• Refine Query
  • Source
  • Publication year
  • to
  • Language
  • 2
  • 2
  • Tagged with
  • 4
  • 4
  • 4
  • 3
  • 3
  • 3
  • 2
  • 2
  • 2
  • 2
  • 2
  • 2
  • 2
  • 2
  • 2
  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
1

I. Completion of a Total Synthesis of Peloruside A. II. Studies toward the Total Synthesis of Spiro-Prorocentrimine

Speed, Alexander William Harrison 05 October 2013 (has links)
I. Completion of a Total Synthesis of Peloruside A: The completion of a 22 step synthesis of the marine natural product peloruside A is presented. The second generation strategy cuts 10 steps from longest linear sequence of the Evans group’s first generation synthesis of peloruside A by changing the order of fragment coupling operations and maintaining \(C_1\) and \(C_9\) at their final oxidation states over the course of most of the synthesis. Key steps include two highly diastereoselective aldol fragment couplings, a tin tetrachloride mediated hydrosilylation and a macrolactonization on a seco acid containing no cyclic templating elements. II. Studies toward the Total Synthesis of Spiro-Prorocentrimine: The development of an intermolecular Diels–Alder approach toward the marine natural product spiro–prorocentrimine is described. This work began with the adaptation of the Evans group’s previous intramolecular Diels–Alder approach. It was found that protonated imines bearing non-coordinating counterions were of sufficient reactivity to allow cycloaddition to occur even on dienes that were unreactive under the previous best conditions. In the course of these studies, isomerization of a macrocyclic diene during the course of a Diels–Alder reaction complicated the stereochemical outcome of the reaction. Reaction conditions to suppress the isomerization and obtain Diels–Alder adducts bearing the correct configuration at both \(C_9\) and \(C_{33}\) were developed based on a qualitative consideration of the pKas of species present in the reaction. The of several macrocyclic dienes was examined to help explain the course of the Diels–Alder reaction. Other key steps include an iron catalyzed olefin formation, the highly diastereoselective hydrogenation of a trisubstituted olefin in the presence of an enol ether, protecting group studies to suppress the contraction of a 15 membered lactone to a 6 membered lactone and studies of a protecting group strategy to allow installation of a sulfate. Lessons learned from this work and previous efforts are combined in a proposal for a bioinspired synthesis of spiro-prorocentrimine with a longest linear sequence of less than 30 steps. / Chemistry and Chemical Biology
2

Theoretical Studies Of II-Facial Selectivity In Sterically Unbiased Systems

Kalyanaraman, P 09 1900 (has links) (PDF)
No description available.
3

Estudos de diastereosseletividade facial em reações de Diels-Alder de sulfinil benzoquinonas e em adições nucleofílicas a sulfinil cicloexanonas sulfaniladas / Studies on facial diastereoselectivity in Diels-Alder reactions of sulfinyl benzoquinones and in nucleophilic additions to sulfanylated sulfinylcyclohexanones

Cardoso Filho, José Eduardo Pandini 05 December 2008 (has links)
Calcando-se na bem conhecida capacidade que os sulfóxidos apresentam em induzir a quiralidade em uma vasta gama de reações, foram preparadas as (±)-2-p-tolilsulfinil-3,6-dimetil- e a (S)-2-p-tolilsulfinil-3-metil-1,4-benzoquinonas e estudadas as suas reações de Diels-Alder com alguns 1,3-dienos. Bons resultados de quimio- e regiosseletividade foram obtidos no caso da primeira quinona com o trans-piperileno e com o 1-vinil-cicloexeno, mas a eliminação espontânea de ácido sulfênico gerou produtos que não puderam ser utilizados posteriormente. O grupo sulfinila, no caso da segunda quinona preparada, não de mostrou capaz de induzir diastereosseletividade facial nas reações com ciclopenta- e cicloexadieno. Também foram estudados os modos de adição do enolato de lítio do acetato de etila às carbonilas das 2-metilsulfinil-2-sulfanil-cicloexanonas. Pelo emprego de espectroscopia de absorção no I. V., ficou evidenciado que a 2-metilsulfinil-2-metilsulfanil-cicloexanona existe como mistura de confôrmeros, sendo o mais abundante aquele para o qual se atribuiu, baseado em cálculos teóricos, que o grupo SOCH3 esteja preferencialmente na posição equatorial e o grupo SCH3, na posição axial. Assim sendo, os excessos enantioméricos observados puderam ser explicados pela proposição de que o ataque do enolato ocorreu de modo axial sobre as carbonilas dos confôrmeros existentes em solução. / Based on the well known ability of the sulfinyl group in controlling the chirality of a broad spectrum of reactions, the new (±)-2-p-tolylsulfinyl-3,6-dimethyl- and (S)-2-p-tolylsulfinyl-3-methyl-1,4-benzoquinones were prepared and their Diels-Alder reactions with some 1,3-dienes investigated. Good chemo- and regioselectivities were observed for the reactions of (±)-2-p-tolylsulfinyl-3,6-dimethylbenzoquinone with both trans-piperilene and 1-vinylcyclohexene. However, spontaneous elimination of sulfenic acid precluded the use of the obtained cycloadducts in further transformations. The sulfinyl group, in the case of (S)-2-p-tolylsulfinyl-3-methyl-1,4-benzoquinone, failed to control diastereoselectivity in Diels-Alder reaction with cyclopentadiene and cyclohexadiene. Studies concerning the addition of ethyl acetate lithium enolate to the carbonyl groups of 2-methylsulfinyl-2-sulfanyl-cyclohexanones were also undertaken. In the case of 2-methylsulfinyl-2-methylsulfanylcyclohexanone, a mixture of conformers was evidenced by I. R. spectroscopy. On the basis of theoretical considerations, it could be advanced that, in the most abundant conformer, the SOCH3 and SCH3 groups lie, respectively, in equatorial and axial arrangements. Therefore, the observed enantiomeric excess can be explained considering that the enolate performs an axial attack to the carbonyl groups of the ketone conformers.
4

