<> "The repository administrator has not yet configured an RDF license."^^ . <> . . "Hydroxylamine-Mediated Arene C-H Amination and C-C Amination via Aza-Hock Rearrangement"^^ . "The thesis is focused on hydroxylamine-mediated direct arene C-H amination and C-C amination from benzyl alcohols, alkylarenes, styrenes and benzyl ethers/esters, which\r\nare used for the anilines synthesis. Additionally, this thesis consists of three parts.\r\n\r\nIn the first part (Chapter 2), a direct metal-free arene C-H amination mediated by hydroxylamines (TsONHBoc or TsONHR) was discovered, accidentally. Besides one literature reported with only three examples, this is the only report for an aniline synthesis via hydroxylamine derivatives under metal-free conditions. Primary anilines and secondary anilines are afforded under open flask conditions with this protocol, by using TsONHBoc or TsONHR, respectively. In contrast to metal-catalyzed processes, the reaction is triggered by an oxygen-accelerated SET (single electron transfer) from the aromatic systems to the electron-deficient hydroxylamine derivatives. The recombination of an arene radical cation and an aminyl radical, which are in close proximity, then affords the aminated products. The methodology can be applied for the amination of a variety of complex molecules, natural bioactive products and bestselling drugs. The operationally easy, broad functional group tolerance and scalability of this reaction in the absence of any metal make it appealing for both academy and industry.\r\n\r\nThe second part (Chapter 3) describes an aza-Hock rearrangement of benzyl alcohols by using hydroxylamines (ArSO2ONHR) as reagents under mild conditions, which\r\nmakes primary anilines accessible from O-(2,4,6-\r\ntrimethylbenzenesulfonyl)hydroxylamine (MSH) and secondary anilines available from other aminating reagents like TsONHR. Mechanistically we could prove that an\r\naza-Hock rearrangement operates. Other benzyl cation precursors (eg. benzyl ethers/esters/halides and alkylarenes) are also potent substrates for this strategy,\r\nexpanding the synthetic utility. In addition, chemoselective C-C brominations and oxygenations are possible under similar conditions. Interestingly, despite some early evidence for such a reactivity pattern, until now the synthetic utility of this process is limited and our report might pave the way for further protocols based on such pattern\r\nin the future.\r\n\r\nA modified aza-Hock rearrangement of benzyl cation precursors – alkylarenes, styrenes and benzyl ethers/esters – mediated by hydroxylamines, was investigated in the third\r\npart (Chapter 4). Notably, i-alkylarenes are differentiated by the aminating reagent MSH over n-alkylarenes, and n-alkylarenes are smoothly converted into anilines with\r\nTsONHMe. This rare phenomenon points out a way to distinguish different kinds of alkylarenes with such a pattern. Moreover, aminodealkenylation (C-C amination of\r\nstyrenes) opens a gateway for employing styrenes in a plethora of known benzyl cation transformations, which should serve as a valuable tool for anilines synthesis, adding to the growing catalogue of C-C functionalization."^^ . "2022" . . . . . . . "Tao"^^ . "Wang"^^ . "Tao Wang"^^ . . . . . . "Hydroxylamine-Mediated Arene C-H Amination and C-C Amination via Aza-Hock Rearrangement (PDF)"^^ . . . "thesis_Tao_Wang (final).pdf"^^ . . . "Hydroxylamine-Mediated Arene C-H Amination and C-C Amination via Aza-Hock Rearrangement (Other)"^^ . . . . . . "lightbox.jpg"^^ . . . "Hydroxylamine-Mediated Arene C-H Amination and C-C Amination via Aza-Hock Rearrangement (Other)"^^ . . . . . . "preview.jpg"^^ . . . "Hydroxylamine-Mediated Arene C-H Amination and C-C Amination via Aza-Hock Rearrangement (Other)"^^ . . . . . . "medium.jpg"^^ . . . "Hydroxylamine-Mediated Arene C-H Amination and C-C Amination via Aza-Hock Rearrangement (Other)"^^ . . . . . . "small.jpg"^^ . . . "Hydroxylamine-Mediated Arene C-H Amination and C-C Amination via Aza-Hock Rearrangement (Other)"^^ . . . . . . "indexcodes.txt"^^ . . "HTML Summary of #30608 \n\nHydroxylamine-Mediated Arene C-H Amination and C-C Amination via Aza-Hock Rearrangement\n\n" . "text/html" . . . "540 Chemie"@de . "540 Chemistry and allied sciences"@en . .