Catalyst-Controlled Divergent Cyclopropene Hydroselenation

Abstract

Selenium plays a vital role as a micronutrient in various biological processes and exhibits unique catalytic properties in synthetic chemistry. While there has been remarkable progress in achieving asymmetric hydroselenation of polar alkenes, the catalytic asymmetric hydroselenation of nonpolar alkenes remains a significant and persistent challenge. Herein, we demonstrate the catalytic hydroselenation of cyclopropenes with a 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 studies reveal the origin of this switchable selectivity. Rh(I)-catalysts promote the 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.