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Modern dehydrogenative amination reactions

  • Nitrogen element is preponderant in Nature. Found in its simplest form as diatomic gas in the air, as well as in elaborated molecules such as the double helix of DNA, this element is indisputably essential for life. Indeed, nitrogen is omnipresent in all metabolic pathways. With the advent of green chemistry, researchers attempt to functionalize arenes without pre-functionalization of the later for the establishment of C-C bond formation. Why not C-N bond formation? We investigated new oxidative amination reactions by cross-dehydrogenative-coupling. Concerned by atom economy and green processes, our objectives were: 1) to obviate pre-activation or pre-oxidation of both C-H coupling partner and N-aminating agent. 2) to avoid the use of chelating directing group. We achieved C-N bond formation for some classes of amines. Thus, we will describe the reactivity of cyclic secondary amines: carbazole, in presence of catalytic amount of ruthenium (II) and copper (II) to build the challenging C-N bond between two carbazoles. The initial mechanistic experiments will be present and discuss. Then, we will describe more challenging hetero-coupling formation between diarylamines and carbazoles. The new ruthenium (II)/ copper (II) catalytic system allowed forming the ortho-N-carbazolation of diarylamines. This reaction performed under mild conditions (O2 as terminal oxidant) displays an unusual intramolecular N-H••N interaction in the novel class of compounds. Finally, we will present a surprising metal free C-N bond formation between the ubiquitous phenols and the phenothiazines. Initially conducted in the presence of transition metals (RuII/CuII), this reaction proved to be efficient with the only effect of cumene and O2. Those components suggest a mechanism initiated by a Hock process. An initial infra-red analysis might point out a strong intramolecular O-H••N interaction in the resulting products. These first elements of reactivity, developed within the laboratory for “modern dehydrogenative amination reactions”, will be presented and discussed.

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Author:Marie-Laure Louillat Habermeyer
URN (permanent link):urn:nbn:de:hbz:386-kluedo-40377
Advisor:Frederic W. Patureau
Document Type:Doctoral Thesis
Language of publication:English
Publication Date:2015/03/24
Year of Publication:2015
Publishing Institute:Technische Universität Kaiserslautern
Granting Institute:Technische Universität Kaiserslautern
Acceptance Date of the Thesis:2015/02/27
Date of the Publication (Server):2015/03/25
Number of page:XIV, 230
Faculties / Organisational entities:Fachbereich Chemie
DDC-Cassification:5 Naturwissenschaften und Mathematik / 540 Chemie
Licence (German):Standard gemäß KLUEDO-Leitlinien vom 13.02.2015