Allen Anthony R, Poon Jia-Fei, McAtee Rory C, Watson Nicholas B, Pratt Derek A, Stephenson Corey R J
Department of Chemistry, Willard Henry Dow Laboratory, University of Michigan, 930 North University Avenue, Ann Arbor, Michigan 48109, United States.
Department of Chemistry and Biomolecular Sciences, University of Ottawa, 10 Marie Curie Pvt. Ottawa, ON K1N 6N5, Canada.
ACS Catal. 2022 Jul 15;12(14):8511-8526. doi: 10.1021/acscatal.2c02577. Epub 2022 Jul 1.
Alkene aminoarylation with arylsulfonylacetamides via a visible-light mediated radical Smiles-Truce rearrangement represents a convenient approach to the privileged arylethylamine pharmacaphore traditionally generated by circuitous, multi-step sequences. Herein, we report detailed synthetic, spectroscopic, kinetic, and computational studies designed to interrogate the proposed mechanism, including the key aryl transfer event. The data are consistent with a rate-limiting 1,4-aryl migration occurring either via a stepwise process involving a radical Meisenheimer-like intermediate or in a concerted fashion dependent on both arene electronics and alkene sterics. Our efforts to probe the mechanism have significantly expanded the substrate scope of the transformation with respect to the migrating aryl group and provide further credence to the synthetic potential of radical aryl migrations.
通过可见光介导的自由基Smiles-Truce重排实现烯烃与芳基磺酰基乙酰胺的氨基芳基化反应，为传统上通过迂回的多步序列生成的特权芳基乙胺药效基团提供了一种便捷的方法。在此，我们报告了详细的合成、光谱、动力学和计算研究，旨在探究所提出的机理，包括关键的芳基转移事件。数据表明，限速的1,4-芳基迁移可能通过涉及类Meisenheimer自由基中间体的逐步过程发生，也可能以协同方式发生，这取决于芳烃电子效应和烯烃空间效应。我们对该机理的探索显著扩大了迁移芳基转化反应的底物范围，并进一步证明了自由基芳基迁移的合成潜力。
