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Application of Transmetalation to the Synthesis of Planar Chiral and Chiral-at-Metal Iridacycles

  • Ross A. Arthurs
    Ross A. Arthurs
    School of Chemistry, University of East Anglia, Norwich Research Park, Norwich, NR4 7TJ, U.K.
  • David L. Hughes
    David L. Hughes
    School of Chemistry, University of East Anglia, Norwich Research Park, Norwich, NR4 7TJ, U.K.
  • Peter N. Horton
    Peter N. Horton
    EPSRC National Crystallography Service, School of Chemistry, University of Southampton, Highfield, Southampton, SO17 1BJ, U.K.
  • Simon J. Coles
    Simon J. Coles
    EPSRC National Crystallography Service, School of Chemistry, University of Southampton, Highfield, Southampton, SO17 1BJ, U.K.
  • , and 
  • Christopher J. Richards*
    Christopher J. Richards
    School of Chemistry, University of East Anglia, Norwich Research Park, Norwich, NR4 7TJ, U.K.
    *E-mail: [email protected]
Cite this: Organometallics 2019, 38, 5, 1099–1107
Publication Date (Web):February 18, 2019
https://doi.org/10.1021/acs.organomet.8b00905
Copyright © 2019 American Chemical Society

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    Abstract

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    Diastereoselective lithiation of (S)-2-ferrocenyl-4-(1-methylethyl)oxazoline, followed by addition of HgCl2, resulted in the formation by transmetalation of an (S,Sp)-configured mercury substituted complex. Addition to this of [Cp*IrCl2]2 and tetrabutylammonium chloride resulted in a second transmetalation reaction and formation of an (S,Sp,RIr)-configured chloride-substituted half-sandwich iridacycle as exclusively a single diastereoisomer. By reversing the lithiation diastereoselectivity by use of a deuterium blocking group, an alternative (S,Rp,SIr)-configured iridacycle was synthesized similarly. Use of (R)-Ugi’s amine as substrate in the lithiation/double transmetalation sequence gave an (R,Sp,SIr)-configured half-sandwich iridacycle, complexes of this type being previously unavailable by direct cycloiridation. Lithium to gold transmetalation was also demonstrated with the synthesis of an (S,Sp)-configured Au(I) ferrocenyloxazoline derivative. Use of the (S,Rp,SIr)-iridacycle as a catalyst for the formation of a chiral product by reductive amination with azeotropic HCO2H/NEt3 resulted in a racemate.

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.organomet.8b00905.

    • Copies of the 1H, 13C, 31P NMR and X-ray crystallography details (PDF)

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    CCDC 1862175, 1873231, and 1873232 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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    Cited By

    This article is cited by 8 publications.

    1. Giovanni Salassa, Luca Salassa. Unconventional Approaches in Coordination Chemistry and Organometallic Reactivity. ACS Omega 2021, 6 (11) , 7240-7247. https://doi.org/10.1021/acsomega.0c05873
    2. Ross A. Arthurs, David L. Hughes, Christopher J. Richards. Ferrocenyloxazoline-Derived Planar Chiral Palladacycles: C–H Activation, Transmetalation, and Reversal of Diastereoselectivity. Organometallics 2019, 38 (21) , 4271-4279. https://doi.org/10.1021/acs.organomet.9b00551
    3. Sebastian Kaufmann, Michael Radius, Eric Moos, Frank Breher, Peter W. Roesky. Rhodium(I) and Iridium(I) Complexes of Ferrocenyl-Functionalized Amidinates and Bis(amidinates): κ2N-Coordination Versus Ferrocenyl Ortho-Metalation. Organometallics 2019, 38 (8) , 1721-1732. https://doi.org/10.1021/acs.organomet.9b00003
    4. Stefan Weigand, Karlheinz Sünkel. Chlorido-pentamethylcyclopentadienyl-[2-(2-pyridyl-кN)-ferrocenyl-кC]-iridium(III). Molbank 2024, 2024 (1) , M1770. https://doi.org/10.3390/M1770
    5. Li Dai, Di Xu, Meng-Jiao Yang. Synthesis of 2-oxazoline ferrocenes: Towards high-efficient chiral ligands and catalysts. Journal of Organometallic Chemistry 2023, 999 , 122831. https://doi.org/10.1016/j.jorganchem.2023.122831
    6. Li Dai, Di Xu, Yifei Mao, Jiaqi Zhu, Mengjiao Yang. Structures and Synthetic Strategies of Chiral Oxazolinyl Ferrocene Derivatives. Chinese Journal of Organic Chemistry 2022, 42 (8) , 2364. https://doi.org/10.6023/cjoc202201037
    7. Zhenyu Chen, Aysecik Kacmaz, Jianliang Xiao. Recent Development in the Synthesis and Catalytic Application of Iridacycles. The Chemical Record 2021, 21 (6) , 1506-1534. https://doi.org/10.1002/tcr.202100051
    8. Jennifer Smith, Aysecik Kacmaz, Chao Wang, Barbara Villa-Marcos, Jianliang Xiao. Chiral cyclometalated iridium complexes for asymmetric reduction reactions. Organic & Biomolecular Chemistry 2021, 19 (1) , 279-284. https://doi.org/10.1039/D0OB02049D

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