PubMed · 6043822
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R Breslow, G Ryan. 1967-06-07. Cyclopropenone.. https://doi.org/10.1021/ja00988a063
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The metal-catalyzed allylic substitution reaction of 5a,b and 6a was examined. Reaction with stabilized nucleophiles led to exclusive attack at the less-hindered allylic terminus, and the stereoselectivity varied with the bidentate ligand used but favored retention. The yields and reaction times were improved with the use of microwaves. Alkylation via transmetalation was only observed with phenyl- and vinylstannatranes and gave regio- and stereoselectivity opposite those observed with the stabilized anions. The epimeric carbonates 5a and 5b displayed very different reactivities. Catalysts containing metals other than palladium were completely unreactive and led to recovered starting material.
The inability of the intrazeolite environment to influence the regiochemistry of addition of singlet oxygen to electron-poor olefins is reported. This divergent behavior with respect to electron-rich alkenes is rationalized with a multicomplexation model that emphasizes the importance of intrazeolite substrate-cation binding.
Cadmium selenide nanoparticles, prepared by known methods, were stabilized with functional phosphine oxide 1, then used to support the polymerization of cyclic olefins radially outward from the surface by ruthenium-catalyzed ring-opening metathesis polymerization (ROMP). The conversion of compound 1 into the new metathesis catalyst 3 by carbene exchange and the subsequent polymerization of cyclic olefins were observed spectroscopically by (1)H NMR to afford for example CdSe-polycyclooctene composite 6. Transmission electron micrographs on thin films of these composites showed good nanoparticle dispersion. This is in stark contrast to the substantial nanoparticle aggregation observed when similar polymerizations were performed in the presence of conventional TOPO-covered nanoparticles. The methods reported here to prepare composite product 6 are applicable to other cyclic olefins, and suggest that this chemistry will be useful for incorporating CdSe nanoparticles into a wide variety of polymer matrices.