Dimethyl (1α,2β, 5β,6α) tricyclo[4.2.1.0^2,5] nona-3,7-dien-3,4-dicarboxylate

Recent Advances in the Chemistry of Pentafulvenes

“…To address this problem, Warrener et al conducted a reaction between 6-adamantylidenefulvene and a reactive dienophile, Smith's diene 119, affording the [4+2] cycloadduct 120 in good yield. 124 Here, the adamantyl group is rigidly bound to the molecular framework by the olefinic linkage originating from the fulvene (Scheme 33). This reaction has also been exploited for the development of bis-adducts by employing a modified Smith's diene under high pressure conditions.…”

Tricyclononenes and tricyclononadienes as efficient monomers for controlled ROMP: understanding structure–propagation rate relationships and enabling facile post-polymerization modification

“…2a). 13,31 We note that upon storage under ambient atmosphere for extended periods, TCND-(CO 2 Me) 2 yellows and a new product is observed via 1 H NMR spectroscopy. A small sample of this impurity was isolated chromatographically; its 1 H NMR spectrum contained no olenic resonances and its high-resolution mass spectrum suggested a mass 16 Da (i.e., 1 oxygen atom) larger than TCND-(CO 2 Me) 2 .…”

“…In addition to their straightforward syntheses and good k p values, TCND-(CO 2 Me) 2 and TCND-CO 2 Me, and their corresponding polymers p(TCND-(CO 2 Me) 2 ) and p(TCND-CO 2 Me), offer unique opportunities for further derivatization and postpolymerization functionalization, respectively, compared to exo-NBs. While their cycloaddition reactivity has been explored, [45][46][47] we suspected that their strained, electron-decient cyclobutene substituents would make them good electrophiles for conjugate addition reactions (e.g., "thiol-Michael" addition). To test this idea, TCND-(CO 2 Me) 2 was exposed to dodecanethiol (1.0 equiv.)…”

Tricyclononenes and Tricyclononadienes as Efficient Monomers for ROMP: Understanding Structure–Propagation Rate Relationships and Enabling Facile Post-Polymerization Modification

“…were synthesized by direct cycloaddition of quadricyclane with dimethylacetylenedicarboxylate and methyl propiolate, respectively (Figure 2a). 13,31 Finally, for comparison of ROMP propagation rates (vide infra), exo-NB analogs of each TCN and TCND were synthesized following previously reported procedures. [32][33][34] All monomers and intermediates were isolated non-chromatographically, and the key intermediates towards TCNs (1) and TCNDs (quadricyclane) were synthesized on the 16 g and 17 g scales, respectively.…”

“…Overall, these data suggest that the overall size and shape of the monomer has a significant impact on polymerization kinetics. been explored, [43][44][45] we suspected that their strained, electron-deficient cyclobutene substituents would make them good electrophiles for conjugate addition reactions (e.g., "thiol-Michael" addition). To test this idea, TCND-(CO2Me)2 was exposed to dodecanethiol (1.0 equiv) in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) (10 mol %) in CDCl3 for 30 min (Table 3, entry 1).…”