5- phenyl-2-norbomene

Norbornene 5-Phenyl-2-norbomene 5-Vinyl-2-norbomene 5-Ethylidene-2-norbomene... 

Abbreviations aapy, 2-acetamidopyridine Aik, alkyl AN, acetoniuile Ar, aryl Bu, butyl cod, 1,5-cyclooctadiene COE, cyclooctene COT, cyclooctatetraene Cp, cyclopentadienyl Cp , penta-methylcyclopentadienyl Cy, cyclohexyl DME, 1,2-dimethoxyethane DME, dimethylformamide DMSO, dimethyl sulfoxide dmpe, dimethylphosphinoethane dppe, diphenylphosphinoethane dppm, diphenylphosphinomethane dppp, diphenylphosphinopropane Et, ethyl Ec, feirocenyl ind, inda-zolyl Me, methyl Mes, mesitylene nb, norbomene orbicyclo[2.2.1]heptene nbd, 2,5-norbomadiene OTf, uiflate Ph, phenyl PPN, bis(triphenylphosphoranylidene)ammonium Pi , propyl py, pyridine pz, pyrazolate pz, substituted pyi azolate pz , 3,5-dimethylpyrazolate quin, quinolin-8-olate solv, solvent tfb, teti afluorobenzobaiTelene THE, tetrahydrofuran THT, tetrahydrothiophene tmeda, teti amethylethylenediamine Tol, tolyl Tp, HB(C3H3N2)3 Tp , HB(3,5-Me2C3HN2)3 Tp, substituted hydrotiis(pyrazol-l-yl)borate Ts, tosyl tz, 1,2,4-triazolate Vin, vinyl. 

A recent report by Kropp(85) indicates that whereas 2-norbomene undergoes radical reactions when irradiated in alcohol solution in the presence of a sensitizer, 2-phenyl-2-norbomene and related analogs undergo polar addition of methanol when irradiated directly (photosensitized irradiation led to no products) ... 

Figure 38 (a) The ADMET polymerization (using Mo and Ru catalysts) of symmetrical a.oj-dienes that yield main-chain boronate polymers (59). (b) The ROMP of several norbomene monomers containing methyl- and phenyl-substituted boronates into unsaturated polymers (60). (Adapted from ref. 84.)... 

Biperiden Biperiden, l-(5-norbomen-2-yl)-l-phenyl-3-piperidinopropan-l-ol (10.2.4), is also synthesized according to the method of making trihexyphenidyl, except by reacting 2-(l-piperidino)propiophenone (10.2.1) with 5-norbomen-2-ylmagnesiumbromide [33,34],... 

Norbomen-2-yl 4-(l-(3-(2,2,5-trimethyl-4-phenyl-3-azahexoxy))ethyl)ben-zyl ether, (V), was previously prepared by the authors (4) and used in the controlled free radical copolymerization of ethylene and 5-norbomen-2-ol. Polymerization were carried out in the presence of the two component catalyst mixture of the current application. 

Aryl azides react with olefins to give 1,2,3-A2-triazolines.201-203 Whereas unactivated olefins are sluggish toward aryl azides, strained bicyclic systems, on the contrary, are particularly reactive.204-208 The rate of phenyl azide addition to a series of olefins parallels the heat of hydrogenation (Table Vffl).107 This thermodynamic parameter is a measure for the degree of strain associated with these molecules.200 Bicyclo[2.2.1]hep-tenes, such as norbomene (37), react readily at room temperature, and the addition occurs at the less hindered exo side (39).,06 1°7 210 211 A striking example of the increased... 

In a manner analogous to classic nitrile unmes, the additions of tnfluoro-methylacetomtnle phenylimine occur regiospecifically with activated terminal alkenes but less selectively with alkynes [39], The nitrile inline reacts with both dimethyl fumarate and dimethyl maleate in moderate yields to give exclusively the trans product, presumably via epimenzation of the labile H at position 4 [40] (equation 42) The nitrile imine exhibits exo selectivities in its reactions with norbomene and norbornadiene, which are similar to those seen for the nitrile oxide [37], and even greater reactivity with enolates than that of the nitrile oxide [38, 41]. Reactions of trifluoroacetomtrile phenyl imine with isocyanates, isothiocyanates, and carbodiimides are also reported [42]... 

In a 100-ml crimped vial, t-butyl 5-norbomene-2-carboxylate (17.5 mmol) and the Step 1 product (7.5 mmol) were dissolved in 40 ml of toluene and then sparged with nitrogen for 30 minutes. The mixture was next treated with the slow addition of freshly prepared bis(toluene)bis(perfluoro-phenyl) nickel (II) catalyst (0.5 mmol) in 10 ml of dry toluene and stirred overnight. The polymer was precipitated into hexane and filtered, and 3.5 g of white powder were isolated. 

