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

被引：38

作者：

Arakawa, Yukihiro ^{[1
]}

Yamanomoto, Ken ^{[1
]}

Kita, Hazuki ^{[1
]}

Minagawa, Keiji ^{[1
,2
]}

Tanaka, Masami ^{[3
]}

Haraguchi, Naoki ^{[4
]}

Itsuno, Shinichi ^{[4
]}

Imada, Yasushi ^{[1
]}

机构：

[1] Tokushima Univ, Dept Appl Chem, Tokushima 7708506, Japan

[2] Tokushima Univ, Inst Liberal Arts & Sci, Tokushima 7708502, Japan

[3] Tokushima Bunri Univ, Fac Pharmaceut Sci, Yamashiro, Tokushima 7708514, Japan

[4] Toyohashi Univ Technol, Dept Environm & Life Sci, Toyohashi, Aichi 4418580, Japan

来源：

CHEMICAL SCIENCE | 2017年 / 8卷 / 08期

关键词：

ASYMMETRIC CATALYSIS; OXIDATION; SULFIDES; ORGANOCATALYSTS; PHOTOOXIDATION; SULFOXIDES; REDUCTION; AMINES;

D O I：

10.1039/c7sc01933e

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

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, Fl(OOH), compared to those of FlEt(+), FlEt(OOH), and Fl-Enz, Fl(OOH)-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 (Fl(OOH)-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.

引用

页码：5468 / 5475

页数：8

共 55 条

[1] Direct asymmetric aldol reaction in aqueous media using polymer-supported peptide [J].

Akagawa, K ;

Sakamoto, S ;

Kudo, K .

TETRAHEDRON LETTERS, 2005, 46 (47) :8185-8187

[2] Histidine-Containing Peptide Catalysts Developed by a Facile Library Screening Method [J].

Akagawa, Kengo ;

Sakai, Nobutaka ;

Kudo, Kazuaki .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2015, 54 (06) :1822-1826

[3] Peptide-Catalyzed Regio- and Enantioselective Reduction of α,β,γ,δ-Unsaturated Aldehydes [J].

Akagawa, Kengo ;

Sen, Jun ;

Kudo, Kazuaki .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2013, 52 (44) :11585-11588

[4] Construction of an All-Carbon Quaternary Stereocenter by the Peptide-Catalyzed Asymmetric Michael Addition of Nitromethane to β-Disubstituted α,β-Unsaturated Aldehydes [J].

Akagawa, Kengo ;

Kudo, Kazuaki .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2012, 51 (51) :12786-12789

[5] FLAVIN-6-CARBOXYLIC ACIDS AS NOVEL AND SIMPLE FLAVOENZYME MODELS - NONENZYMATIC STABILIZATION OF THE FLAVIN SEMIQUINONE RADICAL AND THE 4A-HYDROPEROXYFLAVIN BY INTRAMOLECULAR HYDROGEN-BONDING [J].

AKIYAMA, T ;

SIMENO, F ;

MURAKAMI, M ;

YONEDA, F .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1992, 114 (17) :6613-6620

[6] Aspartyl Oxidation Catalysts That Dial In Functional Group Selectivity, along with Regio- and Stereoselectivity [J].

Alford, Joshua S. ;

Abascal, Nadia C. ;

Shugrue, Christopher R. ;

Colvin, Sean M. ;

Romney, David K. ;

Miller, Scott J. .

ACS CENTRAL SCIENCE, 2016, 2 (10) :733-739

[7]

[Anonymous], MODERN BIOOXIDATION

[8] Enamine Catalysis in Flow with an Immobilized Peptidic Catalyst [J].

Arakawa, Yukihiro ;

Wennemers, Helma .

CHEMSUSCHEM, 2013, 6 (02) :242-245

[9]

Backvall J.-E., 2004, MODERN OXIDATION MET, DOI 10.1002/3527603689

[10]

Ballou D.P., 1982, Flavins andflavoproteins, P301

← 1 2 3 4 5 6 →