Pd‐Catalyzed Selective Bifunctionalization of 3‐Iodo‐<i>o</i>‐Carborane by Pd Migration

Abstract

Abstract A palladium‐catalyzed highly selective 3,4‐bifunctionalization of 3‐I‐ o ‐carborane has been developed, leading to the preparation of 3‐alkenyl‐4‐R‐ o ‐carboranes (R=alkyl, alkynyl, aryl, allyl, CN, and amido) in high to excellent yields. This protocol combines the sequential activation of cage B(3)−I and B(4)−H bonds by Pd migration from exo ‐alkenyl sp 2 C to cage B(4), which is driven by thermodynamic force. This represents a brand‐new strategy for selective bifunctionalization of carboranes with two different substituents.