Cyclohexa-1,4-diene complexes palladium

In the above-mentioned preparation of the u-cyclohexenyl complex, [PdCliV-CeHglb, benzene and cyclohexane are formed. ThisTr-cyclohexenyl complex is also formed from cyclohexa-1,3-diene, either by treating it with sodium chloropalladite 191) or with palladium chlorocarbonyl, [PdCl2-(CO)]2 81, 88). 

The Shibasaki cychzation of mc.vo-cyclohexa-1,4-dienes in the presence of a chiral palladium complex and silver carbonate in l-methyl-2-pyrrolidinone is probably the first example of an enantioselective Heck reaction (Scheme 10.34).60 The enantiomeric excess could be slightly improved by replacing the chiral phosphine ligand BINAP with the corresponding less coordinating arsine ligand, as well as replacing silver carbonate with silver phosphate.61,62... 

Asymmetric hydrosilylation of cyclopentadiene and cyclohexa-1,3-diene using chiral phosphine-palladium complexes gives optically active 3-trimethylsilylcyclohex-1-ene after methylation ... 

---