Iannelli Giulia, Spieß Philipp, Meyrelles Ricardo, Kaiser Daniel, Maryasin Boris, González Leticia, Maulide Nuno
Institute of Organic Chemistry, University of Vienna Währinger Straße 38 1090 Vienna Austria
Institute of Theoretical Chemistry, University of Vienna Währinger Straße 17 1090 Vienna Austria.
Chem Sci. 2025 May 13. doi: 10.1039/d5sc01085c.
Umpolung reactivity facilitated by hypervalent iodine has emerged as an appealing method for the efficient α-functionalization of ketones. However, skeletal reorganisation or migration reactions remain comparatively underexplored, primarily due to the challenging taming of transient carbocationic intermediates. In this study, we introduce a method for the functionalisation of ketones, employing a 6 cyclisation initiated by Umpolung of silyl enol ethers, resulting in the diastereoselective formation of -substituted cyclohexanes. Additional investigations, both experimental and computational, give insight into the mechanistic intricacies of this process, and shed light on an unconventional iodine(iii)-reactivation mechanism.
高价碘促进的极性翻转反应已成为一种颇具吸引力的酮高效α-官能团化方法。然而，骨架重排或迁移反应仍相对较少被探索，主要是因为瞬态碳正离子中间体的调控具有挑战性。在本研究中，我们介绍了一种酮的官能团化方法，该方法利用硅基烯醇醚的极性翻转引发6-环化反应，从而非对映选择性地形成α-取代环己烷。通过实验和计算的进一步研究，深入了解了该过程的机理复杂性，并揭示了一种非常规的碘(III)再活化机制。
