Enantio‐ and Regioconvergent Nickel‐Catalyzed Etherification of Phenols by Allylation to Access Chiral C(sp3)–O Allyl Aryl Ethers

An enantio‐ and regioconvergent allylation of phenols under nickel catalysis with an α‐/γ‐regioisomeric mixture of racemic silylated/germylated allylic chlorides is reported. The silyl/germyl group governs the regioselectivity, and the transformation affords enantiomerically enriched unsymmetrical 1,3‐disubstituted allyl aryl ethers with excellent regiocontrol in good yields and excellent enantioselectivities. Notably, no nickel‐mediated C−O bond activation is observed at room temperature. The synthetic value of these densely functionalized silicon‐containing building blocks is demonstrated in a series of chemoselective transformations, including a [3,3]‐sigmatropic rearrangement for the construction of an α‐chiral silane.