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Catalytic Cleavage of Carbon-Carbon Sigma Bonds Using Transition MetalsDombrowski, James Michael January 2005 (has links)
Thesis advisor: Lawrence T. Scott / The focus of this project was to probe the ability of various transition metal complexes to cleave carbon-carbon bonds in a C30H12 hemifullerene. The hemifullerene was synthesized in our lab from commercial 1-tetralone and bromonaphthalene in six steps. Palladium and nickel complexes were used to open the five membered rings along the periphery of the C30H12 bowl. Diphosphine complexes of nickel were capable of opening either all three five membered rings or one of the periphery five membered rings and the central six membered ring. / Thesis (BS) — Boston College, 2005. / Submitted to: Boston College. College of Arts and Sciences. / Discipline: Chemistry. / Discipline: College Honors Program.
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Development of Radical-Mediated Synthetic Methods via Single-Electron Transfer by Transition Metal Catalysts / 遷移金属触媒の一電子移動によるラジカル的合成手法の開発Oku, Naoki 25 March 2024 (has links)
京都大学 / 新制・課程博士 / 博士(工学) / 甲第25311号 / 工博第5270号 / 京都大学大学院工学研究科合成・生物化学専攻 / (主査)教授 杉野目 道紀, 教授 中尾 佳亮, 教授 石田 直樹 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM
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Contribuição ao estudo de reações mediadas por calcogenetos Zn e Cu: hidrocalcogenação de ácidos e ésteres e síntese de sulfetos arílicos / New contributions for the synthesis of unsymmetrical diaryl thioethers and vinyl chalcogenides compunds promoted by copper Senelenophene-2-carboxylate and zinc chalcogenolatesNunes, Vanessa Loren 04 May 2012 (has links)
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Previous issue date: 2012-05-04 / Conselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNPq / This work describes some studies on the preparation of unsymmetrical
diaryl thioethers catalyzed by Copper(I)-Senelenophene-2-carboxylate. The
results concern to the catalyzed cross-coupling reaction between aryl halides
and aryl or alkylthiols using Copper(I)-Senelenophene-2-carboxylate (CuSC) a
new Cu-catalyzed one-pot protocol. The products were obtained in good to
excellent yields under relatively mild reaction conditions presenting
chemoselectivity and functional group tolerance. Additionally, we have developed a chemio-, regio and stereoselective
synthesis of vinyl chalcogenides compounds promoted by zinc chalcogenolates.
In this protocol the reductive cleavage of chalcogen bond by the Zn/NH4OH
system led to zinc chalcogenolates. The reaction was carried out with acids and
esters propiolics afford β-chalcogenacrillic acids and esters under mild and
basic conditions. The stereochemistry corresponding to anti-Markovnikov
addition of the chalcogenolate constituents across the triple bond were obtained
in good yields. / Este trabalho descreve o estudo das reações de acoplamento cruzado
entre iodetos arílicos e tióis arílicos ou alquílicos catalisada por 2-carboxilato
selenofeno de cobre (I) (CuSC). Apresentamos uma nova metodologia “ one
pote” para a síntese de tioésteres arílicos obtidos em condições reacionais
relativamente brandas, apresentando quimiosseletividade, tolerância a diversos
grupos funcionais e rendimentos que variam entre bons a ótimos (70-100%).
R1I + R2SH
K3PO4, DMSO
S
R1 R2
Adicionalmente, desenvolvemos uma síntese quimio, régio, e
estereosseletiva de compostos vinil calcogenetos promovida por calcogenolato
de zinco. Neste protocolo a clivagem redutiva da ligação calcogênio feita pelo
sistema Zn/NH4OH obteve os calcogenolatos de zinco. A reação foi realizada
com ácidos e ésteres propiólicos formando ácidos acrílicos β-calcogênio e
ésteres sob condições básicas e brandas. A estereoquímica corresponde a
adição anti-Markovnikov dos constituintes calcogenolatos através da ligação
tripla. Os calcogenetos vinílicos foram obtidos em bons rendimentos (40-96).
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Development of luminescent ruthenium complexes for in-vitro fluorescence imaging of angiogenesis with the RGD peptideVictoria, Rosemary 01 May 2012 (has links)
Herein we report the synthesis of an RGD-ruthenium bipyridine [Ru(Bpy)2(BpyRGD)]2+ complex aimed at the detection of angiogenesis. Angiogenesis plays a critical role in many pathophysiological processes, such as tumor growth. The αv-integrins (αv[beta]3, αv[beta]5) are currently used as molecular targeting sites for anti-angiogenic therapies. The [Ru(Bpy)2(BpyRGD)]2+ complex is an organometallic luminescent probe, which enables noninvasive, in vitro imaging of αv[beta]3 expression. Peptides containing the arginine-glycine-aspartic acid (RGD) sequence have been shown to bind strongly to the αvb3 integrin. The RuBpy probes are soluble in water, display long lifetimes, and are photochemically stable. These properties enable the Ru(tris-bpy) complexes to be useful in numerous applications in biophysical and cell biology. The [Ru(Bpy)2(BpyRGD)]2+ complex was synthesized by combining the succinimidyl ester on the RuBpy complex with the lysine of the c(RGDfK) peptide. The results of the one-photon fluorescence bioimaging showed selective binding of the cyclic RGD to αv[beta]3 integrin, which supports previous literature. The high luminescence intensity, long lifetimes, and low cell toxicity levels of dye [Ru(Bpy)2(BpyRGD)]2+, illustrates the potential usage of this probe for future biological applications.
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