The Origins of Enantioselectivity in Rh–Diene Complex Catalysed Arylation of Cyclohex-2-enones

Authors

  • Dr. Silvia Gosiewska,

    1. Chemistry Research Laboratory, University of Oxford, 12 Mansfield Road, Oxford OX1 3TA (UK), Fax: (+ 44) 1865-275-644
    Search for more papers by this author
  • Dr. Jevgenij A. Raskatov,

    1. Chemistry Research Laboratory, University of Oxford, 12 Mansfield Road, Oxford OX1 3TA (UK), Fax: (+ 44) 1865-275-644
    Search for more papers by this author
  • Dr. Ryo Shintani,

    1. Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo, Kyoto 606-8502 (Japan), Fax: (+81) 75-753-3988
    Search for more papers by this author
  • Prof. Tamio Hayashi,

    Corresponding author
    1. Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo, Kyoto 606-8502 (Japan), Fax: (+81) 75-753-3988
    • Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo, Kyoto 606-8502 (Japan), Fax: (+81) 75-753-3988
    Search for more papers by this author
  • Dr. John M. Brown

    Corresponding author
    1. Chemistry Research Laboratory, University of Oxford, 12 Mansfield Road, Oxford OX1 3TA (UK), Fax: (+ 44) 1865-275-644
    • Chemistry Research Laboratory, University of Oxford, 12 Mansfield Road, Oxford OX1 3TA (UK), Fax: (+ 44) 1865-275-644
    Search for more papers by this author

Abstract

original image

Chiral diene ligands: Conjugate addition of aryl boronic acids to cyclohexenone is catalysed by Rh complexes of the simple chiral diene (S)-bicyclo[3.3.1]nona-2,6-diene in unexpectedly high ee. Insight into the reasons, and more generally the TS structure and pathways with other catalysts, was explored by using density functional theory. There was a gratifyingly good agreement between calculation and experiment. A lack of obvious steric discrimination together with systematic variations in TS structure implicated stereoelectronics.

Ancillary