Turning Spiroketals Inside Out: A Rearrangement Triggered by an Enol Ether Epoxidation.

ABSTRACT: Spiroketals organize small molecule structures into well-defined, three-dimensional configurations that make them good ligands of proteins. We recently discovered a tandem cycloisomerization-dimerization reaction of alkynyl hemiketals that delivered polycyclic, enol-ether-containing spiroketals. Here we describe rearrangements of those compounds, triggered by epoxidation of their enol ethers that completely remodel their structures, essentially turning them "inside out". Due to the high level of substitution on the carbon skeletons of the substrates and products, characterization resorted to X-ray crystallography and advanced computation and NMR techniques to solve the structures of representative compounds. In particular, a new proton-detected ADEQUATE NMR experiment (1,1-HD-ADEQUATE) ena

SUBMITTER: Lorenc C 

PROVIDER: S-EPMC4608522 | biostudies-literature | 2015 Oct

REPOSITORIES: biostudies-literature