Enzyme-like Regiodivergent Behavior of a Flavopeptide Catalyst in Aerobic Baeyer-Villiger Oxidation

Authors

  • Ken Yamanomoto Department of Applied Chemistry Tokushima University Minamijosanjima, Tokushima 770-8506, Japan
  • Hazuki Kita Department of Applied Chemistry Tokushima University Minamijosanjima, Tokushima 770-8506, Japan
  • Yukihiro Arakawa Department of Applied Chemistry Tokushima University Minamijosanjima, Tokushima 770-8506, Japan
  • Keiji Minagawa Department of Applied Chemistry Tokushima University Minamijosanjima, Tokushima 770-8506, Japan, Institute of Liberal Arts and Sciences Tokushima University Minamijosanjima, Tokushima 770-8502, Japan
  • Yasushi Imada Department of Applied Chemistry Tokushima University Minamijosanjima, Tokushima 770-8506, Japan;, Email: arakawa.yukihiro@tokushima-u.ac.jp

DOI:

https://doi.org/10.2533/chimia.2018.866

Keywords:

Aerobic oxygenation, Baeyer-villiger oxidation, Biomimetic catalyst, Flavin, Peptide

Abstract

We recently developed a flavopeptide immobilized on polystyrene resin, Fl-Pep-PS, that could realize the first N5-unmodified neutral flavin (Fl)-catalyzed aerobic oxygenation reactions under non-enzymatic conditions. Although a key active species is assumed to be the corresponding 4a-hydroperoxyflavin (Fl4aOOH) from the unprecedented activity and unique chemoselectivity, further circumstantial support would be helpful to be sure since spectroscopic evidence is difficult to obtain due to the compound's insolubility. In this article, we report that the aerobic Baeyer-Villiger oxidation of a fused cyclobutanone, (±)-cis-bicyclo[3.2.0]hept-2-en-6-one (1), can be promoted with Fl-Pep-PS in a FMO-like chemoselectivity and regiodivergent manner via Fl-related catalytic intermediates, which delivers strong evidence of the involvement of Fl4aOOH as an active species in Fl-Pep-PS-catalyzed aerobic oxygenation reactions.

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Published

2018-12-19

How to Cite

[1]
K. Yamanomoto, H. Kita, Y. Arakawa, K. Minagawa, Y. Imada, Chimia 2018, 72, 866, DOI: 10.2533/chimia.2018.866.