Dual role of nucleophiles in palladium-catalyzed Heck, Stille, and Sonogashira reactions
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| 024 | 7 | 0 | |a 10.1351/pac200476030565 |2 doi |
| 035 | |a (NATIONALLICENCE)gruyter-10.1351/pac200476030565 | ||
| 100 | 1 | |a Jutand |D Anny |u École Normale Supérieure, Département de Chimie, UMR CNRS-ENS-UPMC 8640, 24 Rue Lhomond, F-75231,Paris Cédex 5, France | |
| 245 | 1 | 0 | |a Dual role of nucleophiles in palladium-catalyzed Heck, Stille, and Sonogashira reactions |h [Elektronische Daten] |c [Anny Jutand] |
| 520 | 3 | |a In palladium-catalyzed Heck, Stille, or Sonogashira reactions, the nucleophiles-respectively, alkenes, vinylstannanes, or alkynes-are involved in carbopalladation or transmetallation steps that follow the oxidative addition of an aryl halide or triflate to a Pd0 complex. As soon as the nucleophiles possess a C=C or a C 'triple-bond' C bond capable of coordinating the Pd0 complex active in the oxidative addition, they play a dual role since they interfere in the oxidative addition by a decelerating effect due to a partial coordination of the active Pd0 complex. Indeed, its concentration decreases due to the formation of either unreactive complexes (η2-RCH=CH2)Pd0L2 (R = Ph, CO2Et, L = PPh3 ; R = Bu3Sn, L = AsPh3), (η2-RCH=CH2)Pd0L2(OAc)- (R = Ph, L = PPh3), (η2-R-C 'triple-bond' CH)Pd0L2 (R = Ph, L = PPh3) or more slowly reactive complexes (η2-R-C 'triple-bond' CH)Pd0L2 (R = CO2Et, L = PPh3), (η2-RCH=CH2)Pd0L2 (R= CO2Me, L2 = dppf). Whenever the oxidative addition is faster than the ensuing carbopalladation or transmetallation, the decelerating effect of the nucleophiles in the oxidative addition is in favor of a better efficiency for the catalytic cycle by bringing the rate of the fast oxidative addition closer to that of the slow carbopalladation or transmetallation steps. | |
| 540 | |a © 2013 Walter de Gruyter GmbH, Berlin/Boston | ||
| 773 | 0 | |t Pure and Applied Chemistry |d De Gruyter |g 76/3(2004-01-01), 565-576 |x 0033-4545 |q 76:3<565 |1 2004 |2 76 |o pac | |
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| 908 | |D 1 |a research article |2 jats | ||
| 950 | |B NATIONALLICENCE |P 856 |E 40 |u https://doi.org/10.1351/pac200476030565 |q text/html |z Onlinezugriff via DOI | ||
| 950 | |B NATIONALLICENCE |P 100 |E 1- |a Jutand |D Anny |u École Normale Supérieure, Département de Chimie, UMR CNRS-ENS-UPMC 8640, 24 Rue Lhomond, F-75231,Paris Cédex 5, France | ||
| 950 | |B NATIONALLICENCE |P 773 |E 0- |t Pure and Applied Chemistry |d De Gruyter |g 76/3(2004-01-01), 565-576 |x 0033-4545 |q 76:3<565 |1 2004 |2 76 |o pac | ||
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| 949 | |B NATIONALLICENCE |F NATIONALLICENCE |b NL-gruyter | ||