Substrate and stereocontrolled iodocycloetherification of highly functionalized enantiomerically pure allylic alcohols: application to synthesis of cytotoxic 2-epi jaspine B and its biological evaluationElectronic supplementary information (ESI) available: 1H (1D and 2D) and 13C NMR spectra. See DOI: 10.1039/c5ob01123j

Stereoselectivities of electrophilic additions of molecular iodine to enantiomerically pure highly functionalized allylic alcohols with internal nucleophiles have been investigated. The intramolecular nucleophilic attack on the I 2 -π complex by an oxygen nucleophile to obtain tri- and tetrasubstituted THFs is highly regio-, stereoselective and substrate controlled. The application of this study has been shown by utilizing one of the THFs 4a as a key intermediate to complete the total synthesis of marine anti-cancer natural product 2- epi jaspine B. A mechanistic study on iodocycloetherification of enantiopure allylic alcohols is established. Its application to synthesis of marine cytotoxic 2- epi jaspine B has been demonstrated.