Iridium‐Catalyzed Chemo‐, Diastereo‐, and Enantioselective Allyl‐Allyl Coupling: Accessing All Four Stereoisomers of (E)‐1‐Boryl‐Substituted 1,5‐Dienes by Chirality Pairing

Here, we report a highly chemo‐, diastereo‐, and enantioselective allyl‐allyl coupling between branched allyl alcohols and α‐silyl‐substituted allylboronate esters, catalyzed by a chiral iridium complex. The α‐silyl‐substituted allylboronate esters can be chemoselectively coupled with allyl electrophiles, affording a diverse set of enantioenriched (E)‐1‐boryl‐substituted 1,5‐dienes in good yields, with excellent stereoselectivity. By permuting the chiral iridium catalysts and the substrates, we efficiently and selectively obtained all four stereoisomers bearing two consecutive chiral centers. Mechanistic studies via density functional theory calculations revealed the origins of the diastereo‐ and chemoselectivities, indicating the pivotal roles of the steric interaction, the β‐silicon effect, and a rapid desilylation process. Additional synthetic modifications for preparing a variety of enantioenriched compounds containing contiguous chiral centers are also included. We report an iridium‐catalyzed highly chemo‐, diastereo‐, and enantioselective allyl‐allyl coupling between branched allyl alcohols and α‐silyl‐substituted allylboronate esters resulting in enantioenriched (E)‐1‐boryl‐substituted 1,5‐dienes. All four stereoisomers with two adjacent chiral centers were obtained by chirality pairing. Mechanistic studies were conducted to understand the high levels of selectivity.