American Chemical Society
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Chelation-Mediated Palladium(II)-Catalyzed Domino Heck−Mizoroki/Suzuki−Miyaura Reactions Using Arylboronic Acids: Increasing Scope and Mechanistic Understanding

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journal contribution
posted on 2011-04-15, 00:00 authored by Samir Yahiaoui, Ashkan Fardost, Alejandro Trejos, Mats Larhed
A palladium(II)-catalyzed Heck−Mizoroki/Suzuki−Miyaura domino reaction involving metal coordinating dimethylaminoethyl vinyl ethers and a number of electron-rich and electron-deficient arylboronic acids has been developed. Through variation of the temperature and the concentration of the p-benzoquinone (p-Bq) ligand/reoxidant, conditions for the robust and convenient one-pot generation of diarylated-saturated ethers were identified. With the aid of coordination of the dimethylamino group to the arylpalladium intermediate, the otherwise predominant formation of the β-arylated olefin could be reversed. A reaction route involving a chelation-controlled carbopalladation, providing a p-Bq stabilized six-membered palladacycle, followed by transmetalation and reductive elimination is suggested to explain the selective formation of saturated diarylated ether products.