Peptide‐Catalyzed Fragment Couplings that Form Axially Chiral Non‐C₂‐Symmetric Biaryls

Abstract

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.

Recent Advances in the Reactions of β-Naphthol at α-Position

“…继上述研究之后, 2020 年, Miller 课题组 [54] 报道了 具有 Lewis 碱性残基的四聚肽催化的 β-萘酚和含酯对苯 醌的偶联反应, 以较高的对映选择性成功构建了非 C 2 对称的联芳基化合物(Scheme 24). 作者提出, 该反应是 由 Lewis 碱性残基 β-二甲氨基丙氨酸上的胺首先与萘酚 上的羟基相互作用, 促进底物和催化剂之间的密切结 合, 从而推动反应的进行.…”