Journal of Organic Chemistry p. 8760 - 8772 (2020)
Update date:2022-09-26
Topics:
Xue, Jing-Wen
Zeng, Miao
Jiang, Hongwu
Li, Kaiwen
Chen, Zhuqi
Yin, Guochuan
Although Pd(II)-catalyzed C-H activation in arenes has been widely successful in organic synthesis with many palladacycle compounds isolated as the intermediates in ligand-directed C-H activation, direct identification of the reaction intermediates such as the π-complex prior to the C-H activation is still not successful because of their instability. In the present study, we introduce a Pd(II)/LA (LA: Lewis acid)-catalyzed oxidative olefination/annulation reaction between N-methoxybenzamides and acrylates with oxygen as the oxidant source, in which two intermediates, including an unsymmetrical η6-complex and a palladacycle species without the proton releasing to the environment, were identified through NMR characterizations. The in situ formation of the heterobimetallic Pd(II)/LA species such as Pd(II)/Sc(III) may have enhanced the electrophilic properties of the Pd2+ cation, thus improving the stability of the π-complex, herein, an unsymmetrical η6-complex, and improving its catalytic efficiency. The observed insensitive electronic effect preferred the concerted metalation-deprotonation (CMD) mechanism for this C-H activation, and the detected palladacycle intermediate without the proton releasing to the environment offered an experimental clue to support the proposed CMD mechanism.
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Doi:10.1002/anie.201103882
(2011)Doi:10.1021/ja00011a028
(1991)Doi:10.1002/chem.201001981
(2011)Doi:10.1016/j.bmcl.2011.08.047
(2011)Doi:10.1021/jm00112a031
(1991)Doi:10.1016/j.saa.2020.119102
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