Cross‐Coupling of Grignard Reagents with Sulfonyl‐Activated sp3 Carbon‐Nitrogen Bonds

Sulfonyl‐activated sp3 carbon‐nitrogen bonds have been found to be cleaved by Grignard reagents in the presence of 5 mol% of copper(I) iodide (CuI). Significantly, a broad range of sulfonyl‐activated benzylic, allylic, and propargylic amines smoothly undergo the cross‐coupling reaction with Grignard reagents to afford structurally diverse coupling products in good to excellent yields and with high chemo‐, regio‐, and stereoselectivity. Moreover, an SN2 mechanism has been demonstrated to be involved in the cross‐coupling reaction that allows the asymmetric synthesis of chiral hydrocarbons from optically active α‐branched amine derivatives.