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Volumn 11, Issue 4, 2009, Pages 899-902

Synthesis of amidines using N-allyl ynamides. A palladium-catalyzed allyl transfer through an ynamido-π-allyl complex

Author keywords

[No Author keywords available]

Indexed keywords

AMIDINE; IMIDAZOLE DERIVATIVE; LACTONE; PALLADIUM;

EID: 62749198679     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol802844z     Document Type: Article
Times cited : (73)

References (78)
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    • See the Supporting Information. On the basis of NOE experiments (see the Supporting Information for details), these amidines adopt an E-geometry with respect to the C=N bond.
    • See the Supporting Information. On the basis of NOE experiments (see the Supporting Information for details), these amidines adopt an E-geometry with respect to the C=N bond.
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    • As shown below, a non-palladium-involved pathway would entail an aza-Claisen type of rearrangement followed by trapping of the allylketenimine intermediate i with an external amine. However, while this pathway is indeed a possibility, it requires much higher temperature and longer reaction time. When carried out at 65-80 °C in THF, the reaction was sluggish and slow. For a recent account on a related thermal transformation using ynol ethers, see: Sosa, J. R.; Tudjarian, A. A.; Minehan, T. G. Org. Lett. 2008, 10, 5091.
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    • 2] from de-allylation were difficult to isolate. However, we were able to isolate the following allylated amine ii when using piperizine.
    • 2] from de-allylation were difficult to isolate. However, we were able to isolate the following allylated amine ii when using piperizine.
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    • Hartwig observed that in comparison with monodentate phosphine ligands, the usage of bidentate ligands such as xantphos leads to a much faster amidative cross-coupling. This is presumably due to the ability of amido-type carbonyl groups to engage in tight complexation with the palladium met al.. As a result, when using xantphos, its unique bite angle promotes reductive elimination. See: Fujita, K.-I.; Yamashita, M.; Puschmann, F.; Alvarez-Falcon, M. M.; Incarvito, C. D.; Hartwig, J. F. J. Am. Chem. Soc. 2006, 128, 9044.
    • Hartwig observed that in comparison with monodentate phosphine ligands, the usage of bidentate ligands such as xantphos leads to a much faster amidative cross-coupling. This is presumably due to the ability of amido-type carbonyl groups to engage in tight complexation with the palladium met al.. As a result, when using xantphos, its unique bite angle promotes reductive elimination. See: Fujita, K.-I.; Yamashita, M.; Puschmann, F.; Alvarez-Falcon, M. M.; Incarvito, C. D.; Hartwig, J. F. J. Am. Chem. Soc. 2006, 128, 9044.


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