Synthetic studies on dodecahedrane. Generation and reactions of its radical and anion

The radical and anionic chemistry of dodecahedrane (DDH-H) was explored. Dodecahedryl bromide (DDH-Br) was converted to DDH-SePh and both compounds allowed access to the dodecahedryl radical. This radical exhibited a lack of nucleophilic character which severely limited the variety of radical traps successful in derivatization of the dodecahedryl nucleus. Acrylonitrile, cyclopentenone and allyltributyltin were found to trap this unique radical. Other traps allowed hydrogen atom abstraction to produce the parent hydrocarbon as the major product.;The dodecahedryl anion was, for the first time, generated and trapped. Radical anion (DDH-SPh and LiDBB) or transmetalation (DDH-Br and t-BuLi) methodology yielded the lithio species, which after trapping with allyl bromide yielded allydodecahedrane. Unfortunately, in both cases, only a 3 to 7 ratio of anion trapping to reduction was observed. The lack of synthetic utility of the dodecahedryl anion prevented further anion trapping products to be acquired.;The electrophilic chemistry of DDH-Br was extended by making use of ZnI;Dodecahedrene, the mono-olefin of DDH-H was generated and trapped as the epoxide by making use of a phenylselenoxide elimination in the presence of buffered mCPBA. The strain energy of dodecahedrene was also measured by bracketing gas-phase ion molecule reactions in an FT/ICR.;Attempted regiospecific, 1,2-disubstitution was attempted via photochemical reactions of DDH-CH...