Xu Gan, Chan Hok Tsun, Li Shuchang, Wong Tsz Ying, Zhang Lei, Zhang Qichun, Lin Zhenyang, Lu Zhenpin
Department of Chemistry, State Key Laboratory of Marine Pollution, City University of Hong Kong, Hong Kong SAR, PR China.
Department of Chemistry, The Hong Kong University of Science and Technology, Hong Kong SAR, PR China.
Nat Commun. 2025 Jul 10;16(1):6349. doi: 10.1038/s41467-025-61062-z.
Borylation chemistry plays a crucial role in the development of new synthetic methodologies. However, the reactivity of zinc-boryl species has not been fully explored, particularly in relation to diverse reaction pathways. Here we show that a zinc-boryl species is successfully synthesized from bis(catecholato)diboron, exhibiting amphiphilic reactivity. This compound acts as a nucleophilic boron anion with methyl iodide and as an electrophile with N,N'-dicyclohexylcarbodiimide, facilitating zinc-boron bond dissociation and generating zinc-carbon and zinc-nitrogen bonds while cleaving carbon-nitrogen double bonds. The enhanced reactivity is likely due to the stronger covalency of the zinc-boron bond. Additionally, the zinc-boryl compound promotes the catalytic diborylation of azobenzene, underscoring its versatility as a reactive intermediate. Density functional theory studies illuminate the electronic structure and reactivity of the zinc-boron bond, providing insights into potential applications in synthetic chemistry.
硼化反应化学在新合成方法的开发中起着至关重要的作用。然而，锌硼物种的反应性尚未得到充分探索，特别是在不同反应途径方面。在这里，我们表明，一种锌硼物种成功地由双（邻苯二酚）二硼合成，表现出两亲反应性。该化合物与甲基碘反应时作为亲核硼阴离子，与N，N'-二环己基碳二亚胺反应时作为亲电试剂，促进锌硼键解离并生成锌碳键和锌氮键，同时裂解碳氮双键。反应性增强可能是由于锌硼键更强的共价性。此外，锌硼化合物促进了偶氮苯的催化二硼化反应，突出了其作为反应中间体的多功能性。密度泛函理论研究阐明了锌硼键的电子结构和反应性，为合成化学中的潜在应用提供了见解。
