Palladium-catalyzed alkylation of unactivated olefins
| LEADER | caa a22 4500 | ||
|---|---|---|---|
| 001 | 378923110 | ||
| 003 | CHVBK | ||
| 005 | 20180305123610.0 | ||
| 007 | cr unu---uuuuu | ||
| 008 | 161128e20040101xx s 000 0 eng | ||
| 024 | 7 | 0 | |a 10.1351/pac200476030671 |2 doi |
| 035 | |a (NATIONALLICENCE)gruyter-10.1351/pac200476030671 | ||
| 100 | 1 | |a Widenhoefer |D Ross A. |u P.M. Gross Chemical Laboratory, Duke University, Durham, NC 27708-0346, USA | |
| 245 | 1 | 0 | |a Palladium-catalyzed alkylation of unactivated olefins |h [Elektronische Daten] |c [Ross A. Widenhoefer] |
| 520 | 3 | |a The reaction of a 3-butenyl β-diketone with a catalytic amount of PdCl2(CH3CN)2 in dioxane at room temperature led to olefin hydroalkylation and formation of the corresponding 2-acylcyclohexanone in good yield as a single regioisomer. Deuterium-labeling experiments for the hydroalkylation of 7-octene-2,4-dione were in accord with a mechanism involving outer-sphere attack of the pendant enol on a palladium-complexed olefin to form a palladium cyclohexyl species, followed by palladium migration via iterative β-hydride elimination/addition and protonolysis from a palladium enolate complex. In comparison to a 3-butenyl β-diketone, reaction of a 4-pentenyl β-diketone with a catalytic amount of PdCl2(CH3CN)2 in the presence of CuCl2 led to oxidative alkylation and formation of the corresponding 2-acyl-3-methyl-2-cyclohexenone in good yield as a single isomer. Unactivated olefins tethered to less reactive carbon nucleophiles such as β-keto esters, α-aryl ketones, and even dialkyl ketones underwent palladium-catalyzed hydroalkylation in the presence of Me3SiCl or HCl to form the corresponding cyclohexanones in moderate-to-good yield with high regioselectivity. | |
| 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), 671-678 |x 0033-4545 |q 76:3<671 |1 2004 |2 76 |o pac | |
| 856 | 4 | 0 | |u https://doi.org/10.1351/pac200476030671 |q text/html |z Onlinezugriff via DOI |
| 908 | |D 1 |a research article |2 jats | ||
| 950 | |B NATIONALLICENCE |P 856 |E 40 |u https://doi.org/10.1351/pac200476030671 |q text/html |z Onlinezugriff via DOI | ||
| 950 | |B NATIONALLICENCE |P 100 |E 1- |a Widenhoefer |D Ross A. |u P.M. Gross Chemical Laboratory, Duke University, Durham, NC 27708-0346, USA | ||
| 950 | |B NATIONALLICENCE |P 773 |E 0- |t Pure and Applied Chemistry |d De Gruyter |g 76/3(2004-01-01), 671-678 |x 0033-4545 |q 76:3<671 |1 2004 |2 76 |o pac | ||
| 900 | 7 | |b CC0 |u http://creativecommons.org/publicdomain/zero/1.0 |2 nationallicence | |
| 898 | |a BK010053 |b XK010053 |c XK010000 | ||
| 949 | |B NATIONALLICENCE |F NATIONALLICENCE |b NL-gruyter | ||