Of norbomene derivatives

Gunter and co-workers have applied this methodology to the condensation of norbomene derivative 90 (block A, Scheme 32) with epoxide 94 (block B, Scheme 33) <98S593>. Thus, using the Crossley porphyrin-a-dione 47, condensation with 1,2,4,5-benzenetetramine tetrahydrochloride and then the product with a strained dione, gave 90 as block A. 

T. Hasan, T. Ikeda, and T. Shiono, Homo- and copolymerization of norbomene derivatives with ethene by ansa-fluorenylamidodimeth-yltitanium activated with methylaluminoxane,. Polym. Sci., Part A Polym. Chem., 45(20) 4581-4587, October 2007. 

J.P. Mathew, A. Reinmuth, J. Melia, N. Swords, and W. Risse, (ry-3-allyl) palladium (ii) and palladium (ii) nitrile catalysts for the addition polymerization of norbomene derivatives with functional groups, Macromolecules, 29(8) 2755-2763,1996. 

Due to its versatile applicability, the CuOTf-catalyzed [2 + 2] photocycloaddition was used successfully to study the topology of the intermolecular and intramolecular dimerization of norbomene derivates. When a racemic mixture of compound 27 is transformed in the presence of CuOTf, a 1 1 mixture of two stereoisomers (28a,b) is... 

Other Pd Derivatives and Related Reactions. Other chiral palladium complexes, such as (DIOP)2Pd° or (DIOP)(alkene)Pd°, can be prepared from (DIOP)PdCl2. These catalysts have afforded low levels of asymmetric induction (10% ee) in the hydro-cyanation of norbomene derivatives. ... 

Cross-metathesis of trialkoxy- and trisiloxy-substituted vinylsilanes [21] as well as octavinylsilsesquioxane [15] with vinyl sulfides proceeds efficiently but only in the presence of the 2nd generation Grubbs catalysts (IV) to offer a new and very attractive route for syntheses of [alkyl(aiyl)]sulfide-substituted vinylsilanes and vinyl-silsesquioxane with high preference for the -isomer, as illustrated by exclusive isolation of such isomers. The Fischer-type ruthenium carbene complex Ru(=CHSPh)Cl2(PCy3)2 has recently been reported as an effective catalyst in the ring opening/cross-metathesis of norbomene derivatives with vinyl sulfide [22], suggesting that these carbenes can be reactive in the cross-metathesis. 

In assessing data on the proportions of cc, ct and tt pairs it is first necessary to ensure that the cis content has not been modified by the occurrence of secondary metathesis reactions. These can occur extremely rapidly with some polymer/catalyst systems. For example a polymer of cycloocta-1,4-diene initially contains no tt junctions, alternate double bonds in the polymer chain being derived from preformed cis double bonds in the monomer but under certain catalyst conditions tt junctions appear within a matter of seconds by secondary metathesis (14,15). These problems do not appear to be serious in polymers of norbomene derivatives presumably because the double bonds in the polymer are protected from secondary metathesis by the adjacent C5 rings and cannot compete when highly reactive monomer is still present. 

Complex 10 is a very active catalyst for ring-opening cross-metathesis of norbomene derivatives. ... 

Harke, H. P., C.J. Drews, and D. Schuller Uber das Vorkommen von Norbomenderivaten in Tabakrauch-kondensaten [On the occurrence of norbomene derivatives in tobacco smoke condensate] Tetrahedron Lett. 3 (1970)3789-3790. 

An example of this type of forward reaction has already been given in Seheme 2.4. Further examples are provided by (i) the use of norbomene epoxide with W-based catalysts to enhance the ROMP of norbomene derivatives (Devine 1982) (ii) the use of oxygen with norbomene in Ru-based systems to generate such an epoxide (Ivin 1981b) (iii) the use of cyclopropane derivatives with Re207/Al203 (Anisimov 1991) see Ch. 2. 

Table 11.7 Polymers of norbomene derivatives showing m r splitting of the trans HH olefmic resonance in the C NMR spectrum X = eATO-5-substituent, Y = e/i o-5-substituent. Catalyst RUCI3.3H2O in EtOH/PhCl at 50-70°C, except where indicated otherwise (Ivin...

A very large number of norbomene derivatives has been cyclopropanated in good yields giving the exo distereomer in all cases (Scheme 7).[5],[6],[21],[23],[26H29]... 

We were able to synthesize silicon compounds with two terminal double bonds selectively by ringopening metathesis reaction of norbomene derivatives in the presence of ethylene. 

Synthetic Aspects.—Continuing interest has been shown in the use of norbomene derivatives, produced by Diels-Alder reactions, for t ie synthesis of carbocyclic analogues of C-nucleosides. ... 

These complexes spontaneously not only promote the ROMP of norbomene derivatives to high molecular weight polynorbomenes, but also they are effective at polymerising... 

Detection of a rare alkylidene-alkene complex is possible by NMR spectioscopy using 22. The metallacyclobutane remains undetected (the ROMP propagation rate is higher than that of initiation). These ideas are supported by the kinetics studies of norbomene derivatives using 22.290... 

A mechanism analogous to that described by sdieme (8) has been proposed by Batog et al. for the reaction of norbomene-derived carboxylic acid with alicydic monoepoxides. The reaction, which is carried out in the bulk, is second order. 

Breunig, S. Risse, W. Transition metal-catalyzed vinyl addition polymerizations of norbomene derivatives with ester groups. Makromol. Chem. 1992,193, 2915-2927. 

Gringolts ML, Bermeshev MV, Makovetsky KL, Finkelshtein ESh (2009) Effect of substituents on addition polymerization of norbomene derivatives with two Mes Si-groups using Ni(ll)/MAO catalyst. Eur Polym J 45 2142-2149... 

MATsuMOTO ET AL. Polymerization of Norbomene Derivatives TABLE II Polymerization of Norbomene Derivatives... 

Warrener et al. have shown that cyclobutene epoxides 126 undergo C-C ring opening into cyclic carbOTiyl ylides 127 that can be quenched by alkenes in 1,3-dipolar cycloaddititMis, generating 7-oxanorbomane derivatives 128 (Scheme 19) [159, 160], The method has been applied to construct molecular devices such as 131 by double cycloadditions of norbomene derivatives 129 to the bis-epoxide 130. 

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