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TheSecond-Generation Electrochemical Labeling of Hydroxyindoles with Chemoselectivity (eCLIC) for Site-Specific Protein Bioconjugation:Jeoung, Kun Yong January 2023 (has links)
Thesis advisor: Abhishek Chatterjee / Electrochemistry has gained recognition for its precise control over reactions, mild conditions, and scalability in small molecule synthesis. However, its application in modifying complex biomolecules, including proteins, specifically through electrochemical site-specific labeling, is still relatively unexplored. The eCLIC, electrochemically-promoted coupling reaction, developed by the Chatterjee group enables the selective labeling of proteins using 5-HTP and aromatic amines under mild conditions. By incorporating 5-HTP through genetic code expansion, eCLIC allows for specific labeling of recombinant proteins. Although the technique offers advantages such as high conversion rates, broad substratescope, cost-effectiveness, and compatibility with existing labeling methods, its optimization for incorporating hydrophobic molecules is essential. Initial attempts to conjugate 5-HTP with hydrophobic molecules through eCLIC were challenging, but the incorporation of negatively charged functional groups, such as carboxylic acids, has shown to be promising in enhancing the reactivity of eCLIC reactions. This study investigates the use of tertiary aniline warheads with negatively charged functional groups in conjunction with hydrophobic molecules to improve reaction efficiency and stability. The results demonstrate that these functional groups facilitate more efficient carbon-carbon bond formation, leading to stable conjugation between the warhead and the target protein. The findings emphasize the potential of incorporating negatively charged functional groups in designing eCLIC reactions and their role in developing effective and versatile site-specific labeling strategies for complex biomolecules. / Thesis (MS) — Boston College, 2023. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.
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An examination of the synthesis, substitution reactions, and kinetic behaviour of pentacarbonyl(thiocarbonyl)chromium(0) and its precursorsUhm, Hae Won January 1991 (has links)
Note:
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A statistical treatment of annihilation reactions /Weiss, Nathan S. January 1976 (has links)
No description available.
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Realistic residual interaction in finite nuclei.Lee, Hoong-Chien January 1968 (has links)
No description available.
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Excited state proton transfer in microheterogeneous conditionsLinares-Samaniego, Sandra I. 05 1900 (has links)
No description available.
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Zum Mechanismus nucleophiler Substitutionen an bifunktionellen BenzolderivatenJung, Dietmar, January 1962 (has links)
Thesis (doctoral)--Ludwig-Maximilians-Universität München 1962. / Vita. Includes bibliographical references (p. 57-59).
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Synthesis of Heterocycles and Carbocycles Through Tandem and Domino Palladium-catalyzed ReactionsChai, David 29 August 2011 (has links)
We have described two important classes of palladium-catalyzed reactions for the synthesis of heterocycles and carbocycles: tandem Pd-catalyzed reactions of gem-dibromoolefins and domino Pd-catalyzed reactions via an ortho C−H functionalization.
Chapter 1 describes the tandem Pd-catalyzed reaction of gem-dibromoolefins via an intramolecular direct arylation and an intermolecular Suzuki-Miyaura cross-coupling. A number of aromatic carbocycles were synthesized by this method.
Chapter 2 describes the tandem Pd-catalyzed reactions of β,β-dibromoenamides via an intramolecular C−O bond formation and an intermolecular Suzuki-Miyaura cross-coupling. Depending on the substituent on the nitrogen of β,β-dibromoenamides, either aromatic heterocycles or acyclic compounds can be synthesized.
Chapter 3 and 4 describe the domino Pd-catalyzed reactions via an ortho C−H functionalization of aryl iodides. 2-Pyrrole substituted phenyl iodides were coupled with alkyl bromides in the presence of norbornene to provide aromatic tetracyclic compounds through three C−C bond formations (Chapter 3). However, the reaction between 2-methyl substituted phenyl iodides and the alkyl bromides in the presence of norbornene provided tetrasubstituted helical alkenes with the norbornene incorporated in the final product through four C−C bond formations (chapter 4).
In Chapter 5, detailed mechanistic studies including kinetic and NMR studies were described for the regioselective C−H functionalization of 2-pyrrole substituted phenyl iodides. The studies provided advanced and important understanding of the mechanism, and a rationale for the high regioselectivity.
