Molecular mechanism of azoxy bond formation for azoxymycins biosynthesis

Yuan-Yang Guo, Zhen-Hua Li, Tian-Yu Xia, Yi-Ling Du, Xu-Ming Mao () and Yong-Quan Li ()
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Yuan-Yang Guo: Zhejiang University School of Medicine
Zhen-Hua Li: Zhejiang University School of Medicine
Tian-Yu Xia: Zhejiang University School of Medicine
Yi-Ling Du: Zhejiang University School of Medicine
Xu-Ming Mao: Zhejiang University School of Medicine
Yong-Quan Li: Zhejiang University School of Medicine

Nature Communications, 2019, vol. 10, issue 1, 1-9

Abstract: Abstract Azoxy bond is an important chemical bond and plays a crucial role in high energy density materials. However, the biosynthetic mechanism of azoxy bond remains enigmatic. Here we report that the azoxy bond biosynthesis of azoxymycins is an enzymatic and non-enzymatic coupling cascade reaction. In the first step, nonheme diiron N-oxygenase AzoC catalyzes the oxidization of amine to its nitroso analogue. Redox coenzyme pairs then facilitate the mutual conversion between nitroso group and hydroxylamine via the radical transient intermediates, which efficiently dimerize to azoxy bond. The deficiency of nucleophilic reactivity in AzoC is proposed to account for the enzyme’s non-canonical oxidization of amine to nitroso product. Free nitrogen radicals induced by coenzyme pairs are proposed to be responsible for the efficient non-enzymatic azoxy bond formation. This mechanism study will provide molecular basis for the biosynthesis of azoxy high energy density materials and other valuable azoxy chemicals.

Date: 2019
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DOI: 10.1038/s41467-019-12250-1

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