Pyridylketenes. Structure reactivity effects in nucleophilic and radical addition
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| 024 | 7 | 0 | |a 10.1351/pac200476111953 |2 doi |
| 035 | |a (NATIONALLICENCE)gruyter-10.1351/pac200476111953 | ||
| 245 | 0 | 0 | |a Pyridylketenes. Structure reactivity effects in nucleophilic and radical addition |h [Elektronische Daten] |c [A. D. Allen, A. V. Fedorov, K. Najafian, T. T. Tidwell, S. Vukovic] |
| 520 | 3 | |a 2-, 3-, and 4-Pyridylketenes have been generated in CH3CN by photochemical Wolff rearrangements and identified by their ketenyl absorption in the infrared at 2127, 2125, and 2128 cm-1, respectively. Reaction of these pyridylketenes with n-BuNH2 results in the formation of intermediate amide enols from the 3- and 4-pyridylketenes, which are then converted to the corresponding pyridylacetamides. However , 2-pyridylketene forms a long-lived 1,2-dihydropyridine intermediate stabilized by an intramolecular hydrogen bond, and this is converted to the 2-pyridylacetamide with a rate constant 107 less than those for the conversion of the amide enols from the 3- and 4-pyridylketenes to amides. Hydration of the pyridylketenes results in the formation of an acid enol intermediate in the case of the 3-isomer, while the 2- and 4-isomers form longer-lived dihydropyridines. The pyridylketenes react with the stable free radical tetramethylpiperidinyloxyl (TEMPO,TO) forming 1,2-diaddition products ArCH(OT)CO2T. | |
| 540 | |a © 2013 Walter de Gruyter GmbH, Berlin/Boston | ||
| 700 | 1 | |a Allen |D A. D. |u Department of Chemistry, University of Toronto, Toronto, Ontario M5S 3H6, Canada |4 aut | |
| 700 | 1 | |a Fedorov |D A. V. |u Department of Chemistry, University of Toronto, Toronto, Ontario M5S 3H6, Canada |4 aut | |
| 700 | 1 | |a Najafian |D K. |u Department of Chemistry, University of Toronto, Toronto, Ontario M5S 3H6, Canada |4 aut | |
| 700 | 1 | |a Tidwell |D T. T. |u Department of Chemistry, University of Toronto, Toronto, Ontario M5S 3H6, Canada |4 aut | |
| 700 | 1 | |a Vukovic |D S. |u Department of Chemistry, University of Toronto, Toronto, Ontario M5S 3H6, Canada |4 aut | |
| 773 | 0 | |t Pure and Applied Chemistry |d De Gruyter |g 76/11(2004-01-01), 1953-1966 |x 0033-4545 |q 76:11<1953 |1 2004 |2 76 |o pac | |
| 856 | 4 | 0 | |u https://doi.org/10.1351/pac200476111953 |q text/html |z Onlinezugriff via DOI |
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| 950 | |B NATIONALLICENCE |P 856 |E 40 |u https://doi.org/10.1351/pac200476111953 |q text/html |z Onlinezugriff via DOI | ||
| 950 | |B NATIONALLICENCE |P 700 |E 1- |a Allen |D A. D. |u Department of Chemistry, University of Toronto, Toronto, Ontario M5S 3H6, Canada |4 aut | ||
| 950 | |B NATIONALLICENCE |P 700 |E 1- |a Fedorov |D A. V. |u Department of Chemistry, University of Toronto, Toronto, Ontario M5S 3H6, Canada |4 aut | ||
| 950 | |B NATIONALLICENCE |P 700 |E 1- |a Najafian |D K. |u Department of Chemistry, University of Toronto, Toronto, Ontario M5S 3H6, Canada |4 aut | ||
| 950 | |B NATIONALLICENCE |P 700 |E 1- |a Tidwell |D T. T. |u Department of Chemistry, University of Toronto, Toronto, Ontario M5S 3H6, Canada |4 aut | ||
| 950 | |B NATIONALLICENCE |P 700 |E 1- |a Vukovic |D S. |u Department of Chemistry, University of Toronto, Toronto, Ontario M5S 3H6, Canada |4 aut | ||
| 950 | |B NATIONALLICENCE |P 773 |E 0- |t Pure and Applied Chemistry |d De Gruyter |g 76/11(2004-01-01), 1953-1966 |x 0033-4545 |q 76:11<1953 |1 2004 |2 76 |o pac | ||
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