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Re-Evaluation of Product Outcomes in the Rh-Catalyzed Ring Expansion of Aziridines with N-Sulfonyl-1,2,3-Triazoles
The Journal of Organic Chemistry ( IF 3.6 ) Pub Date : 2022-08-10 , DOI: 10.1021/acs.joc.2c01186
Hillary J Dequina 1 , Josephine Eshon 1 , Steven C Schmid 1 , William T Raskopf 1 , Kyana M Sanders 1 , Israel Fernández 2 , Jennifer M Schomaker 1
Affiliation  

N-heterocycles are prevalent in pharmaceuticals and natural products, but traditional methods often do not introduce significant stereochemical complexity into the ring. We previously reported a Rh-catalyzed ring expansion of aziridines and N-sulfonyl-1,2,3-triazoles to furnish dehydropiperazines with excellent diastereocontrol. However, later studies employing ketone-containing carbene precursors showed that [3,9]-bicyclic aziridine formation competes with production of the desired heterocyclic scaffolds. In light of these surprising results, our initial findings were re-examined both experimentally and computationally to reveal how noncovalent interactions and restricted bond rotation in the aziridinium ylide intermediate promote this unexpected reaction pathway.

中文翻译:

用 N-Sulfonyl-1,2,3-Triazoles 重新评估 Rh 催化的氮丙啶扩环产品结果

N-杂环在药物和天然产物中普遍存在,但传统方法通常不会将显着的立体化学复杂性引入环中。我们之前报道了Rh催化的氮丙啶和N-磺酰基-1,2,3-三唑的扩环,以提供具有优异非对映控制的脱氢哌嗪。然而,后来使用含酮卡宾前体的研究表明,[3,9]-双环氮丙啶的形成与所需杂环支架的产生竞争。鉴于这些令人惊讶的结果,我们在实验和计算上重新检查了我们的初步发现,以揭示氮丙啶鎓叶立德中间体中的非共价相互作用和受限的键旋转如何促进这种意想不到的反应途径。
更新日期:2022-08-10
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