Counteranion‐Directed Catalysis in the Tsuji–Trost Reaction: Stereocontrolled Access to 2,5‐Disubstituted 3‐Hydroxy‐Tetrahydrofurans

Hydrogen bonds can play a prominent role in organometallic catalysis, as shown for the title reaction, in which a counteranion directs the cyclization through the formation of hydrogen bonds that likely involve a proton of the π‐allyl/palladium species itself. The reaction allows access to four out of the eight stereoisomers of 2,5‐disubstitued 3‐hydroxy‐tetrahydrofurans and thus fragments of complex natural products.