( R )‐BINOL‐6,6’‐bistriflone: Shortened Synthesis, Characterization, and Enantioselective Catalytic Applications

The title compound, characterized by X-ray crystallography, was accessed in 4 steps with 92 % ee. and 25 yield from an O-protected (R)-BINOL precursor. This revised synthetic route relied on a chlorosulfonylation reaction, as shortcut to previously developed sequence requiring the use of toxic SO2 gas bromine. strongly electron-impoverished (R)-6,6′-Tf2-BINOL proved effective ligand metal-catalyzed enantioselective transformations such Zr-based Mannich-type reaction. catalytic species crystallography unique tetrameric metal cluster. 6,6′-bistriflone groups also allowed exalt H-bond donor capacity BINOL moiety, illustrated organocatalyzed Morita-Baylis-Hillman transformation. Theoretical study indicated that induce drop phenol acidity 5 pKa units DMSO. Overall, this work simplified access, completed characterization, confirmed potential promising platform further elaborate activated chiral ligands or organocatalysts.