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%0 Thesis
%A Wen, Jian
%T Copper-catalyzed dealkylations and rhodium-catalyzed C−H functionalizations of NH-sulfoximines
%I RWTH Aachen University
%V Dissertation
%C Aachen
%M RWTH-2018-00926
%P 1 Online-Ressource (III, 127 Seiten) : Illustrationen
%D 2018
%Z Veröffentlicht auf dem Publikationsserver der RWTH Aachen University
%Z Dissertation, RWTH Aachen University, 2018
%X In recent years, functionalizations of sulfoximines have attracted much attention because of interesting biological activities of the resulting products. For example, to novel heterocycles. In this thesis, the three types of functionalizations of NH-sulfoximines for the construction of sulfonimidamides, 1,2-benzothiazine 1-oxides and 1,2-benzothiazepine 1-oxides are presented. Firstly, copper-catalyzed dealkylation/amination sequences which provides sulfonimidamides from NH-sulfoximines under an atmosphere of dioxygen. A wide range of sulfoximines were tolerated affording the corresponding products in moderate to good yields. Mechanistic studies suggested the involvement of radicals in both the C–S bond cleavage and the formation of the new N–S bond. Then, 4-unsubstituted 1,2-benzothiazines were prepared from NH-sulfoximines and allyl methyl carbonate by Rh(III)-catalyzed domino allylation/oxidative cyclization.  The reaction exhibited a broad scope with respect to NH-sulfoximines. A plausible mechanism was proposed, and chemical potential of the products has been demonstrated by some functionalization reactions. In the last part of the work, Rh(III)-catalyzed [4 + 3] annulations of NH-sulfoximines with α,β-unsaturated ketones leading to 1,2-benzothiazepine 1‑oxides was presented. For a wide range of substrates with various functional groups, product were obtained in moderate to good yields. A mechanistic scheme has been proposed, and the oxidative cleavage of the double bond in the heterocycle was demonstrated.
%F PUB:(DE-HGF)11
%9 Dissertation / PhD Thesis
%R 10.18154/RWTH-2018-00926
%U https://publications.rwth-aachen.de/record/713112