Exo-Dicyclopentadiene

The polymerization of norbornene, Eq. (19), is stopped by cooling the reaction mixture to room temperature. The active polymer 11 can be stored for long periods of time. Heating 11 to temperatures above 65 °C in the presence of monomer causes renewed chain propagation. The subsequent addition of different cyclic olefins, such as endo- and exo-dicyclopentadiene, benzonorbomadiene and 6-methylbenzonorbornadiene resulted in the formation of well-defined AB- and ABA-type block copolymers, Eq. (21) [38]. Triblock copolymers 13 with narrow molecular weight distributions (polydispersity = 1.14) were prepared. Thus, the living character enables the preparation of new uniform block copolymers of predictable composition, microstructure and molecular weight. 

Figure 7. NMR spectrum of the sulfurated products of exo-dicyclopentadiene (almost an equimolar mixture of cis-exo and trans addition products as shown) in CSt using TMS as internal standard...

Limonene is oxidized regioselectively by PBA (Eq. 8) and stereoselectivity can be observed for endo- and exo-dicyclopentadienes. ... 

Olefins containing isolated double bonds with different reactivity towards thiyl radicals are selectively co-oxidized at the more reactive unsaturation centre . This is the case of co-oxidation of endo and exo dicyclopentadienes with 4-chlorobenzenethiol (equations 102, 103). (The bracket indicates that the stereochemistry is unknown.)... 

Hamilton, J. G Ivin, K. J. Rooney, J. J. Ring-opening polymerization of endo- and exo-dicyclopentadiene and their 7,8-dihydro derivatives. J. Mol. Catal. 1986, 36, 115-125. 

An improved procedure for the preparation of exo-dicyclopentadiene (207) from the cndo-isomer has been reported. Cycloaddition of norboradiene to anthracene affords the cxo-adduct (208), the bromination of which gives (209) Dehydrobromination of (209) yields (210 X = Br) which on reductive debromination is converted into the cndo-adduct (210 X = H). The dihydro-derivatives of (208) and (210 X = H) were also synthesized. 

The polymerization of endo- or exo-dicyclopentadiene using Pd(PhCN)2Cl2 as the catalyst formed the corresponding polymers of the C=C bond in the six-membered ring (eqs 210 and 21... 

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