,2-Diamino Compounds Using Advanced Marfey's Method

質量分析 = Mass spectroscopy 57(2), 71-74, 2009-04-01
NAID 10024837327

Successive Synthesis of Well-Defined Star-Branched Polymers by Iterative Methodology Based on Living Anionic Polymerization

Polymer journal 40(10), 923-941, 2008-10-15
NAID 10024341768

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hypochlorite chemical formula - best hypochlorite chemical formula 1,1-Diphenylethylene oxide, ACROS Organics :Chemicals:Organic Compounds 2,3,5,4'-Tetrahydroxyl diphenylethylene-2-O-glucoside | CAS:82373-94-2 | Product Use 1 1 Diphenylethylene 99 25g from Cole-Parmer