Asymmetric Ring‐Opening Reactions of Donor‐Acceptor Cyclopropanes and Cyclobutanes

Abstract Donor‐acceptor (DA) cyclopropanes are particularly useful synthetic building blocks, which have been widely applied in the total synthesis of natural products and important chiral molecules in organic synthesis. The asymmetric ring‐opening reactions of racemic DA cyclopropanes and cyclobutanes, for example, aryl‐substituted 1,1‐cyclopropane diesters and aryl‐substituted 1,1‐cyclobutane diesters, with nucleophiles provides versatile access to optically active γ‐ and δ‐functionalized carbon skeletons, as well as the kinetic resolution of racemic DA cyclopropanes, which are useful chiral skeletons in organic synthesis. Recently, we have developed a series of highly enantioselective ring‐opening and annulation reactions of DA cyclopropanes and cyclobutanes with various nucleophiles, such as amines, alcohols, nitrones, azomethine imines, enol silyl ethers, and indoles, by employing nickel and copper catalysts with TOX and SaBOX as ligands. The reactions worked smoothly with excellent diastereoselectivities and enantioselectivities (up to >99/1 dr and up to 99 % ee ) over broad substrate scopes.