Copper-Catalyzed Asymmetric Carbocyanation of 1,3-Dienes and Vinylarenes with Simple Aldehydes and Alkanes

The asymmetric radical carbocyanation of alkenes represents a powerful strategy for synthesizing chiral nitriles. While readily available aldehydes and alkanes are unique and atom-economical carbon radical precursors via hydrogen atom transfer (HAT), their utilization in the asymmetric carbocyanation of alkenes remains underdeveloped. Herein, we report a copper-catalyzed asymmetric radical carbocyanation of 1,3-dienes and vinylarenes, employing both aldehydes and alkanes as carbon radical sources. This protocol utilizes organic peroxides as radical initiators in combination with chiral bisoxazoline-based copper catalysts. The choice of organic peroxide proved critical in controlling reactivity: tert-butyl hydroperoxide (TBHP) enabled efficient aldehyde-derived acylcyanation, while di-tert-butyl peroxide (DTBP) under photoinduced conditions was optimal for alkane-derived alkylcyanation. This strategy provides a practical and versatile approach to accessing structurally diverse chiral allylic and benzylic nitriles.