Asymmetric Synthesis of Chiral 1,2‐Bis(Boronic) Esters Featuring Acyclic, Non‐Adjacent 1,3‐Stereocenters

The construction of acyclic, non‐adjacent 1,3‐stereogenic centers, prevalent motifs in drugs and bioactive molecules, has been a long‐standing synthetic challenge due to acyclic nucleophiles being distant from the chiral environment. In this study, we successfully synthesized highly valuable 1,2‐bis(boronic) esters featuring acyclic and nonadjacent 1,3‐stereocenters. Notably, this reaction selectively produces migratory coupling products rather than alternative deborylative allylation or direct allylation byproducts. This approach introduces a new activation mode for selective transformations of gem‐diborylmethane in asymmetric catalysis. Additionally, we found that other gem‐diborylalkanes, previously challenging due to steric hindrance, also successfully participated in this reaction. The incorporation of 1,2‐bis(boryl)alkenes facilitated the diversification of the alkenyl and two boron moieties in our target compounds, thereby enabling access to a broad array of versatile molecules. DFT calculations were performed to elucidate the reaction mechanism and shed light on the factors responsible for the observed excellent enantioselectivity and diastereoselectivity. These were determined to arise from ligand‐substrate steric repulsions in the syn‐addition transition state.