Vinyl-substituted germanes react stereo- and regioselectively with olefins in the presence of complexes containing Ru-H and Ru-Ge bonds with the formation of functionalized vinylgermanes that cannot be synthesized by olefin cross-metathesis procedures. The reaction opens a new catalytic route for preparation of a class of organogermanes that are potent organometallic reagents for organic synthesis because they show very low toxicity and could replace organotin compounds. The mechanism of this new catalytic route was proven to involve an interesting insertion of the vinylgermane into the Ru-H bond and beta-Ge transfer to the metal with elimination of ethylene and generation of an Ru-Ge bond, followed by insertion of the alkene into the Ru-Ge bond and beta-H transfer to the metal to eliminate the substituted vinylgermane.

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A series of substituted vinylgermanes and divinylgermanes have been synthesized in moderate or high yield via two reactions of olefins and dienes catalyzed by [RuHCl(CO) (PCy 3 ) 2 ], i.e. germylative coupling with vinylgermanes and dehydrogenative germylation with hydrogermanes. While the former reaction can be a versatile way of regioselective synthesis of products (particularly useful for the stereoselective synthesis of germylsilylethenes), the latter could be used as a complement, especially in synthesis of germylate dioxol ethene and vinyl ethers.

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Synthesis of Functionalized Vinylgermanes Through a New Ruthenium-Catalyzed Coupling Reaction. -Vinyl-substituted germanates react stereo-and regioselectively with olefins in the presence of a Ru-complex to give functionalized vinylgermanes that cannot be synthesized by olefin cross-metathesis procedures. The mechanism of the reaction is discussed. -(MARCINIEC*, B.; LAWICKA, H.; MAJCHRZAK, M.; KUBICKI, M.; KOWNACKI, I.; Chem. Eur. J. 12 (2006) 1, 244-250; Dep. Organomet. Chem., Fac. Chem., Adam Mickiewicz Univ., PL-60-780 Poznan, Pol.; Eng.) -Bartels 19-170