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Doctoral Thesis
DOI
10.11606/T.46.2008.tde-19122008-114737
Document
Author
Full name
José Eduardo Pandini Cardoso Filho
E-mail
Institute/School/College
Knowledge Area
Date of Defense
Published
São Paulo, 2008
Supervisor
Committee
Di Vitta, Cláudio (President)
Andrade, Leandro Helgueira de
Bazito, Fernanda Ferraz Camilo
Cunha, Rodrigo Luiz Oliveira Rodrigues
Miranda, Maria Terêsa Machini de
Title in Portuguese
Estudos de diastereosseletividade facial em reações de Diels-Alder de sulfinil benzoquinonas e em adições nucleofílicas a sulfinil cicloexanonas sulfaniladas
Keywords in Portuguese
Benzoquinona
Cicloexanona
Compostos de enxofre
Diels-Alder
Reações químicas
Seletividade facial
Síntese orgânica
Sulfóxido
Abstract in Portuguese
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.
Title in English
Studies on facial diastereoselectivity in Diels-Alder reactions of sulfinyl benzoquinones and in nucleophilic additions to sulfanylated sulfinylcyclohexanones
Keywords in English
Benzoquinone
Cyclohexanone
Diels-Alder
Facial selectivity
Organic reactions
Organic synthesis
Sulfoxide
Abstract in English
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.
 
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Publishing Date
2009-03-10
 
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