Catalyst-Controlled Regiodivergence in Rearrangements of Indole-Based Onium Ylides,Journal of the American Chemical Society

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Catalyst-Controlled Regiodivergence in Rearrangements of Indole-Based Onium Ylides
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2021-06-14 , DOI: 10.1021/jacs.1c00283
Vaishnavi N Nair ₁ , Volga Kojasoy ₂ , Croix J Laconsay ₂ , Wang Yeuk Kong ₂ , Dean J Tantillo ₂ , Uttam K Tambar ₁

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We have developed catalyst-controlled regiodivergent rearrangements of onium-ylides derived from indole substrates. Oxonium ylides formed in situ from substituted indoles selectively undergo [2,3]- and [1,2]-rearrangements in the presence of a rhodium and a copper catalyst, respectively. The combined experimental and density functional theory (DFT) computational studies indicate divergent mechanistic pathways involving a metal-free ylide in the rhodium catalyzed reaction favoring [2,3]-rearrangement, and a metal-coordinated ion-pair in the copper catalyzed [1,2]-rearrangement that recombines in the solvent-cage. The application of our methodology was demonstrated in the first total synthesis of the indole alkaloid (±)-sorazolon B, which enabled the stereochemical reassignment of the natural product. Further functional group transformations of the rearrangement products to generate valuable synthetic intermediates were also demonstrated.

中文翻译：

吲哚基鎓叶立德重排中催化剂控制的区域发散

我们开发了由吲哚底物衍生的鎓叶立德的催化剂控制区域发散重排。由取代的吲哚原位形成的氧鎓叶立德分别在铑和铜催化剂存在下选择性地进行[2,3]-和[1,2]-重排。实验和密度泛函理论 (DFT) 相结合的计算研究表明，不同的机制途径涉及铑催化反应中的无金属叶立德有利于 [2,3]-重排，以及铜催化反应中的金属配位离子对 [1 ,2]-在溶剂笼中重新组合的重排。我们的方法的应用在吲哚生物碱 (±)-sorazolon B 的首次全合成中得到了证明，这使得天然产物的立体化学重新分配成为可能。还展示了重排产物的进一步官能团转化以产生有价值的合成中间体。

更新日期：2021-06-23

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