Premium
A Pyrene‐Linked Cavity within a β‐Barrel Protein Promotes an Asymmetric Diels–Alder Reaction
Author(s) -
Himiyama Tomoki,
Taniguchi Naomasa,
Kato Shunsuke,
Onoda Akira,
Hayashi Takashi
Publication year - 2017
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201704524
Subject(s) - moiety , pyrene , chemistry , regioselectivity , maleimide , cyclopentadiene , diels–alder reaction , coupling reaction , quenching (fluorescence) , photochemistry , stereochemistry , fluorescence , polymer chemistry , organic chemistry , catalysis , physics , quantum mechanics
A unique π‐expanded reaction cavity tethering a polycyclic moiety which provides a platform for substrate binding was constructed within the robust β‐barrel structure of nitrobindin (NB). NB variants with cavities of different sizes and shapes are coupled with N ‐(1‐pyrenyl)maleimide ( Pyr ) to prepare a series of NB‐ Pyr conjugates. The orientation of the pyrene moiety is fixed within the cavity by the coupling reaction. The fluorescent quenching analysis of NB‐ Pyr indicates that azachalcone ( aza ), which is a dienophile for a Diels–Alder (DA) reaction, is efficiently incorporated within the pyrene‐linked reaction cavity by the aromatic interaction. The DA reaction between aza and cyclopentadiene proceeds within the reaction cavity of NB‐ Pyr in the presence of Cu II ion in high yield and high enantio‐ and regioselectivity.