Methyl norbornadiene-2-carboxylate

Homo-Diels-Alder reactions of norbornadiene, In the presence of Ni(COD)2 and P(C6H5)3 (1 2) norbornadienes can react with activated alkenes at 80° to give [2 + 2 + 2] adducts. Preliminary studies of the regioselectivity indicate that this homo-Diels-Alder reaction can be useful for synthesis of complex molecules. Thus reaction of methyl norbornadiene-2-carboxylate with acrylonitrile results in only two... 

The process of synchronous enantiomeric enrichment of both reactant and product using circularly polarized light (CPL), for which the term new absolute asymmetric synthesis (NAAS) has been coined, was studied in detail for the case of methyl norbornadiene-2-carboxylate 41This photorearrangement (irreversible NAAS) of racemic 41 produces the chiral product 42. When 41 was irradiated with r-CPL at 290 nm, enantiomeric enrichment by (-l-)-41 and (+)-42 occurs. The inverse process was observed for /-CPL. The enantiomeric enrichment of 41 increases up to 100% enantiomeric excess (ee) at nearly 100% conversion, and the ee of 42 gradually decreases to zero at the end of reaction. These results suggest that one can obtain about 40% ee of 41 and 42 at 50% conversion if a starting material with an anisotropy factor g g = Ae/e) of unity is used. 

Nishino, H., Nakamura, A., and Inoue, Y., Theoretical and experimental verification of the asymmetric photoisomerization of methyl norbornadiene-2-carboxylate to methyl quadricyclane-1-carboxylate,/. Chem. Soc., Perkin Trans. 2, 1693-1700, 2001. 

Carbonylation of Dichloro(norbornadiene)palladium(II) in Methanol Methyl exo-S-Methoxytricy-clo[2.2.1.0 ]heptane-endo-3-carboxylate (18) Single Procedure ... 

Nakabayashi, K. and Takamuki, S., Triplet sensitized quadricyclane-norbornadiene valence isomerization of methyl 5-(4-biphenyl)tetracyclo[3.2.0.2 0. ]heptane-l-carboxylate, Bull. Chem. Soc. Jpn., 65, 3177-3179, 1992. 

Nishikubo, X, Kawashima, X, and Watanabe, S., Synthesis of polymers bearing pendant norbor-nadiene moieties by addition reaction of poly(glycidyl methacrylate-co-methyl methacrylate) s with 2,5-norbornadiene-2-carboxylic acids, f. Polym. Sci, Part A Polym. Chem., 31, 1659-1665, 1993. 

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