期刊
ADVANCED SYNTHESIS & CATALYSIS
卷 363, 期 13, 页码 3258-3266出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/adsc.202100009
关键词
N-alkenyl compounds; imidoyl halides; 1,2,3-triazoles; building blocks; haloalkenes
资金
- Czech Academy of Sciences [RVO: 61388963]
- Ministry of Education, Youth and Sports in the program INTER-EXCELLENCE [LTAUSA18037]
This study presents a novel aluminum halide-mediated synthesis of N-haloalkenyl imidoyl halides, which is highly versatile and provides highly functionalized products. The reaction mechanism involves the opening of the triazole ring, N-2 elimination, and halide exchange reactions.
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, N-2 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.
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