Issue 8, 2017

Design of peptide-containing N5-unmodified neutral flavins that catalyze aerobic oxygenations

Abstract

Simulation of the monooxygenation function of flavoenzyme (Fl-Enz) has been long-studied with N5-modified cationic flavins (FlEt+), but never with N5-unmodified neutral flavins (Fl) despite the fact that Fl is genuinely equal to the active center of Fl-Enz. This is because of the greater lability of 4a-hydroperoxy adduct of Fl, FlOOH, compared to those of FlEt+, FlEtOOH, and Fl-Enz, FlOOH-Enz. In this study, Fl incorporated into a short peptide, flavopeptide (Fl-Pep), was designed by a rational top-down approach using a computational method, which could stabilize the corresponding 4a-hydroperoxy adduct (FlOOH-Pep) through intramolecular hydrogen bonds. We report catalytic chemoselective sulfoxidation as well as Baeyer–Villiger oxidation by means of Fl-Pep under light-shielding and aerobic conditions, which are the first Fl-Enz-mimetic aerobic oxygenation reactions catalyzed by Fl under non-enzymatic conditions.

Graphical abstract: Design of peptide-containing N5-unmodified neutral flavins that catalyze aerobic oxygenations

Supplementary files

Article information

Article type
Edge Article
Submitted
30 Apr 2017
Accepted
20 May 2017
First published
30 May 2017
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2017,8, 5468-5475

Design of peptide-containing N5-unmodified neutral flavins that catalyze aerobic oxygenations

Y. Arakawa, K. Yamanomoto, H. Kita, K. Minagawa, M. Tanaka, N. Haraguchi, S. Itsuno and Y. Imada, Chem. Sci., 2017, 8, 5468 DOI: 10.1039/C7SC01933E

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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