It has been known for some time that on heating certain organic di- or polysulfanes seemingly split off S2, which may then add to a substrate to form another disulfane. Only recently, transfer reactions for the S3 and even the S3O unit have been observed. When a snbshtuted ( labeled ) norbomanetrisulfane is heated with norbomene in benzene to 100 °C, a clean transfer of the S3 unit is observed for R = phenyl (equation 128). 

The rate and the yield of the reaction shown in equation (128) depend on the nature of R and of the alkene to which the S3 unit is to be transferred. If this norbomene is also substituted in the 2-position the yields differ greatly depending on the substituent phenyl results in high, methyl in low, and methoxycarbonyl in intermediate yields. When an unsymmetrically-substituted norbomadiene is used as acceptor molecule, the two double bonds react at the same rate to give equal amounts of the two trithiolanes. Most probably, the transfer reaction proceeds by a concerted bimolecular mechanism. 

The course of the decomposition reaction is much dependent on the relative stereochemistry of the substituents on the C—C bond of the triazoline At intermediate temperatures (40-90°) the stereochemistry is conserved and usually only one product is detected. Cyclopentene, cycloheptene and cu-cyclooctene reacted with phenyl azide to give the corresponding iV-phenylimino derivatives in excellent yields, while cyclohexene and (mnj-cyclooctene did not yield imines at all, iziridines being the sole products . When higher temperatures are used, the stereochemical selectivity is apparently lost and a mixture of products is generally observed. In the reaction of norbomene... 

The carbocations generated by nonKolbe electrolysis can rearrange by alkyl, phenyl or oxygen migration. Some examples are given in Table 11. The carbocations generated from exo- or en[Pg.653]

Z, )-4-Phenyl-l-bromobuta-l,3-diene [(Z, )-15], if converted with norbomene (9) in the presence of a hydride source, gives cyclopentene 17 and cyclopropane 18 if catalyzed with pallad-ium(O) complexes. In the absence of a hydride source a substituted nortricyclene product 16 is formed. ... 

There are two reports of an alkyl to aryl rhodium migration process. The first example was reported in 2000 by Miura [75], It was discovered that, upon reaction of phenyl boronic acid with norbomene under rhodium-catalyzed conditions, a merry-go-around type sequential alkylation occurred up to four times on the aromatic ring, resulting in a 1,2,3,4-tetranorbomylated benzene as the final product (Scheme 16). Mechanistically, this reaction involves an alkyl to aryl migration of rhodium. Thus, aryl rhodium intermediate 29, generated via an initial transmetalation step,... 

An unusual influence of water on the rate of 1,3-dipolar cydoadditions was first observed when 2,6-dichlorobenzonitrile N-oxide was allowed to react with 2,5-di-methyl-p-benzoquinone [50]. Likewise, bromonitrile oxide, generated in water at acidic pH, gave cycloadducts effidendy with water-soluble alkenes and alkynes [51]. In highly aqueous media remarkable accelerations for the cycloaddition of phenyl azide to norbomene were observed [52]. 

As expected, 2-ethoxycarbonyl-5-phenyl-l,3,4-oxadiazin-6-one (102 R = Ph, R = C02Et) shows enhanced diene reactivity over the 2,5-diphenyl compound (102 R = R = Ph) and will react with norbornadiene at room temperature. Additionally, in some cases (e.g. with norbomene) the initial cycloadducts (103 R = Ph, R = C02Et) are isolable <85AG(E)886,90CB2031>. 

Kropp and coworkers have been concerned with systems in which homolysis is followed by rapid electron transfer, such as the photolysis of certain alkyl halides [55]. Photolysis of the norbomyl phenyl sulfoxide 110 was examined. The notion was that sulfide photolysis is usually homolytic, but the sulfinyl radical is more electronegative than the sulfenyl (thiyl) radical, which might assist in electron transfer reactions. Thus, it was thought, ionic reactivity might be observed. In addition to inversion of the sulfur center and deoxygenation (yide infra), norbomane 111 and norbomene 112, both presumed to... 

With the exception of norbomene, internal olefins do not undergo hydrosilylation. Hydrosilylation of 3-phenylpropene with PhSiDj forms a unique product and the process tolerates a variety of fianctional groups, halides, ethers and acetals, despite the well known strong Lewis acidity of the catalysts. Cyclisation/silylation of 1,5-dienes or 1,6-enynes has been reported to give a single product (Scheme 14) [26]. In the case of metallocene complexes bearing a menthyl substituent, ee values near 70% were obtained for the asymmetric hydrosilylation of 2-phenyl-but-l-ene [31]. 

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