Addition to Olefins or Acetylenes

Sulfonyl thiocyanates undergo free radical addition to olefins or acetylenes to give p-thiocyanate sulfones in fair to good yields (equation 111)97. p-Toluenesulfonyl thiocyanate (224) is prepared from sodium p-toluenesulfinate and thiocyanogen in benzene... 

Perfluoroalkylation of perfluoroalkylethylenes and addition of perfluoroalkyl iodides to olefins or acetylenes are catalyzed by copper metal [238, 239] Similar copper-catalyzed addition of iododifluoroacetates to olefins has been observed [241]... 

S.7.2.3.3. by Addition to Olefins and Acetylenes or Cyclopropanes by Ring Opening. 

The addition of hydrogen to olefinic or acetylenic bonds is symmetry-forbidden [87, 88]. However, the participation of a catalyst subdivides the addition of H2 to an unsaturated system into a series of successive steps which do not suffer from these symmetry restrictions. These successive steps are oxidative addition of hydrogen, insertion of the coordinated unsaturated system into a metal-hydrogen bond, and reductive elimination of the hydrogenation product. Irrespective of the individual mechanism there is overwhelming evidence from D2 addition experiments that the catalytic addition of H2 to carbon-carbon double and triple bonds is a cA-addition [20]. 

Derivation (1) Electrolysis of solutions in hydrogen fluoride (Simons process) (2) replacement of chlorine or bromine by fluorine with hydrogen fluoride in the presence of a catalyst (antimony trifluoride or pentafluoride) (3) addition of hydrogen fluoride to olefins or acetylene. 

This discussion, however, is restricted to those organoborane interconversions that either occur thermally or involve addition of the B—C bond to olefinic or acetylenic linkages. Organoboranes can undergo three types of thermal reactions ... 

The addition of the C—Al bond to olefinic or acetylenic substrates (carbalumination) is of interest in organometallic synthesis " . 

A chain branching process can result from addition reactions of an alkyl peroxy radical to olefins or acetylenes, where vinyl, or acetyl peroxides are formed. The initial radical formed by the addition of the peroxy radical would undergo an addition reaction with molecular oxygen, then undergo molecular elimination of HO2 to form an unsaturated peroxide. The unsaturated peroxide would then undergo rapid cleavage of the weak peroxide bonds. A mechanism that implements this chain branching results from ROO addition to olefins is illustrated by ... 

The 0x0 reaction is probably the best-known addition reaction of carbon monoxide to olefins (or acetylenes). The 0x0 process has been developed extensively in industry to produce primary alcohols by the reduction of the... 

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