Oxidative Difunctionalization of Alkenyl MIDA Boronates: A Versatile Platform for Halogenated and Trifluoromethylated α‐Boryl Ketones

The synthesis of halogenated and trifluoromethylated α‐boryl ketones via a one‐pot oxidative difunctionalization of alkenyl MIDA boronates is reported. These novel densely functionalized organoborons bearing synthetically and functionally valuable carbonyl, halogen/CF₃ and boronate moieties within the same molecule are synthetically challenging for the chemist, but have great synthetic potential, as demonstrated by their applications in a straightforward synthesis of borylated furans. The generality of this reaction was extensively investigated. This reaction is attractive since the starting materials, alkenyl MIDA boronates, are easily accessible.     

Divergent Synthesis of Heteroatom‐Centered 4,8,12‐Triazatriangulenes

The increasing attention devoted to triangulenes and their heteroatom derivatives inspired us to explore a divergent synthesis of heteroatom‐centered 4,8,12‐triazatriangulenes, which involved the preparation of a nitrogen‐containing macrocyclic precursor and subsequent central heteroatom introduction by electrophilic C−Li and C−H substitution. The boron‐centered triangulene has a planar structure unlike the bowl‐shaped phosphorus‐ and silicon‐centered triangulenes. The described synthetic procedure can be used to fabricate a broad range of attractive functional materials, for example, for organic light‐emitting diodes, based on heteroatom‐centered triangulenes.     

Synthesis of γ‐Boryl‐Substituted Homoallylic Alcohols with anti Stereochemistry Based on a Double‐Bond Transposition

The stereoselective synthesis of anti isomers of γ‐boryl‐substituted homoallylic alcohols is disclosed. (E)‐1,2‐Di(boryl)alk‐1‐enes undergo Ru‐catalyzed double‐bond transposition with control of the geometry. The in situ generated (E)‐1,2‐di(boryl)alk‐2‐enes add to aldehydes in a stereospecific manner. The alkenylboron group within the product is amenable to a variety of synthetic derivatizations.