An unusual reaction of a Reissert compound involving alkylation, rearrangement, SNAr and SET processes
| Autor: | Terry L. Price, Zhenbin Niu, Minjae Lee, Michael A. G. Berg, Harry W. Gibson, Daniel V. Schoonover |
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| Rok vydání: | 2018 |
| Předmět: |
chemistry.chemical_classification
010405 organic chemistry Chemistry Radical Organic Chemistry Iodide Alkylation 010402 general chemistry 01 natural sciences Biochemistry Medicinal chemistry Isopropyl iodide 0104 chemical sciences chemistry.chemical_compound Electron transfer Drug Discovery Lactam Isoquinoline Isopropyl |
| Zdroj: | Tetrahedron Letters. 59:1055-1058 |
| ISSN: | 0040-4039 |
| DOI: | 10.1016/j.tetlet.2018.02.002 |
| Popis: | Reaction of isoquinoline Reissert compound 1 with NaH and then isopropyl iodide in DMF at 22 °C led to four isolated products. Ketone 3 is the expected product of the well-known rearrangement of the intermediate Reissert anion. Cyano lactam 4 results from SNAr intramolecular displacement of the fluoride ion from the activated aroyl moiety of the anion. Isopropyl lactam 5 is proposed to result from a SET (single electron transfer) process via formation of the radical anion of 4, subsequent loss of the cyanide ion, and coupling of the resultant radical with isopropyl radicals formed via copper used to “stabilize” the alkyl iodide. The expected alkylated product 2 is also formed via a SET process involving electron transfer from the Reissert anion to 4, leading to the Reissert radical. Use of “non-stabilized” bromide or iodide led to 3 and 4, but did not produce 2 or 5. |
| Databáze: | OpenAIRE |
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