Angewandte Chemie - International Edition
Angewandte Chemie - International Edition
4 years ago

A Pyrene-Linked Cavity within a β-Barrel Protein Promotes an Asymmetric Diels–Alder Reaction

A Pyrene-Linked Cavity within a β-Barrel Protein Promotes an Asymmetric Diels–Alder Reaction
Naomasa Taniguchi, Takashi Hayashi, Shunsuke Kato, Akira Onoda, Tomoki Himiyama
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 CuII ion in high yield and high enantio- and regioselectivity. Selectivity by the barrel-load: A reaction cavity with a tethered polycyclic pyrene moiety, which acts as a platform to provide aromatic interactions, is constructed within the rigid scaffold of the β-barrel nitrobindin protein. An asymmetric Diels–Alder reaction between azachalcone and cyclopentadiene proceeds within the reaction cavity of the pyrene-linked nitrobindin with high stereoselectivity.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/anie.201704524

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