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Synthesis of Heterocycles and Carbocycles Through Tandem and Domino Palladium-catalyzed ReactionsChai, David 29 August 2011 (has links)
We have described two important classes of palladium-catalyzed reactions for the synthesis of heterocycles and carbocycles: tandem Pd-catalyzed reactions of gem-dibromoolefins and domino Pd-catalyzed reactions via an ortho C−H functionalization.
Chapter 1 describes the tandem Pd-catalyzed reaction of gem-dibromoolefins via an intramolecular direct arylation and an intermolecular Suzuki-Miyaura cross-coupling. A number of aromatic carbocycles were synthesized by this method.
Chapter 2 describes the tandem Pd-catalyzed reactions of β,β-dibromoenamides via an intramolecular C−O bond formation and an intermolecular Suzuki-Miyaura cross-coupling. Depending on the substituent on the nitrogen of β,β-dibromoenamides, either aromatic heterocycles or acyclic compounds can be synthesized.
Chapter 3 and 4 describe the domino Pd-catalyzed reactions via an ortho C−H functionalization of aryl iodides. 2-Pyrrole substituted phenyl iodides were coupled with alkyl bromides in the presence of norbornene to provide aromatic tetracyclic compounds through three C−C bond formations (Chapter 3). However, the reaction between 2-methyl substituted phenyl iodides and the alkyl bromides in the presence of norbornene provided tetrasubstituted helical alkenes with the norbornene incorporated in the final product through four C−C bond formations (chapter 4).
In Chapter 5, detailed mechanistic studies including kinetic and NMR studies were described for the regioselective C−H functionalization of 2-pyrrole substituted phenyl iodides. The studies provided advanced and important understanding of the mechanism, and a rationale for the high regioselectivity.
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Reactivity of rhodium-heteroatom bonds: from catalytic bond activation to new strategies for olefin functionalizationvan Rooy, Sara Emily 05 1900 (has links)
Rhodium complexes bearing multidentate nitrogen donor ligands were investigated for their ability to promote alkyne and olefin functionalization reactions. This thesis work is comprised of two projects in which rhodium-heteroatom reactivity is investigated: P-H bond activation reactions and olefin functionalizations via rhodaoxetane intermediates.
[Tp*Rh(PPh3)2] [Tp* = hydrotris(3,5-dimethylpyrazolyl)borate] and
[Tp*Rh(cod)]2 (cod = cyclooctadiene) were evaluated for their activity in alkyne hydrophosphinylation in comparison to known catalysts for this reaction. [Tp*Rh(PPh3)2]and [Tp*Rh(cod)]2 were both shown to effect hydrophosphinylation of 1-octyne with diphenylphosphine oxide with high regioselectivity but moderate yields in comparison with Wilkinson's catalyst [C1Rh(PPh3)3]. [Tp*Rh(PPh3)2] was further shown to effect hydrophosphinylation of a range of aromatic and aliphatic alkynes with diphenylphosphine oxide, in each case exclusively providing the E-linear vinylphosphineoxide product. 1H and 31P NMR spectroscopy provided evidence that alkyne hydrophosphinylation in the presence of pyrazolylborate rhodium complexes follows an analogous mechanism to that proposed for this reaction catalyzed by [C1Rh(PPh3)3] or[C1Rh(cod)]2.
The 2-rhodaoxetane [(TPA)Rhmec2_,-4u, 0-2-oxyethypr BPh4- (TPA = tris[(2-pyridal)methyl]amine) was investigated for its potential as an intermediate in proposed functionalization reactions of olefins. RTPA)Rh111(K2-C,0-2-oxyethyl)]+ BPh4- was prepared by two published methods with limited success. A third method involved the use of nitrous oxide to oxygenate [(12-ethene)(K4-TPA)Rh1]+ to RTPA)Rh1110(-2-C,0-2-oxyethyDr. Only a trace amount of [(TPA)Rhmoc2 -C,0-2-oxyethypr was observed in the 1I-1 NMR spectrum of this reaction mixture. Initial test reactions of [(TPA)Rhilioc2_C,0-2-oxyethypr combined with substrates (aniline, toluenesulfonamide, phenylboronic acid, or benzaldehyde) were inconclusive since the results were obscured by the impurity of the samples.
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Excited state proton transfer in ortho substituted naphthols : Part II Mechanistic studies of ortho allyl-naphthol photocyclizationsHarvey, Lilia Cuesta 12 1900 (has links)
No description available.
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