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Titel:Asymmetric Catalysis with Octahedral Chiral-at-Metal Iridium and Rhodium Complexes
Autor:Wang, Chuanyong
Weitere Beteiligte: Meggers, Eric (Prof.Dr.)
Veröffentlicht:2016
URI:https://archiv.ub.uni-marburg.de/diss/z2016/0869
DOI: https://doi.org/10.17192/z2016.0869
URN: urn:nbn:de:hebis:04-z2016-08691
DDC:540 Chemie
Titel (trans.):Asymmetrische Katalyse mit Oktaedrischer Chiralität-am-Metall Iridium und Rhodium Komplexe
Publikationsdatum:2017-01-12
Lizenz:https://creativecommons.org/licenses/by/4.0

Dokument

Schlagwörter:
Katalyse, asymmetric catalysis, rhodium complex

Summary:
This thesis details the applications of a class of chiral-at-metal iridium(III) and rhodium(III) complexes for asymmetric catalysis. A rhodium-based asymmetric catalyst Δ-RhO is introduced which derives its optical activity from octahedral centrochirality. Besides serving as the exclusive source of chirality, the rhodium center functions as a Lewis acid to activate α,β-unsaturated 2-acyl imidazoles by two point binding and thereby catalyzes the asymmetric Michael addition of CH-acidic β-dicarbonyl compounds, for which the rhodium catalyst is found to be superior to its iridium congener (chapter 3.1). Due to its straightforward proline-mediated synthesis, high catalytic activity, and tolerance towards moisture and air, this chiral-at-rhodium complex has been used as chiral Lewis acid catalyst for many other asymmetric transformations in the Meggers group. The chiral-at-metal complexes Δ-IrO and Δ-IrS are investigated as highly efficient dual function photoredox/chiral Lewis acid catalysts in asymmetric photoactivated reactions. A simple chiral iridium complex Δ-IrO is capable of catalyzing the visible light activated α-aminoalkylation of 2-acyl-1-phenyl imidazoles, thereby serving as a “2-in-1” catalyst by combining photoinduced oxidation with asymmetric alkylation (chapter 3.2). Moreover, its derivative Δ-IrS is successfully utilized to the catalytic enantio- and diastereoselective redox coupling of trifluoromethyl ketones with tertiary amines to form 1,2-diamino alcohols (chapter 3.3). This single catalyst strategy provides new avenues for the synthesis of non-racemic molecules. An alternative strategy of merging the chiral Lewis acid Δ-RhS with photoredox catalyst fac-[Ir(ppy)3] is well applied to the asymmetric photoredox-mediated C(sp3)-H functionalization. This synthetic strategy exploits a radical translocation (1,5-hydrogen transfer) from an oxygen-centered to a carbon-centered radical with a subsequent stereocontrolled radical addition, affording C-C bond formation products with high enantioselectivities (up to 97% ee). Notably, the previously developed dual function catalyst Δ-IrS is not applicable for this asymmetric transformation (chapter 3.4).

Bibliographie / References

  1. 4. C. Wang, L.-A. Chen, H. Huo, X. Shen, K. Harms, L. Gong, E. Meggers, Asymmetric Lewis Acid Catalysis Directed by Octahedral Rhodium Centrochirality, Chem. Sci. 2015, 6, 1094−1100.
  2. 8. H. Huo, X. Shen, C. Wang, L. Zhang, P. Röse, L.-A. Chen, K. Harms, M. Marsch, G. Hilt, E. Meggers, Asymmetric Photoredox Transition-Metal Catalysis Activated by Visible Light, Nature 2014, 515, 100−103.
  3. 2. C. Wang, J. Qin, X. Shen, R. Riedel, K. Harms, E. Meggers, Asymmetric Radical-Radical CrossCoupling through Visible-Light Activated Iridium Catalysis, Angew. Chem. Int. Ed. 2016, 55, 685-688.
  4. 1. C. Wang, K. Harms, E. Meggers, Catalytic Asymmetric Csp3H Functionalization under Photoredox Conditions by Radical Translocation and Stereocontrolled Alkene Addition, Angew. Chem. Int. Ed. 2016, 55, 13495-13498.
  5. 6. H. Huo, C. Wang, K. Harms, E. Meggers, Enantioselective, Catalytic Trichloromethylation through Visible-Light-Activated Photoredox Catalysis with a Chiral Iridium Complex, J. Am. Chem. Soc. 2015, 137, 9551−9554.
  6. 3. C. Wang, Y. Zheng, H. Huo, P. Röse, L. Zhang, K. Harms, G. Hilt, E. Meggers, Merger of Visible Light Induced Oxidation and Enantioselective Alkylation with a Chiral Iridium Catalyst, Chem. Eur. J. 2015, 21, 7355−7359.
  7. 7. X. Shen, H. Huo, C. Wang, B. Zhang, K. Harms, E. Meggers, Octahedral Chiral-at-Metal Iridium Catalysts: Versatile Chiral Lewis Acids for Asymmetric Conjugate Additions, Chem. Eur. J. 2015, 21, 9720−9726.
  8. 5. M. Helms, C. Wang, B. Orth, K. Harms, E. Meggers, Proline and α-Methylproline as Chiral Auxiliaries for the Synthesis of Enantiopure Bis-Cyclometalated Iridium(III) Complexes, Eur. J. Inorg. Chem. 2016, 2896-2901.


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