Silylative cyclocarbonylations

Design of Reactions Starting from Insertion into a Rh-Si Bond 125 Tab. 6.7 Silylative cyclocarbonylation of 63 catalyzed by Rh4(CO)i2-... 

Table 14 Silylative cyclocarbonylation of 1,6-diynes with Bu Me2SiH...

The reaction was successfully extended to the hydroformylation of propargyl-type alcohols [154] and propargylamine [155], the silylative cyclocarbonylation of alkynes [156], silylcarbocyclization of alkenynes and diynes [157-160], and other transformations of C=C bonds in the presence of HSiRa and CO (e. g., [161]). A generalized catalytic cycle for the silylformylation of 1-alkynes catalyzed by rhodium-cobalt clusters is illustrated in Scheme 6. 

Bicyclo[3.3.0]octenones. Silylative cyclocarbonylation of alkynes provides an easy access to these substances. 

Onitsuka et al. [27] have developed a novel qfclocarbonylation of l,l -bis[(trimethyl-silyl)ethynyl]ferrocene catalyzed by [Ru3(CO)i2] under CO. Treatment of l,l -bis ((trimethylsilyl)-ethynyl)ferrocene 81 with Ru3(CO)i2 (5 mol%) under CO pressure (lOkgcm ) in toluene at 150 °C for 24h gave the cyclocarbonylation product 82 in... 

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