Transnitrilation from Dimethylmalononitrile to Aryl Grignard and Lithium Reagents: A Practical Method for Aryl Nitrile Synthesis
| Autor: | C. Avery Sader, Christian A. Malapit, Maurice A. Marsini, Frederic G. Buono, Kanwar Sidhu, Keith R. Fandrick, Chris H. Senanayake, Jonathan T. Reeves, Carl A. Busacca |
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| Rok vydání: | 2015 |
| Předmět: |
chemistry.chemical_classification
Ketone Nitrile Aryl Imine Chemistry Techniques Synthetic General Chemistry Lithium Cyanation Biochemistry Combinatorial chemistry Catalysis Adduct chemistry.chemical_compound Colloid and Surface Chemistry chemistry Reagent Nitriles Electrophile Organometallic Compounds Organic chemistry Indicators and Reagents |
| Zdroj: | Journal of the American Chemical Society. 137:9481-9488 |
| ISSN: | 1520-5126 0002-7863 |
| Popis: | An electrophilic cyanation of aryl Grignard or lithium reagents, generated in situ from the corresponding aryl bromides or iodides, by a transnitrilation with dimethylmalononitrile (DMMN) was developed. DMMN is a commercially available, bench-stable solid. The transnitrilation with DMMN avoids the use of toxic reagents and transition metals and occurs under mild reaction conditions, even for extremely sterically hindered substrates. The transnitrilation of aryllithium species generated by directed ortho-lithiation enabled a net C-H cyanation. The intermediacy of a Thorpe-type imine adduct in the reaction was supported by isolation of the corresponding ketone from the quenched reaction. Computational studies supported the energetic favorability of retro-Thorpe fragmentation of the imine adduct. |
| Databáze: | OpenAIRE |
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