Intramolecular free-radical functionalisation of the methyl group of 5′-deoxyadenosine

Abstract

Anaerobic irradiation of 2′,3′-O-isopropylidene-8-phenylthio-5′-deoxyadenosine in the presence of t-butyl hydroperoxide causes rapid conversion into the 5′,8-cycloadenosine, formed by reaction of the C(8)-radical with the neighbouring 5′-methyl group; this provides an in vitro analogy for the functionalisation of this methyl group involved in many of the coenzyme B₁₂-controlled rearrangement reactions.