Addition of C-H Bond to Alkynes

Many methods of ruthenium-promoted C-C bond formation implicating alkynes have been discovered. Most of these have involved oxidative coupling at a ruthe-nium(O) or (II) site, rather than addition of carbonucleophiles to electrophilically activated alkynes. These methods have been reported in several reviews [3,122]. 

The above results show that the ruthenium-catalyzed activation of alkynes towards nucleophiles has first led to classical electrophilic activation, leading to Markovnikov additions as observed for addition of carboxylic acids and the synthesis of enol esters. In 1986, the regioselective anfi-Markovnikov addition of in-situ-generated 

Whereas the catalytic hydrosilylation of alkynes was one of the first methods of controlled reduction and functionalization of alkynes, the ruthenium-catalyzed hydroamination of alkynes has emerged only recently, but represents a potential for the selective access to amines and nitrogen-containing heterocydes. It is also noteworthy that, in parallel, the ruthenium activation of inert C-H bonds allowing alkyne insertion and C-C bond formation also represents innovative aspects that warrant future development. Among catalytic additions to alkynes for the production of useful products, the next decade will clearly witness an increasing role for ruthenium-vinylidenes in activation processes, and also for the development of ruthenium-catalyzed hydroamination and C-H bond activation. 

Ftirstner, Ed Alkene Metathesis in Organic Chemistry. Topics in OrganometalUc Chemistry. Springer 1998. 

Philippot, D. Devanne, P. H. Dkneuf /. Chem. Soc. Chem. Commun. 1990. 

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