Catalyst-Controlled Divergent Cyclopropene Hydroselenation

We demonstrate the hydroselenation of cyclopropenes with catalyst-controlled divergent reactivity. Rh-catalysis enables asymmetric ring-retentive hydroselenation to produce chiral cyclopropyl selenides, while Cu-catalysis leads to ring-opening hydroselenation to yield vinyl selenides. Experimental and density functional theory (DFT) studies reveal the origin of this switchable selectivity. Rh(I)-catalysts promote oxidative addition of selenols, followed by migratory insertion and reductive elimination to afford ring-retentive hydroselenation products. In contrast, Cu(I)-catalysts have difficulty with the oxidative addition of selenols, but effectively activate cyclopropenes, leading to the formation of ring-opening vinyl selenides