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Synlett 2009(19): 3103-3106  
DOI: 10.1055/s-0029-1218339
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Catalytic Amide-Directed Palladadesilylation-Alkenylation

Waqar Rauf, John M. Brown*
Chemistry Research Laboratory, Mansfield Rd., Oxford OX1 3TA, UK
Fax: +44(1865)285002; e-Mail: john.brown@chem.ox.ac.uk;
Further Information

Publication History

Received 11 September 2009
Publication Date:
05 November 2009 (online)

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Abstract

Palladium(II) complexes catalyse the amide-directed displacement of an aryl-Si group and its replacement by an electrophilic alkene at ambient temperature, analogous to an oxidative Heck reaction. A palladacyclic intermediate is involved, and the reaction enables substitution to occur specifically in the electron-poor ring of benzanilides. The procedure described provides a formal link between directed lithiation and the Heck reaction.

Key words

palladium - oxidative Heck reaction - palladacycle - benz­anilides - regiocontrol

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18

The standard anilide C-H activations are run in the presence of an equivalent of PTSA, whose function is to activate Pd(OAc)2 through the formation of a more electrophilic Pd tosylate; fuller mechanistic details are contained in: Rauf W.; D. Phil. Thesis; University of Oxford: UK, 2008; and manuscript in preparation

21

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