Estudos de diastereosseletividade facial em reações de Diels-Alder de sulfinil benzoquinonas e em adições nucleofílicas a sulfinil cicloexanonas sulfaniladas / Studies on facial diastereoselectivity in Diels-Alder reactions of sulfinyl benzoquinones and in nucleophilic additions to sulfanylated sulfinylcyclohexanones

José Eduardo Pandini Cardoso Filho 05 December 2008 (has links)
Calcando-se na bem conhecida capacidade que os sulfóxidos apresentam em induzir a quiralidade em uma vasta gama de reações, foram preparadas as (±)-2-p-tolilsulfinil-3,6-dimetil- e a (S)-2-p-tolilsulfinil-3-metil-1,4-benzoquinonas e estudadas as suas reações de Diels-Alder com alguns 1,3-dienos. Bons resultados de quimio- e regiosseletividade foram obtidos no caso da primeira quinona com o trans-piperileno e com o 1-vinil-cicloexeno, mas a eliminação espontânea de ácido sulfênico gerou produtos que não puderam ser utilizados posteriormente. O grupo sulfinila, no caso da segunda quinona preparada, não de mostrou capaz de induzir diastereosseletividade facial nas reações com ciclopenta- e cicloexadieno. Também foram estudados os modos de adição do enolato de lítio do acetato de etila às carbonilas das 2-metilsulfinil-2-sulfanil-cicloexanonas. Pelo emprego de espectroscopia de absorção no I. V., ficou evidenciado que a 2-metilsulfinil-2-metilsulfanil-cicloexanona existe como mistura de confôrmeros, sendo o mais abundante aquele para o qual se atribuiu, baseado em cálculos teóricos, que o grupo SOCH3 esteja preferencialmente na posição equatorial e o grupo SCH3, na posição axial. Assim sendo, os excessos enantioméricos observados puderam ser explicados pela proposição de que o ataque do enolato ocorreu de modo axial sobre as carbonilas dos confôrmeros existentes em solução. / Based on the well known ability of the sulfinyl group in controlling the chirality of a broad spectrum of reactions, the new (±)-2-p-tolylsulfinyl-3,6-dimethyl- and (S)-2-p-tolylsulfinyl-3-methyl-1,4-benzoquinones were prepared and their Diels-Alder reactions with some 1,3-dienes investigated. Good chemo- and regioselectivities were observed for the reactions of (±)-2-p-tolylsulfinyl-3,6-dimethylbenzoquinone with both trans-piperilene and 1-vinylcyclohexene. However, spontaneous elimination of sulfenic acid precluded the use of the obtained cycloadducts in further transformations. The sulfinyl group, in the case of (S)-2-p-tolylsulfinyl-3-methyl-1,4-benzoquinone, failed to control diastereoselectivity in Diels-Alder reaction with cyclopentadiene and cyclohexadiene. Studies concerning the addition of ethyl acetate lithium enolate to the carbonyl groups of 2-methylsulfinyl-2-sulfanyl-cyclohexanones were also undertaken. In the case of 2-methylsulfinyl-2-methylsulfanylcyclohexanone, a mixture of conformers was evidenced by I. R. spectroscopy. On the basis of theoretical considerations, it could be advanced that, in the most abundant conformer, the SOCH3 and SCH3 groups lie, respectively, in equatorial and axial arrangements. Therefore, the observed enantiomeric excess can be explained considering that the enolate performs an axial attack to the carbonyl groups of the ketone conformers.

Page generated in 0.0776 seconds