Site-Selective and Chemoselective C–H Functionalization for the Synthesis of Spiroaminals via a Silver-Catalyzed Nitrene Transfer Reaction,ACS Catalysis

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Site-Selective and Chemoselective C–H Functionalization for the Synthesis of Spiroaminals via a Silver-Catalyzed Nitrene Transfer Reaction
ACS Catalysis ( IF 11.3 ) Pub Date : 2020-11-02 , DOI: 10.1021/acscatal.0c04057
Shingo Harada ₁ , Mayu Kobayashi ₁ , Masato Kono ₁ , Tetsuhiro Nemoto _{1,

2}

Affiliation

Although intense research over the last 2 decades revealed a diverse proficiency of nitrene species in chemistry disciplines, control of the selectivity in the reaction manifold has remained a challenge. We report herein the development of site-selective and chemoselective C–H functionalization involving nitrene species to synthesize densely functionalized spiroaminals. A rhodium catalyst generally used in nitrene chemistry gave amide C–N insertion products and/or the corresponding ketones, whereas a silver catalyst with an achiral bisoxazoline (BOX) ligand provided C–H insertion products. Mechanistic analysis based on integrated experimental and computational studies indicated that the nitrene transfer occurred through an asynchronous concerted process involving triplet spin-correlated radical pairs, affording the corresponding stereodefined spiromolecules.

中文翻译：

通过银催化的丁二烯转移反应合成螺氨基化合物的位点选择性和化学选择性CH官能团

尽管在过去的20年中进行了深入研究，但在化学领域中，不同种类的氮烯的熟练程度不同，但控制反应歧管中的选择性仍然是一个挑战。我们在这里报道了涉及腈类物质以合成高密度官能化螺氨基化合物的位点选择性和化学选择性C–H功能化的发展。通常在腈化学中使用的铑催化剂可生成酰胺C–N插入产物和/或相应的酮，而具有非手性双恶唑啉（BOX）配体的银催化剂可提供CH–H插入产物。基于综合实验和计算研究的机理分析表明，氮转移是通过涉及三重态自旋相关自由基对的异步协同过程发生的，

更新日期：2020-11-21

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