Norbomadiene hydrocyanation

Hydrocyanation is also catalyzed by [Pd(PPh3)4] (103) and [Pd P(OPh), 4] (132), again in both cases in the presence of excess ligand. Complex (132) is an effective catalyst for the addition of hydrogen cyanide to cyclic monoenes and dienes such as norbomene and norbomadiene ethylene also reacted readily. The product obtained from norbomene was the exo isomer (equation 165). When norbomadiene was the substrate, some of the endo product was formed. ... 

Asymmetric hydrocyanation has now been achieved using norbomene and norbomadiene as substrates. The reduction of either [PdCl2(+)-DIOP] or PdCl2 in presence of (-I )-DIOP led to a palladium(O) species formulated simply as [Pd(-l-)-DIOP]. This gave, in reaction (164), an optical yield of 30% for the 2-cxo-cyanonorbornane formed. Norbomadiene with the same catalyst gave 2-cxo-cyanonorborn-5-ene with an optical purity of 17%. When the ligand CHIRAPHOS (51) was used, the catalytic activity was greatly diminished. In addition to the review of the early work already mentioned, two more recent reviews of hydrocyanation have appeared. ... 

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