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Dioxygen-Promoted Regioselective Oxidative Heck Arylations of Electron-Rich Olefins with Arylboronic Acids

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Murugaiah M. S. Andappan, Peter Nilsson, Henrik von Schenck, and Mats Larhed*

Organic Pharmaceutical Chemistry, Department of Medicinal Chemistry, BMC, Uppsala University, Box-574, SE-751 23 Uppsala, Sweden

J. Org. Chem., 2004, 69 (16), pp 5212–5218

DOI: 10.1021/jo049434t

Publication Date (Web): July 9, 2004

In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

, mats@orgfarm.uu.se

Abstract

Arylations of electron-rich heteroatom-substituted olefins were performed with arylboronic acids. This appears to constitute the first example of palladium(II)-catalyzed internal Heck arylations. The novel protocol exploits oxygen gas for environmentally benign reoxidation and a stable 1,10-phenanthroline bidentate ligand to promote the palladium(II) regeneration and to control the regioselectivity. Internal arylation is strongly favored with electron-rich arylboronic acids. DFT calculations support a charge-driven selectivity rationale, where phenyls substituted with electron-donating groups prefer the electron-poor α-carbon of the olefin. Experiments, verified by calculations, confirm the cationic nature of the catalytic route. This Heck methodology provides a facile and mild access to functionalized enamides. Controlled microwave heating and increased oxygen pressure were used to further reduce the reaction time to 1 h.

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Published In Issue August 06, 2004
Received April 6, 2004

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Article

Dioxygen-Promoted Regioselective Oxidative Heck Arylations of Electron-Rich Olefins with Arylboronic Acids

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Efficient Palladium(II) Catalysis under Air. Base-Free Oxidative Heck Reactions at Room Temperature or with Microwave Heating

Oxygen-Promoted Pd(II) Catalysis for the Coupling of Organoboron Compounds and Olefins

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