Highly Enantioselective Rhodium‐Catalyzed Asymmetric 1,4‐Addition Reactions of Arylboronic Acids to Acyclic α,β‐Unsaturated Compounds: The Formal Synthesis of (−)‐Indatraline

It's do or diene: Stable chiral bicyclo[2.2.1]diene ligands were synthesized from (−)-5-oxobornyl acetate and utilized in the asymmetric 1,4-addition reaction of arylboronic acids with acyclic α,β-unsaturated compounds. Low catalytic loading of the complex, generated in situ from 1 and [{RhCl(C2H4)2}2], provides adducts in good to excellent yields and excellent enantioselectivities. This method was used for the formal total synthesis of (−)-indatraline.