Dehydrogenative Syntheses of Biazoles via a “Pre-Join” Approach

The structural motif
of biazoles is the predominant substructure
of many natural products, pharmaceuticals, and organic materials.
Considerable efforts have focused on synthesizing these compounds;
however, a limited number of processes have been reported for the
efficient formation of biazoles. Herein, we report a “pre-join”
approach for the dehydrogenative synthesis of biazoles, which are
challenging to prepare using conventional methods. A bench-stable
and easily synthesized pyrazine-based group is critical for this transformation.
This strategy enables the homocoupling of biazoles and the heterocoupling
of two different azoles. Due to the broad substrate scope, this strategy
exhibits potential for use in other fields, such as medicine, materials,
and natural product chemistry.

双唑类（biazoles）的结构基元是众多天然产物、药物及有机材料的核心亚结构。学界已围绕此类化合物的合成展开了大量研究，但目前仅有少数工艺可实现双唑类的高效构建。本文报道了一种用以双唑类脱氢合成的“预偶联”策略，该类化合物通过传统方法制备颇具挑战。一种室温稳定且易于合成的吡嗪基官能团，是该转化反应的关键要素。该策略可实现双唑类的均偶联以及两种不同唑类的交叉偶联。鉴于该策略具备宽泛的底物适用范围，其在医药、材料科学及天然产物化学等领域均展现出良好的应用潜力。