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

Abstract

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 great regiocontrol in good yields and with 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.