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Master's Dissertation
DOI
10.11606/D.9.2012.tde-10092012-112502
Document
Author
Full name
Daiana Martins Leal
E-mail
Institute/School/College
Knowledge Area
Date of Defense
Published
São Paulo, 2012
Supervisor
Committee
Stefani, Helio Alexandre (President)
Santos, Alcindo Aparecido dos
Vieira, Adriano Siqueira
Title in Portuguese
Síntese de 4-organocalcogenoil-1H-1,2,3-triazol: funcionalização da unidade triazólica via acoplamento de Negishi catalisado por níquel
Keywords in Portuguese
1,2,3-Triazóis
1,3-dipolar
Acoplamento tipo Negishi
Cicloadição
Organocalcogênios
Reatividade
Síntese orgânica
Abstract in Portuguese
No presente trabalho, uma série de calcogenotriazóis (3a-o,5a-f) foi sintetizada empregando reações de cicloadição entre azidas e alquinos catalisadas por cobre (CAACu), com duas diferentes metodologias: uma aplicada aos selenetos e outra aos teluretos triazólicos. Os selenetos acetilênicos (1a,b) foram submetidos ao sistema catalítico Cu(OAc)2/ascorbato de sódio, enquanto os teluretos (4a,b) sumetidos à CuI e PMDTA. Foi possível obter 14 diferentes selenotriazóis (3a-o) e 6 telurotriazóis (5a-f). Em seguida, os produtos obtidos através da cicloadição foram empregados como eletrófilos em reações de acoplamento cruzado tipo Negishi com nucleófilos de organozinco. Assim, o emprego de catalisador de níquel associado à fosfinas como ligantes permitiu a síntese de diversos compostos triazólicos (6a-k) partindo dos calcogenetos triazólicos (3k, 3l, 3o, 5a). Os resultados obtidos com a metodologia desenvolvida demonstraram a eficiência da catálise de níquel em reações de acoplamento tipo Negishi além da aplicabilidade dos produtos originados das reações de cicloadição catalisada por cobre.
Title in English
4-Organochalcogenoyl-1H-1,2,3-triazole synthesis: functionalization of the triazole scaffold by nickel-catalyzed Negishi cross-coupling
Keywords in English
1,2,3-Triazoles
Cycloaddition
Negishi-type cross-coupling
Organic syntesis
Organochalcogen compounds
Reactivity
Abstract in English
In this work it was synthesized a range of different 4- organochalcogenoyl-triazoles (3a-o, 5a-f) employing the Copper Catalyzed Azide-Alkyne Cycloadittion (CAACu) 1,3-dipolar in two distinct methodologies: one of them applied to the selenium compounds and the other one to the tellurium triazoles. To the acetylenic selenides (1a,b) was employed the catalytic system composing of Cu(OAc)2 and sodium ascorbate, while with the telurides (4a,b), CuI and PMDTA was used. Practicing these methodologies it was possible to obtain 14 differents selenium-triazoles (3a-o) and 6 tellurotrizoles (5a-f). In the next step of the work, the products previously obtained through the CAACu were employed as the eletrophile partner in Negishi-type cross coupling reactions, with organozinc nucleophiles. Thereby, the use of nickel catalyst and fosfines ligands allowed some triazolic compounds (6a-k) synthesis starting from 1,2,3-triazole chalcogenides (3k, 3l, 3o, 5a). The results described here showed the nickel catalysis efficiency in Negishi-type cross-coupling reaction. Furthermore, it is remarkable the applicability of the products obtained from the CAACu.
 
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Publishing Date
2012-10-19
 
WARNING: The material described below relates to works resulting from this thesis or dissertation. The contents of these works are the author's responsibility.
  • Pena, Jesus M., et al. Negishi cross-coupling of organotellurium compounds: synthesis of biaryls, aryl-, and diaryl acetylenes [doi:10.1016/j.tetlet.2011.06.025]. Tetrahedron Letters [online], 2011, vol. 52, p. 4398-4401.
  • STEFANI, H. A., Leal, Daiana M., and Manarin, Flávia. 4-Organochalcogenoyl-1H-1,2,3-triazoles: synthesis and functionalization by a nickel-catalyzed Negishi cross-coupling reaction [doi:10.1016/j.tetlet.2012.09.062]. Tetrahedron Letters [online], 2012, vol. 53, p. 6495-6499.
  • Stefani, Helio A., et al. Functionalization of 5-Telluro-1,2,3-triazoles via Te-Li Transmetallation Exchange. European Journal of Organic Chemistry , 2013.
  • Stefani, Hélio A., et al. Synthesis of 5-Organotellanyl-1 H -1,2,3-triazoles: Functionalization of the 5-Position Scaffold by the Sonogashira Cross-Coupling Reaction [doi:10.1002/ejoc.201300009]. European Journal of Organic Chemistry [online], 2013, vol. 5, p. n/a-n/a.
  • Leal, Daiana M., MANARIN, FLÁVIA, and STEFANI, H. A. Synthesis of 4- Organochalcogenyl-1-H-1,2,3-Triazoles. In 14th Brazilian Meeting on Organic Synthesis, Brasíia, 2011. Synthesis of 4- Organochalcogenyl-1-H-1,2,3-Triazoles., 2011. Abstract.
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