We describe the kinetic resolution of α‐silyl‐substituted allylboronate esters via chiral phosphoric acid‐catalyzed chemo‐, diastereo‐ and enantioselective allylboration of aldehydes. This process provides two synthetically versatile enantioenriched compounds, (Z)‐δ‐silyl‐substituted anti‐homoallylic alcohols and α‐silyl‐substituted allylboronate esters, with a selectivity factor up to 328. We propose that the reaction proceeds through a closed chair‐like transition state with the silane moiety occupying a pseudo‐axial position, thus readily resolving α‐silyl‐substituted allylboronate esters. The synthetic utility of the obtained enantioenriched compounds is highlighted by their further transformations to give a diverse set of enantioenriched molecules.

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.

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.

Here, we report a transition-metal-free chemo-, regio-, and stereoselective electrophilic fluorodesilylation of α-silyl-substituted allylboronate esters. The α-silyl-substituted allylboronate esters can be chemoselectively coupled with selectfluor resulting in a variety of (E)-boryl-substituted allyl fluorides in good yields with γ- and (E)-selectivity. The utilities of the obtained (E)-boryl-substituted allyl fluorides are highlighted by further modifications to afford allyl or alkyl fluoride derivatives.

The front cover picture, provided by Seung Hwan Cho and co‐workers, illustrates (R)‐TRIP‐catalyzed kinetic resolution of α‐silyl‐substituted allylboronate esters through chemo‐, diastereo‐, and enantioselective allylation of aldehydes. The reaction is proposed to proceed via a chair‐like transition state by the double coordination of (R)‐TRIP to the C−H bond of aldehydes and the oxygen atom of Bpin group, thus effectively resolving α‐silyl‐substituted allylboronate esters with high enantiomeric ratios. Details can be found in the communication by Seung Hwan Cho and co‐workers (J. Park, Y. Jung, J. Kim, E. Lee, S. Y. Lee, S. H. Cho, Adv. Synth. Catal. 2021, 363, 2371–2376; DOI: 10.1002/adsc.202001170).