Details

Autor(en) / Beteiligte

• Ni, Hui‐Qi
• Dai, Jing‐Cheng
• Yang, Shouliang
• Loach, Richard P.
• Chuba, Matthew D.
• McAlpine, Indrawan J.
• Engle, Keary M.

Titel

Catalytic σ‐Bond Annulation with Ambiphilic Organohalides Enabled by β‐X Elimination

Ist Teil von

• Angewandte Chemie International Edition, 2023-08, Vol.62 (34), p.e202306581-n/a

Auflage

International ed. in English

Ort / Verlag

Germany: Wiley Subscription Services, Inc

Erscheinungsjahr

2023

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• 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. We report a σ‐bond annulation strategy that combines strong bond activation via β‐heteroatom elimination and redox‐neutral annulation along a PdII/PdIV redox manifold to access 5‐ and 6‐membered carbo‐ and heterocycles. Various alkyl C(sp3)−O, N, and S bonds can be selectively activated, allowing for enantioenriched amino acid derivatives and low‐strain heterocycles to be converted into value‐added products.