Haloalkenyl Imidoyl Halides as Multifacial Substrates in the Stereoselective Synthesis of N-Alkenyl Compounds,Advanced Synthesis & Catalysis

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Haloalkenyl Imidoyl Halides as Multifacial Substrates in the Stereoselective Synthesis of N-Alkenyl Compounds
Advanced Synthesis & Catalysis ( IF 4.4 ) Pub Date : 2021-02-24 , DOI: 10.1002/adsc.202100009
Athanasios Markos ₁ , Lukáš Janecký ₁ , Tomáš Chvojka ₁ , Tomáš Martinek ₁ , Hector Martinez-Seara ₁ , Blanka Klepetářová ₁ , Petr Beier ₁

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N-Alkenyl compounds are versatile synthetic building blocks and their stereoselective transformations are key processes in the synthesis of many prominent classes of natural products, pharmaceuticals, and agrochemicals. However, a large structural variety of known N-alkenyl compounds and their diverse reactivity have so far precluded the development of a general method for their stereoselective synthesis. Herein we present an aluminum halide-mediated, highly stereoselective, efficient and scalable transformation of commercially available N-fluoroalkyl-1,2,3-triazoles to N-haloalkenyl imidoyl halides, and demonstrate their use in the synthesis of stereodefined N-alkenyl amides, amidines, imines, hydrazonoamides, imidothioates, iminophosphonates, 1,2,4-triazoles and tetrazoles. The reaction is of wide scope on both the triazole substrate and aluminum halide, providing highly functionalized products. Mechanistic and computational investigations suggest a reaction mechanism involving the triazole ring opening, initiated by the coordination of nitrogen one of the triazole ring to the Lewis acid, N₂ elimination and the formation of a vinyl cation intermediate, which reacts with nitrogen-bound aluminum halide, followed by a series of halide exchange reactions on C−X and Al−X bonds.

中文翻译：

卤代烯基亚氨基卤化物作为 N-烯基化合物立体选择性合成中的多面底物

N -烯基化合物是通用的合成构件，它们的立体选择性转化是合成许多主要类别的天然产物、药物和农用化学品的关键过程。然而，迄今为止，已知N-烯基化合物的大量结构变化及其不同的反应性阻碍了其立体选择性合成的通用方法的开发。在此，我们提出了一种卤化铝介导的、高度立体选择性、高效且可扩展的将市售N-氟烷基-1,2,3-三唑转化为N-卤代烯基亚胺酰卤化物的方法，并展示了它们在立体定义N的合成中的应用-烯基酰胺、脒、亚胺、腙酰胺、亚氨基硫代酸酯、亚氨基膦酸酯、1,2,4-三唑和四唑。该反应在三唑底物和卤化铝上的范围很广，可提供高度官能化的产物。机理和计算研究表明反应机制涉及三唑环开环，由三唑环中的一个氮与路易斯酸的配位、N ₂消除和乙烯基阳离子中间体的形成引发，该中间体与氮结合的卤化铝反应，然后是 C-X 和 Al-X 键上的一系列卤化物交换反应。

更新日期：2021-02-24

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