Mono endo-6- And bis endo,endo-12-N,N-diethylcarbamoyl derivatives of Tröger’s Base. Synthesis and exo-endo isomerization study

An efficient synthetic route to the mono-endo-6- and bis-endo,endo-6,12-N,N-diethylcarbamoyl derivatives of Tröger’s base (TB), endo-7 and endo-8, is reported. Studies of reaction time, proton source, and additive allowed establishment of optimized conditions for the conversion of exo-7 into the corresponding isomer endo-7. With a longer reaction time, the exo,exo-6,12 bis-carbamoyl derivative exo-8 was converted into the corresponding endo,endo-bis-carbamoyl product endo-8. Single crystal X-ray crystallographic analysis confirmed the structural and stereochemical assignments made on the basis of 1H NMR, mechanistic, and calculational studies. Deuterium quench experiments using LDA, CD3ONa/CD3OD and DCl/CD3OD conditions of both exo-7 and exo-8 afforded exo-7d1 and exo-8d2, respectively (> 95% deuterium incorporation), supporting an enolate mechanism for the isomerization. In contrast, when repeating the experiment with DCl/CD3OD, no deuterium was incorporated, suggesting the traditional ring-opening mechanism involving an iminium ion

A Double Conformationally Restricted Dynamic Supramolecular System for the Substrate-Selective Epoxidation of Olefins-A Comparative Study on the Influence of Preorganization

A double conformationally restricted kinetically labile supramolecular catalytic system, the third generation, was designed and synthesized. We investigated the substrate selectivity of this system by performing competitive pairwise epoxidations of pyridyl-and phenyl-appended olefins. We compared the obtained substrate selectivities to previous less preorganized generations of this system. Five different substrate pairs were investigated, and the present double conformationally restricted system showed higher normalized substrate selectivities ( pyridyl versus phenyl) for two of the substrate pairs than the previous less conformationally restricted generations. As for the preorganization of the components of the system, the catalyst, and the receptor part, it was shown that for each substrate pair there was one generation that was better than the other to generate substrate-selective catalysis