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@PHDTHESIS{Pei:855909,
      author       = {Pei, Chao},
      othercontributors = {Königs, René Michael and Patureau, Frederic W.},
      title        = {{T}heoretical mechanistic investigations of carbene and
                      nitrene transfer reactions},
      school       = {RWTH Aachen University},
      type         = {Dissertation},
      address      = {Aachen},
      publisher    = {RWTH Aachen University},
      reportid     = {RWTH-2022-10534},
      pages        = {1 Online-Ressource : Illustrationen, Diagramme},
      year         = {2022},
      note         = {Veröffentlicht auf dem Publikationsserver der RWTH Aachen
                      University 2023; Dissertation, RWTH Aachen University, 2022},
      abstract     = {My PhD thesis focuses on the study of transition-metal
                      catalyzed or photochemical carbene and nitrene transfer
                      reactions. Firstly, detailed computational studies revealed
                      that electrophilic gold(I)-carbene prefers a site-selective
                      C−H functionalization of carbazole, in which trace amounts
                      of water play a crucial role to rationalize the selectivity.
                      Secondly, gem-difluoro olefinations of electron-rich
                      anilines with trifluoromethyl diazoalkanes under copper(I)
                      catalysis were investigated by DFT calculations. It
                      indicated that anilines play a dual role in this reaction -
                      stabilizing the zwitterion intermediate and promoting the
                      deprotonation process. In addition, trifluoromethyl
                      diazoalkanes could be utilized in Pd-catalyzed cross
                      couplings with vinyl bromides, leading to synthetically
                      challenging trifluoromethylated tetrasubstituted allenes.
                      Moreover, theoretical investigations uncovered the potential
                      mechanisms of several Rh(II)-catalyzed
                      1,3-difunctionalization reactions of triazoles with
                      selenides or sulfides.Instead of metal catalysis, the
                      emerging photochemical carbene transfer reactions opened up
                      several unsolved mechanism questions. Firstly, under blue
                      light irradiation, the spin states of photochemically
                      generated diaryl carbenes are controlled by substituents on
                      the aryl rings, which results in divergent reactivity such
                      as cyclopropenations, C(sp)−H insertion, or cascade
                      cyclization reactions with alkynes. Moreover, computational
                      study indicated that photoinduced O-H insertion reactions of
                      diaryl diazomethanes or aryl diazoacetates involve
                      hydrogen-bond-assisted intersystem crossing processes. In
                      addition, calculations supported the formation of an oxonium
                      ylide in three-component reaction with
                      N-fluoro-benzenesulfonimide (NFSI), aryl diazoacetates and
                      1,4-dioxane. In the last section, our theoretical studies
                      revealed that the photosensitizer-promoted decomposition of
                      ethyl diazoacetate (EDA) opens up its radical or triplet
                      reactivity, which were successfully applied in
                      gem-difluoroolefinations reactions. In the next part, we
                      conducted theoretical studies on photochemical formal C−H
                      aminations of α-methyl styrene with iminoiodinane via
                      triplet nitrene intermediates, and nitrene radical anion
                      reactivity in aziridinations of styrenes under photoredox
                      catalysis.Last but not least, detailed calculations were
                      performed on novel Ru(II)-catalyzed C(sp3)−C(sp3) coupling
                      reactions of methylpyridyl-substituted amides and alkyl
                      bromides. We identify that cyclometalated
                      metal-substrate-bound complexes can be regarded as a
                      photosensitizer, which promote further intramolecular single
                      electron transfer (ISET) processes and C(sp3)−C(sp3)
                      diradical couplings. In addition, photoinduced palladium
                      catalysis has also been applied in the radical
                      transformations, such as the cascade radical cyclization of
                      isonitriles, which afforded phenanthridines in high
                      efficiency.},
      cin          = {155830 / 150000},
      ddc          = {540},
      cid          = {$I:(DE-82)155830_20160414$ / $I:(DE-82)150000_20140620$},
      typ          = {PUB:(DE-HGF)11},
      doi          = {10.18154/RWTH-2022-10534},
      url          = {https://publications.rwth-aachen.de/record/855909},
}