Peptide‐Catalyzed Fragment Couplings that Form Axially Chiral Non‐ C 2 ‐Symmetric Biaryls

We have demonstrated that small, modular, tetrameric peptides featuring the Lewis‐basic residue β‐dimethylaminoalanine (Dmaa) are capable of atroposelectively coupling naphthols and ester‐bearing quinones to yield non‐ C 2 ‐symmetric BINOL‐type scaffolds with good yields and enantioselectivity. The study culminates in the asymmetric synthesis of backbone‐substituted scaffolds similar to 3,3′‐disubstituted BINOLs, such as ( R )‐TRIP, with good (94:6 e.r.) to excellent (>99.9:0.1 e.r.) enantioselectivity after recrystallization, and a diastereoselective net arylation of the minimally modified nonsteroidal anti‐inflammatory drug (NSAID) naproxen.