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Haloalkenyl Imidoyl Halides as Multifacial Substrates in the Stereoselective Synthesis of N ‐Alkenyl Compounds
Author(s) -
Markos Athanasios,
Janecký Lukáš,
Chvojka Tomáš,
Martinek Tomáš,
MartinezSeara Hector,
Klepetářová Blanka,
Beier Petr
Publication year - 2021
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.202100009
Subject(s) - chemistry , stereoselectivity , halide , lewis acids and bases , ring (chemistry) , combinatorial chemistry , stereochemistry , organic chemistry , catalysis
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.