Copper- and Cobalt-Catalyzed Syntheses of Thiophene-Based Tertiary Amines

Salima Bouarfa (1) , Simon Graβl (2) , Maria Ivanova (2) , Timothy Langlais (1) , Ghenia Bentabed-Ababsa (3) , Frédéric Lassagne (1) , William Erb (4) , Thierry Roisnel (1) , Vincent Dorcet (1) , Paul Knochel (5) , Florence Mongin (1)

1 ISCR - Institut des Sciences Chimiques de Rennes
2 LMU - Ludwig-Maximilians-Universität München
3 Université d'Oran 1 Ahmed Ben Bella [Oran]
4 ICSN - Institut de Chimie des Substances Naturelles
5 LMU - Ludwig Maximilian University [Munich]

Thienylzinc halides and related compounds prepared by deprotonation followed by transmetalation were used in copper-catalyzed amination using N-benzoyloxy secondary amines. By extending the reaction to 1,5-naphthyridine, it was showed that the competitive dimer formation observed in the case of thiophenes was linked with the low stability of some thienylamines rather than homocoupling. Interestingly, thienylzinc halides and related compounds prepared by transmetalation of thienylmagnesium halides, either prepared from their bromo-precursors or generated by deprotometalation, were satisfactorily employed in cobalt-catalyzed aminations. Finally, aminothiophenes were involved in copper-catalyzed mono-and diN -arylations, affording differently substituted di-and triphenylamines.

Domains: Chemical Sciences; Organic chemistry; Chemical Sciences; Catalysis

Salima Bouarfa, Simon Graβl, Maria Ivanova, Timothy Langlais, Ghenia Bentabed-Ababsa, et al.. Copper- and Cobalt-Catalyzed Syntheses of Thiophene-Based Tertiary Amines. European Journal of Organic Chemistry, 2019, 2019 (20), pp.3244-3258. ⟨10.1002/ejoc.201900276⟩. ⟨hal-02177982⟩