Synthesis of biologically active molecules: Novel macrocycles and guanine nucleotides.
Item
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Title
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Synthesis of biologically active molecules: Novel macrocycles and guanine nucleotides.
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Identifier
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AAI9521258
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identifier
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9521258
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Creator
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Chen, Cunxiang.
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Contributor
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Adviser: Valeria Balogh-Nair
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Date
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1995
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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 (3+2) condensation of terephthaldicarboxaldehyde with tris(2-aminoethyl)amine and subsequent oxidation of the resulting imino macrocycle afforded a macrobicyclic oxaziridine, the first example of a macrocycle containing the oxaziridine functionality. The potential of this novel class of macrocycles as oxidizing agents and oxygenase mimics was demonstrated. The (3+2) condensation of terephthaldicarboxaldehyde with tris(4-hydroxylaminobenzoyloxyethyl)amine yielded a macrobicyclic nitrone, the first example of a macrocycle containing the nitrone group. Light-induced ring closure of the six nitrone moieties to the corresponding oxaziridines was investigated. (1+1) and (2+1) Condensations followed by ring closure and/or oxidations led to a series of podands containing nitrone or sulfonyloxaziridine moieties.;Syntheses of a series of isotopically labelled and otherwise modified GDP and GTP analogs were undertaken to serve as model compounds in Raman spectroscopic studies of G protein-guanine nucleotide interactions. Deuterated analogs, (8-{dollar}\sp2{dollar}H) GDP, (8-{dollar}\sp2{dollar}H) GTP, and (8-{dollar}\sp2{dollar}H) GMPPCP were obtained by high yield exchange reactions. An efficient synthesis was developed to obtain (6-{dollar}\sp{18}{dollar}O) GDP in three steps, from ({dollar}-{dollar})-2-amino-6-chloropurine riboside by its conversion to the (6-{dollar}\sp{18}{dollar}O) guanosine followed by chemical and enzymatic phosphorylations. ({dollar}\sp{18}{dollar}O) -Labelled analogs, ({dollar}\beta{dollar}-{dollar}\sp{18}{dollar}O) GDP and ({dollar}\beta{dollar}-{dollar}\sp{18}{lcub}\rm O{rcub}\sb4{dollar}) GDP, were obtained by chemical phosphorylation of an activated GMP derivative, and by conversion of ({dollar}\beta{dollar}-S) GDP to ({dollar}\beta{dollar}-{dollar}\sp{18}{lcub}\rm O{rcub}\sb4{dollar}) GDP. The (6-H) GDP and 9-butylguanine were prepared via multistep syntheses.
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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.
