1-Norbornene dimerization

Norbornene is a good olefin to use as a probe for the triplet-triplet transfer process since the norbornene triplet yields dimers. When carbonyl compounds are irradiated in the presence of norbornene, the ratio of photocycloaddition product to norbornene dimers is dependent upon the n,ir triplet energy of the carbonyl compound. A series of experiments which illustrate this effect is summarized in Table VII. 

Benzophenone 68.6 Oxetane Oxetane no norbornene dimers Strong emission... 

Acetophenone 73.6 Oxetane, reaction inefficient Norbornene dimers — trace of oxetane ... 

The addition of aliphatic aldehydes and ketones to alkenes is less successful as a preparative procedure for oxetanes. An essential requirement for addition is that the triplet energy of the alkene must be considerably greater than that of the carbonyl. If this condition is not fulfilled, energy transfer to the alkene can occur,279 sensitizing, for example, dimerization of the alkene. This is clearly illustrated 280, 281 for norbornene (264) which on irradiation in the presence of benzophenone (ET 68.5 kcal/mole) forms the adduct 265 photolysis in acetone (ET 75 kcal/mole) affords only norbornene dimers (266 and 267), whereas acetophenone, which has intermediate triplet energy (Et 73.6 kcal/mole) forms both oxetanes and norbornene dimers. 

From mass spectral data alone it is difficult to determine molecular structure or to distinguish between different isomers of the same mass. Therefore, the two norbornene dimers representing 96% of the total were separated and collected by preparative GC and subjected to NMR analysis. The C NMR spectrum of a mixture of the two dimers is shown in Fig. 4.17, along with the spectra of the dimers after separation. 

From the spectra, it is clear that the dimer with m/z 216 is a norbornene dimer terminated with a vinyl group (dimer-4, 113.36 and 141.91 ppm). The compound with m/z 244 is a norbornene dimer with an ethyl and a vinyl group at the head (14.11 and 22.18 ppm) and the tail (113.72 and 142.87 ppm) of the molecule (di-mer-5), respectively. Assignments have been made based on analysis of a C 2D-INADEQUATE spectrum and are presented in Fig. 4.18. Both dimers are enchained in the 2,3-fashion consistent with the proposal based on the NMR analysis of the norbornene polymer made with naked nickel . 

Thus, it was not until 1990 that the group of Kaminsky and Arndt-Rosenau took a more detailed look at the homopolymerization of norbornene and the structures of the resulting polymers. Driven by the growing interest in copolymers with high norbornene contents and high glass transition (Tg) temperatures, as well as the unusual properties of PNBs, Arndt-Rosenau et al. used the hydrooligomerization technique to produce saturated model norbornene dimers and trimers with metallocene catalysts known to produce atactic, isotactic, and syndiotactic poly(a-olefins) (1-3, Table 16.1). 

Ruthenium hydride complexes, e.g., the dimer 34, have been used by Hofmann et al. for the preparation of ruthenium carbene complexes [19]. Reaction of 34 with two equivalents of propargyl chloride 35 gives carbene complex 36 with a chelating diphosphane ligand (Eq. 3). Complex 36 is a remarkable example because its phosphine ligands are, in contrast to the other ruthenium carbene complexes described so far, arranged in a fixed cis stereochemistry. Although 36 was found to be less active than conventional metathesis catalysts, it catalyzes the ROMP of norbornene or cyclopentene. 

AuCl(alkene)] (alkene = m-cyclooctene. norbornene, CHf/o-dicyclopentadiene ) complexes have been obtained by reaction of [AuCl(CO)] with the alkene.2280,2281 The structure of [AuC1(Ci0H12)] shows the ligand //2-bonded to gold via the C=C bond in the norbornene ring and the molecules are associated into dimers through Au Au interactions.2281... 

The side products of the reaction between benzoylnitromethane 279 and dipolarophiles (norbornene, styrene, and phenylacetylene) in the presence of l,4-diazabicyclo[2.2.2]octane (DABCO) were identified as furazan derivatives (Scheme 72). The evidence reported indicates that benzoylnitromethane gives the dibenzoylfuroxan as a key intermediate, which is the dimerization product of the nitrile oxide. The furoxan then undergoes addition to the dipolarophile, hydrolysis, and ring rearrangement to the final products (furazans and benzoic acid) <2006EJ03016>. 

Codimerization of butadiene with dicyclopentadiene (example 8, Table II) was shown to proceed via a crotyl-nickel complex (62). Ring contraction of cyclooctadiene (example 10, Table II) appears to be a hydride promoted reaction. The hydride-promoted dimerization of norbomadiene to -toly 1 norbornene (example 9, Table II) appears to be quite different from dimerization via a metallacycle (see Table I, example 16). 

Bazan and Schrock were the first to use ROMP of norbornene to prepare star polymers [108], As the coupling agent of the living polymer they used a norbor-nadiene dimer that plays the role of difunctional core-forming monomer as shown below ... 

The kinetics of the reaction of [Ru (0)2(poi with various alkenes have been investigated either in CH2Cl2/MeOH or CH2Cl2/Hpz. In the absence of MeOH or Hpz, clean kinetics are not always observed, presumably because dimerization or disproportionation of the intermediate Ru =0 species occurs at comparable rates as epoxidation. The reactions have the following rate law rate = k[Ru (0)2(por)][alkenel. The rate constants for the oxidation of styrene are in the range 6 x 10 —4.8 x 10 s. The oxidation of norbornene occurs at... 

The influence of the oxime geometry on the base-promoted rearrangement is pointed out for compounds 29 (85T5181). Thus, when treated with aqueous potassium hydroxide at room temperature, Z isomers 29Z (R = H, -oxyiminomethyl), arising as cycloadducts of the dimer or trimer of fulminic acid and norbornene, rearrange into 30. On the contrary, the E isomer 29E remains unchanged under similar conditions of aqueous bases (Scheme 6). 

Certain olefins have been converted into l-chloro-2-nitrosoalkane dimers on treatment with nitrosyl chloride (Eq. 3). Terminal olefins appear to be active only if they are not allylic in nature. The addition of nitrosyl chloride to norbornene is of particular interest, and details are presented in the body of... 

The most commonly observed dimerization is that of alkenes to form cyclobutane derivatives. Nonconjugated alkenes such as cyclopentene and norbornene are dimerized in the presence of a sensitizer, whereas conjugated alkenes dimerize directly dimerizations of the second type have been observed in dienes, phenyl-ethylenes, and a,/9-unsaturated carbonyl, cyano, and nitro derivatives. The precise structure and stereochemistry of many of these dimers is uncertain, although it is known to be influenced by the solvent, by the presence and nature of substituents, and by the use of a sensitizer. The structures of dimers formed in solid-state irradiations are often determined by crystal structure. 

Scheme 5.6 CuOTf-catalyzed [2 + 2] photocycloaddition used for a topology study of inter and intramolecular dimerization of a norbornene derivates.

II. Dimerization of norbornene and derivatives. Journal of the American Chemical Society, 88, 3021-3026. 

The auraoxetane is depicted at the bottom right-hand side of Scheme 12.1. The reaction of the bridged /x-oxo dimer with norbornene led to a gold alkene complex (these are a rare species to date) and the unique auraoxetane. The epoxynorbornane was identified as the final product of the reaction. 

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