Allénylsilanes, allénylzincs et allénylboranes: préparation stéréosélective à partir d'électrophiles propargyliques et étude de réactivité

Translated title of the contribution: Allenylsilanes, allenylzincs and allenylboranes: stereoselective synthesis from propargylic electrophiles and study of their reactivity

Research output: External Thesis Doctoral Thesis

Abstract

During this research, the synthesis and use of 4-amino- and 4-hydroxy-1-allenylmetals have been studied.Two stereoselective and stereospecific syntheses of 4-sulfinamido- and 4-acetamido-1-allenylsilanes have been developed. These two synthetic routes rely on the reaction of lithium tris(dimethylphenylsilyl)zincate with acetylenic N-tert-butanesulfinylaziridines on one hand, and propargylic -acetamidoalkyl acetates on the other hand. The scope and limitations of these two complementary methods have been explored. The electrophilic fluorodesilylation reaction of 4-sulfinamido- and 4-acétamido-1-allenylsilanes with Selecfluor® gave access to propargylic -fluoroacetates in a stereoselective manner. A transition state model has also been postulated to explain the level of the chirality transfer observed. Finally, different synthetic routes towards 4-sulfinamido- and 4-sulfonylamido-1-allenylzincs through the 1,2-metalate rearrangement of acetylenic lithium tris(dimethylphenylsilyl)zincates, obtained from N-tert-butanesulfinyl- and N-tert-butanesulfonylaziridines, were proven to be unsuccessful. However, in the context of a French-Belgian collaboration, the study of the copper-catalyzed borylation of acetylenic epoxides led to promising results and paved the way for a new stereoselective synthesis of 4-hydroxy-1-allenylboranes.
Translated title of the contributionAllenylsilanes, allenylzincs and allenylboranes: stereoselective synthesis from propargylic electrophiles and study of their reactivity
Original languageFrench
QualificationPh.D.
Awarding Institution
  • Sorbonne University, UPMC University, Paris, France.
Supervisors/Advisors
  • Ferreira, Franck, Supervisor, External person
  • Chemla, Fabrice, Supervisor, External person
Publication statusUnpublished - 17 Oct 2016

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