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Oxidant Evolution in Metal-Free Redox Amination Reactions

  • The N-containing heterocycles have received strong attention from the organic synthesis field because of their importance for pharmaceutical and material sciences. Nitrogen element plays an important role between inorganic salts and biomolecules, to search convenient methods combine C-N bond together become a hot topic in recent decades. Since the early beginning of 20th century, transition-metal-catalyzed coupling reactions had been well-known and world widely spread in organic researchs, achieved abundant significant progress. In the other side, the less toxic and more challenging transition metal free coupling method remained further potential value. With the evolution of amination reactions and oxidants, more and more effective, simplified, and atom economic organic synthesis methods will come soon. And these stories also drove me to think about investigating the novel cross-dehydrogenative-coupling amination methods development as the topics of my PhD research. Thus, we selected the phenothiazine derivatives as the N-nucleophile reagents and the phenols as the C-nucleophile reagents. To achieve the transition metal-free CDC aminations of phenols with phenothiazines, we scanned the chemical toolbox and tested a series of both common and uncommon oxidants. Firstly, we start the condition in the presence of cumene and O2. The proposed mechanism initiated by a Hock process, which would form in situ peroxo-species as initiator of the reaction. And the initial infra-red analysis predicted there is a strong O-H..N interaction. In the second method, a series of iodines with different valance have been tested to achieve the C-N bond formation of phenols with phenothiazines. This time, a simplified and more efficient method had been developed, which also provides a wider scope of phenols. Several controlling experiments had been conducted for the plausible pathway research. Large-scale synthesis of target molecular was also successfully performed. And then, we focus the research on the cross-coupling reaction of pre-oxidized(iminated) phenothiazine with ubiquitous phenols and indoles. In this task, we first regio-selectively synthesized the novel iminated phenothiazine derivatives with the traditional biocide and mild disinfectant, Chloramine T. Then the phenothiazinimine performed an ultra-simple condensation technique with phenol or indole coupling partners in a simplified condition. Parallel reactions were also performed to investigate the plausible pathway.
Author:Rongwei Jin
URN (permanent link):urn:nbn:de:hbz:386-kluedo-52638
Advisor:Frederic Patureau
Document Type:Doctoral Thesis
Language of publication:English
Publication Date:2018/05/28
Year of Publication:2018
Publishing Institute:Technische Universität Kaiserslautern
Granting Institute:Technische Universität Kaiserslautern
Acceptance Date of the Thesis:2018/05/03
Date of the Publication (Server):2018/06/01
Tag:Amination; Metal-Free; Oxidant Evolution
Number of page:X, 170, 6
Faculties / Organisational entities:Fachbereich Chemie
DDC-Cassification:5 Naturwissenschaften und Mathematik / 540 Chemie
Licence (German):Creative Commons 4.0 - Namensnennung, nicht kommerziell (CC BY-NC 4.0)