Journal of the American Chemical Society 2006-12-20

Stereospecific palladium-catalyzed cross-coupling of (E)- and (Z)-alkenylsilanolates with aryl chlorides.

Scott E Denmark, Jeffrey M Kallemeyn

Index: J. Am. Chem. Soc. 128 , 15958, (2006)

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Abstract

The cross-coupling of geometrically defined (E)- and (Z)-alkenyl- and styrylsilanolates with a wide variety of aromatic and heteroaromatic chlorides has been achieved. Under catalysis by bulky, biphenyl-derived phosphines and allylpalladium chloride, the (preformed, stable) potassium salts of di-, tri- and tetrasubstituted alkenyldimethylsilanols undergo high yielding and highly stereospecific coupling to aryl chlorides in THF or dioxane. A variety of functional groups are compatible with these reaction conditions including nitro, ester, ketone, and nitrile. Both (E)- and (Z)-alkenylsilanolates coupled with nearly identical rate and efficiency.