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Master's Dissertation
DOI
10.11606/D.46.2016.tde-08082016-183730
Document
Author
Full name
Marcus Vinicius Craveiro
E-mail
Institute/School/College
Knowledge Area
Date of Defense
Published
São Paulo, 2004
Supervisor
Committee
Silva Junior, Luiz Fernando da (President)
Coelho, Fernando Antonio Santos
Kato, Massuo Jorge
Title in Portuguese
Estudos visando à síntese assimétrica de indanos através de reações de contração de anel promovidas por tálio(III)
Keywords in Portuguese
Compostos aromáticos
Compostos organometálicos (Estudo)
Indanos
Oxidação (Química)
Sais de Tálio
Síntese Assimétrica
Síntese orgânica (Estudo)
Abstract in Portuguese
Esta dissertação apresenta estudos visando à síntese de indanos oticamente ativos, através da contração de anel de 3-alquenóis promovida por tálio(III). Dois novos sais de tálio(III) foram preparados - o (S)-(-)-triacetoxipropionato de tálio (TTAP) e o tripropionato de tálio (TTP) - a partir do triacetato de tálio (TTA) e dos ácidos (S)-(-)-2-acetoxipropiônico e propiônico, respectivamente. A ciclização do isopulegol foi realizada com TTAP e com TTP, em rendimentos similares aos obtidos com TTA e com trinitrato de tálio (TTN). O rearranjo oxidativo do 2-(3,4-diidronaftalen-1-il)-etanol, que é um 3-alquenol, também pôde ser efetuado com o TTAP e com o TTP, embora rendimentos inferiores aos obtidos com TTN, com TTA, ou com trifluoroacetato de tálio (TTFA) tenham sido alcançados. Nestas contrações de anel, fica evidente que a ordem de reatividade segue a força elétron atraente dos ânions ligados ao tálio. Além disso, as melhores condições reacionais obtidas foram as que utilizam como solvente uma mistura de água e do ácido correspondente ao ligante do sal de tálio(III). Finalmente, na reação de contração de anel com o sal de tálio(III) quiral TTAP, o produto de contração de anel foi obtido como uma mistura racêmica. Os testes preliminares de resolução enzimática do 3-hidroxi-1-indan-1-il-propan-1-ona realizados com lipases mostraram-se promissores, abrindo novas perspectivas para a obtenção de indanos oticamente ativos com bom excesso enantiomérico.
Title in English
Studies toward the asymmetric synthesis of Indian through ring contraction reactions promoted by thallium (III)
Keywords in English
Aromatic compounds
Asymmetric synthesis
Indans
Organic synthesis (Studies)
Organometallic compounds (Study)
Oxidation (Chemistry)]
Thallium salts
Abstract in English
This dissertation presents a study toward the synthesis of optically active indans by the thallium(III) promoted ring contraction of 3-alkenols. Two new thallium(III) salts were prepared - thalllium (S)-(-)-triacetoxypropionate (TTAP) and thallium tripropionate (TTP) - from thallium triacetate (TIA) and (S)-(-)-2-acetoxypropionic acid and propionic acid, respectively. The cyclization of isopulegol was performed using TTAP or TTP. The isolated yields for these reactions are similar to that obtained with TTA or with thallium trinitrate (TTN) The oxidative rearrangement of the 2-(3,4-dihydro-naphthalen-1-yl)-ethanol, which is a 3alkenol, could also be performed by TTAP or by TTP, although the isolated yields were lower from that in a similar reaction with TTN, TTA or thallium trifluoroacetate (TTFA). In these ring contractions, the reactivity c1early depends on the eletron-withdrawing ability of the anion bonded to the thallium atom. In addition, the best reaction conditions are those where the solvent is a mixture of H2O and the acid corresponding to the ligand of the thallium(III) salt. Finally, in the reaction using the chiral non-racemic TTAP, the ring contraction product was obtained as a racemic mixture. The preliminary results on the enzymatic resolution of 3-hydroxy-1-indan-1-yl-propan-1-one using lipases show that optically active indan might be obtained in good e.e. using this approach.
 
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Publishing Date
2016-08-08
 
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