Cobalt‐Catalyzed [2σ+2π] Cycloaddition via Site‐Selective Capture of Bicyclobutane Diradical
We report a Co(II)‐catalyzed strategy that combines thermal activation of bicyclo[1.1.0]butane (BCBs) with site‐selective radical capture to furnish head‐to‐head fused bicyclo[2.1.1]hexanes via [2σ+2π] cycloaddition with indoles. Detailed mechanistic studies (31P NMR, EPR, CV, and DFT) support the catalytic pathway, while phosphine‐oxide trapping and X‐
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