Palladium‐Catalyzed Chemoselective Allylic Substitution,Suzuki–Miyaura Cross‐Coupling,and Allene Formation of Bifunctional 2‐B(pin)‐Substituted Allylic Acetate Derivatives

A formidable challenge at the forefront of organic synthesis is the control of chemoselectivity to enable the selective formation of diverse structural motifs from a readily available substrate class. Presented herein is a detailed study of chemoselectivity with palladium‐based phosphane catalysts and readily available 2‐B(pin)‐substituted allylic acetates, benzoates, and carbonates. Depending on the choice of reagents, catalysts, and reaction conditions, 2‐B(pin)‐substituted allylic acetates and derivatives can be steered into one of three reaction manifolds: allylic substitution, Suzuki–Miyaura cross‐coupling, or elimination to form allenes, all with excellent chemoselectivity. Studies on the chemoselectivity of Pd catalysts in their reactivity with boron‐bearing allylic acetate derivatives led to the development of diverse and practical reactions with potential utility in synthetic organic chemistry.