Use of the (2+2) macrocyclization in the synthesis of macrocyclic imines.
Item
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Title
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Use of the (2+2) macrocyclization in the synthesis of macrocyclic imines.
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Identifier
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AAI9510637
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identifier
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9510637
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Creator
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Brathwaite, Claude-Earl.
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Contributor
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Adviser: Valeria Balogh-Nair
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Date
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1994
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Language
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English
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Publisher
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City University of New York.
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Subject
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Chemistry, Organic
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Abstract
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The (2+2) macrocyclization of dicarbonyl and diamine moieties were applied to the synthesis of metal-free macrocyclic imines. This method also permitted systematic syntheses of sidearm derivatives. In the design and syntheses of macrocycles, one was not limited to the syntheses of imines, as the procedure was equally efficient in the synthesis of amides. This extension of the (2+2) cyclization to the synthesis of the more hardy macrocyclic amide expanded even further the potential uses of this macrocyclization process. The metal-free nature of the synthesis brought with it enormous flexibility and application possibilities.;Sidearm derivatized macrocycles enable the building of function specific macrocyclic systems such as chiral, lipophilic, coordinative, photoactive, polymeric, and responsive macrocyclic imines; they have all been synthesized by this methodology. Because of the similarity in cavity size in the series of imine and amide macrocycles synthesized, and the flexibility of sidearm derivatizations, the solubility, association, cation and guest binding behavior of the macrocycles can be modified at will. Increased flexibility in the type of macrocycle to be synthesized is also achieved by the choice of the dicarbonyl moiety used in the synthesis. Sidearm derivatization to yield anthracenyl macrocyclic imines, produced macrocycles that possessed not only the ability to coordinate cations, but also took advantage of the photochemical, association and luminescence properties of the anthracenyl moiety.;All new compounds were characterized by spectroscopic studies. Fluorescence and {dollar}\sp1{dollar}H nmr spectroscopy were used to probe the self-association properties of selected macrocycles. Monolayer formation and cation recognition at the water/air interface by the sidearm derivatized macrocycles demonstrated the potential of these macrocyclic imines in the construction of supramolecular assemblies. FAB mass and uv/vis spectroscopies employed to explore the cation binding demonstrated the ability of these macrocycles to bind Ni{dollar}\sp{lcub}2+{rcub}{dollar} ions, hence the oxidation chemistry of two selected macrocycles were explored to develop oxidation catalysts and nucleic acid cleaving agents.
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Type
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dissertation
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Source
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PQT Legacy CUNY.xlsx
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degree
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Ph.D.
