Rhodium-catalyzed carbonylative domino

In summary, we have summarized representative examples of transition-metal-catalyzed carbonylative domino reactions. In the area of carbonylations, palladium, rhodium, and cobalt are still the main actors. The abihty of palladium catalysts in carbonylative cross-coupling, rhodium catalysts in carbonylative C-H activation, and cobalt catalyst in carbonylative reactions with unsaturated bonds is impressive. 

There are two important rhodium-catalyzed transformations that are broadly used in domino processes as the primary step. The first route is the formation of keto carbenoids by treatment of diazo keto compounds with Rh11 salts. This is then followed by the generation of a 1,3-dipole by an intramolecular cyclization of the keto carbenoid onto an oxygen atom of a neighboring keto group and an inter- or intramolecular 1,3-dipolar cycloaddition. A noteworthy point here is that the insertion can also take place onto carbonyl groups of aldehydes, esters, and amides. Moreover, cycloadditions of Rh-carbenes and ring chain isomerizations will also be discussed in this section. 

A broad range of olefins, acetals, epoxides, alcohols, and chlorides were demonstrated effective alternative starting materials. Cobalt and rhodium carbonyls and bimetallic complexes were shown to catalyze the domino hydro-... 

A broad range of olefins, acetals, epoxides, alcohols, and chlorides were demonstrated effective alternative starting materials. Cobalt and rhodium carbonyls and bimetallic complexes catalyzed the domino hydroformylation-amidocarbonylation of olefins (17-22). Addition of 0.1 mol% RheCCOie to the cobalt catalyst gave branched AT-acetyltrifluorovaline, which indicated that the hydroformylation step governs the regioselectivity of the domino process (Scheme 4) (22). 

---