Asymmetric Syntheses of (Z)- or (E)-β,γ-Unsaturated Ketones via Silane-Controlled Enantiodivergent Catalysis

Palladium‐Catalyzed Atroposelective Suzuki–Miyaura Coupling to Construct Axially Chiral Tetra‐Substituted α‐Boryl Styrenes

“…The observed conservation of enantioselectivity is likely due to the low acidity of the H atom α to the carbonyl group induced by the stereoelectronic effect. [ 19 ]…”

Catalytic Synthesis of Carbonyl Compounds Using Acyl Fluorides, Carbamoyl Fluorides, and Fluoroformates: An Overview

“…In 2023, Chen and co-workers reported a copper-catalyzed methods for the borylative acylation of silyl-substituted 1,3dienes with acyl fluorides (Scheme 13). [30] Both E-and Zselective access to enantioenriched β,γ-unsaturated ketones could be achieved by the judicious choice of ligand and the silyl group of the diene substrate. The reaction is likely to be initiated by the 1,2-addition of CuÀ BPin complex to a diene substrate.…”

Chiral bisphosphine Ph-BPE ligand: a rising star in asymmetric synthesis

“…70 Recently, Cu-catalyzed asymmetric carboboration of acyl fluorides with triisopropylsilyl-substituted 1,3-butadiene in the presence of Ph-BPE has been reported to afford ( E )-β,γ-unsaturated ketones with high optical purity and excellent E -selectivity (Scheme 15c). 71 Sieber et al reported a Cu-catalyzed carboboration of N -substituted allenes using aldehydes as carbon sources to access boryl-substituted 1,2-aminoalcohol synthons (Scheme 15d). 72 They provided three different post-transformation ways for the boronic ester group, and the reaction exhibited good dr and ee values.…”