Estudos sinteticos para a obtenção de derivados do biciclo [4.4.0]deceno, via reações de Diels-Alder

AUTOR(ES)

Domingos Savio de Miranda

DATA DE PUBLICAÇÃO

1999

RESUMO

Assessing the synthesis of compounds possessing the bicycle[ 4.4.0]decene skeletons like 6-hydroxy-1,2,5,5-tetramethyl-1,2,3,5,6,7,8,8a-octahydronaphthalene derivatives via Diels-Alder was the primary objective of the present thesis. The (1S)-(-)- and (1R,S)-()-2,2-dimethyl-3-vinyl-3-cyclohexenol (17 e 17a, respectively) were the dienes four choice to react with methyl tyglate (19), methyl angelate (23), 1-methanesulfonyl-3-(E-2 -methyl-butenoyl)-indole (35) and 1-benzenesulfonyl-2-(E-2 -methyl-butenoyl)-indole (37) (scheme i). The reaction of ()-17a with methyl tiglate (19), furnished a mixture of cycloaddition products which required reverse phase HPLC separation yielding: ()-6, ()-40, ()-41 and ()-42. Detailed spectroscopic characterization of these compounds lead to their structural and conformational determination. Compounds ()-6 and ()-42, had their structures confirmed by X-ray diffraction analyses. Among the six cycloaducts, obtained as a complex mixture, in the reaction of the methyl angelate (23) with (-)-17, only (-)-43 and ()-44, were obtained as pure samples by reverse phase HPLC. The remaining fractions were two distinct mixtures of two components depicted in scheme i, by: 45/45a and 46/46a. Formation of indole derivatives containing bicycle[4.4.0]decene moiety, were detected by GC/MS analyses, in the reaction of 1-methanesulfonyl-3-(E-2 -methyl-butenoyl)-indole (35) with (-)-17. Nevertheless, low reaction yields, forbade any further characterization (scheme i). Furthermore, no reaction was detected between diene (-)-17 and dienophile 37. Finally, the acyl chloride derivatives of compounds ()-6, ()-40, ()-41 and ()-42 used as a diastereoisomeric mixture, depicted in scheme ii as 51, were evaluated as a means to directly introduce the bicycle[ 4.4.0]decene moiety into the indole nucleus (scheme ii).

ASSUNTO(S)

reação de sintese organica diels-alder

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