Kinetics and Mechanism of the Platinum(II)-Catalyzed Hydroarylation of Vinyl Arenes with 1,2-Dimethylindole |
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Authors: | Zhibin Zhang Scott Liu Ross A. Widenhoefer |
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Affiliation: | French Family Science Center, Duke University, Durham, NC 27708-0346 |
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Abstract: | The mechanism of the intermolecular hydroarylation of vinyl arenes ( 1 ) with 1,2-dimethylindole ( 2 ) catalyzed by PtCl2 has been evaluated through a combination of kinetic analysis, deuterium labeling studies, and stereochemical analysis. The results of these and additional experiments are consistent with a mechanism for hydroarylation involving rapid and reversible complexation of vinyl arene to the catalytically inactive platinum mono(vinyl arene)complex trans-PtCl2(H2C=CHAr)(solvent) to form the reactive platinum bis(vinyl arene) complex trans-PtCl2(H2C=CHAr)2, which undergoes turnover-limiting, outer-sphere attack of indole. Rapid protodemetallation of the resulting platinum alkyl complex releases product and regenerates the equilibrating mixture of platinum π-vinyl arene complexes. |
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Keywords: | Hydroarylation C−C bond formation mechanism kinetics platinum catalysis alkene |
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