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  • Catalytic & sigma;-Bond Annulation with Ambiphilic Organohalides Enabled by & beta;-X Elimination ANGEWANDTE CHEMIE-INTERNATIONAL EDITION Ni, H., Dai, J., Yang, S., Loach, R. P., Chuba, M. D., McAlpine, I. J., Engle, K. M. 2023: e202306581


    We describe a catalytic cascade sequence involving directed C(sp3 )-H activation followed by β-heteroatom elimination to generate a PdII (π-alkene) intermediate that then undergoes redox-neutral annulation with an ambiphilic aryl halide to access 5- and 6-membered (hetero)cycles. Various alkyl C(sp3 )-oxygen, nitrogen, and sulfur bonds can be selectively activated, and the annulation proceeds with high diastereoselectivity. The method enables modification of amino acids with good retention of enantiomeric excess, as well as σ-bond ring-opening/ring-closing transfiguration of low-strain heterocycles. Despite its mechanistic complexity, the method employs simple conditions and is operationally straightforward to perform.

    View details for DOI 10.1002/anie.202306581

    View details for Web of Science ID 001030444500001

    View details for PubMedID 37306958