Azides are energy-rich compounds with diverse representation in a broad range of scientific disciplines, including material science, synthetic chemistry, pharmaceutical science and chemical biology. Despite ubiquitous usage of the azido group, the underlying biosynthetic pathways for its formation remain largely unknown. Here we report the characterization of an enzymatic route for de novo azide construction. We demonstrate that Tri17, a promiscuous ATP- and nitrite-dependent enzyme, catalyses organic azide synthesis through sequential N-nitrosation and dehydration of aryl hydrazines. Through biochemical, structural and computational analyses, we further propose a plausible molecular mechanism for azide synthesis that sets the stage for future biocatalytic applications and biosynthetic pathway engineering.

叠氮化物是富含能量的化合物，在广泛的科学学科中具有多种代表性，包括材料科学、合成化学、制药科学和化学生物学。尽管叠氮基无处不在，但其形成的潜在生物合成途径在很大程度上仍然未知。在这里，我们报告了从头叠氮化物构建的酶途径的表征。我们证明 Tri17 是一种混杂的 ATP 和亚硝酸盐依赖性酶，通过芳基肼的连续 N-亚硝化和脱水催化有机叠氮化物合成。通过生化、结构和计算分析，我们进一步提出了叠氮化物合成的合理分子机制，为未来的生物催化应用和生物合成途径工程奠定了基础。