A Fluorination/Aryl Migration/Cyclization Cascade for the Metal-Free Synthesis of Fluoro-Benzoxazepines
| Autor: | Christoph Brunner, Andreas M. Arnold, Anna Ulmer, Tanja Gulder, Alexander Pöthig |
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| Rok vydání: | 2015 |
| Předmět: |
Reaction mechanism
010405 organic chemistry Chemistry Aryl Organic Chemistry Electrophilic fluorination Hypervalent molecule General Chemistry 010402 general chemistry 01 natural sciences Combinatorial chemistry Catalysis 0104 chemical sciences chemistry.chemical_compound Cascade Reagent Organic chemistry Chemoselectivity Selectfluor |
| Zdroj: | Chemistry - A European Journal. 22:3660-3664 |
| ISSN: | 0947-6539 |
| DOI: | 10.1002/chem.201504749 |
| Popis: | Fluorinated organic molecules are of high interest for many applications across chemical and medical disciplines. Efficient methods for the synthesis of such compounds are thus needed. Within this work, application of the bench-stable cyclic hypervalent iodine(III) fluoro reagent 1 facilitated the development of an efficient, metal-free method for the preparation of the novel class of 4-fluoro-1,3-benzoxazepines starting from readily available styrenes. The efficacy and broad applicability of this concept is demonstrated by the synthesis of 20 structurally diverse congeners in high yields, regio-, and diastereoselectivities. The presented method provides complementary chemoselectivity when compared to the common, commercially available electrophilic fluorination reagents, such as selectfluor. First mechanistic investigations with isotopically labeled substrates reveal a complex reaction mechanism, proceeding via an unusual fluorination/1,2-aryl migration/cyclization cascade. |
| Databáze: | OpenAIRE |
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