We have demonstrated that small, modular,t etrameric peptides featuring the Lewis-basic residue b-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.T he study culminates in the asymmetric synthesis of backbone-substituted scaffolds similar to 3,3'-disubstituted BINOLs,s uch as (R)-TRIP,w ith good (94:6 e.r.)t oe xcellent (> 99.9:0.1 e.r.)e nantioselectivity after recrystallization, and ad iastereoselective net arylation of the minimally modified nonsteroidal anti-inflammatory drug (NSAID) naproxen. Scheme 1. Approaches toward construction of enantioenriched atropisomers through naphthol-quinone coupling.

The atroposelective synthesis of N-aryl 1,2,4-triazoles was developed. A cyclodehydration reaction was rendered asymmetric with the use of a chiral phosphoric acid catalyst to afford atropisomeric N-aryl 1,2,4-triazoles in up to 91:9 er. Recrystallization of the isolated heterocycle further enriched the atropisomeric ratio of several analogs to 99:1 er or greater. A divergent and substrate-dependent reaction pathway yielding a different heterocyclic product is also disclosed. Note pubs.acs.org/joc

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‐C2‐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.