de Carvalho Renato L, Wood James M, Almeida Renata G, Berry Neil G, da Silva Júnior Eufrânio N, Bower John F
Instituto de Ciências Exatas, Departamento de Química, Universidade Federal de Minas Gerais - UFMG, 31270-901, Belo, Horizonte - MG, Brazil.
Department of Chemistry, University of Liverpool, Crown Street, Liverpool, L69 7ZD, United Kingdom.
Angew Chem Int Ed Engl. 2024 Apr 24;63(18):e202400188. doi: 10.1002/anie.202400188. Epub 2024 Mar 25.
The first systematic exploration of the synthesis and reactivity of naphthoquinonynes is described. Routes to two regioisomeric Kobayashi-type naphthoquinonyne precursors have been developed, and the reactivity of the ensuing 6,7- and 5,6-aryne intermediates has been investigated. Remarkably, these studies have revealed that a broad range of cycloadditions, nucleophile additions and difunctionalizations can be achieved while maintaining the integrity of the highly sensitive quinone unit. The methodologies offer a powerful diversity oriented approach to C6 and C7 functionalized naphthoquinones, which are typically challenging to access. From a reactivity viewpoint, the study is significant because it demonstrates that aryne-based functionalizations can be utilized strategically in the presence of highly reactive and directly competing functionality.
本文描述了对萘醌炔的合成及反应活性的首次系统探索。已开发出两种区域异构体小林型萘醌炔前体的合成路线，并对随后生成的6,7 - 和5,6 - 芳炔中间体的反应活性进行了研究。值得注意的是，这些研究表明，在保持高度敏感的醌单元完整性的同时，可以实现广泛的环加成、亲核试剂加成和双官能化反应。这些方法为C6和C7官能化萘醌提供了一种强大的多样化导向方法，而C6和C7官能化萘醌通常难以获得。从反应活性的角度来看，该研究具有重要意义，因为它表明基于芳炔的官能化可以在存在高反应性且直接竞争的官能团的情况下进行策略性应用。
