The oxidative treatment of vinyltris(trimethylsilyl)germanes with hydrogen peroxide (NaOH/H(2)O/THF) or tert-butyl peroxide (KH/THF) generates reactive germanol or germanoxane species that undergo Pd-catalyzed cross-couplings with aryl and alkenyl halides and aryl triflates in the presence of Pd(PPh(3))(4). Vinylgermanes having either a conjugated or isolated double bond serve as versatile transmetalation reagents. The E-germanes undergo coupling with retention of stereochemistry under aqueous and anhydrous conditions, while coupling of Z-germanes occurs with less stereoselectivity to produce a mixture of E/Z products.

Vinyl tris(trimethylsilyl)germanes can be used as versatile transmetalation reagents, allowing for the formation of various aryl and alkenyl halides and aryl triflates.

Paper

Application of vinyl tris(trimethylsilyl)germanes in Pd-catalyzed couplings.

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