Efficient functionalization of acylnitroso cycloadducts: Application to the syntheses of carbocyclic nucleoside precursors

1,4-cis-disubstituted cyclopentene precursors of carbocyclic nucleotides were readily prepared utilizing acylnitroso hetero Diels-Alder reactions and Pd(0)-catalyzed alkylation reactions as the key steps. The chemistry was explored in both racemic and asymmetric fashion. The hydroxymethyl components of the carbocyclic nucleoside precursors were obtained from nitromethyl groups under oxidative Nef conditions and may be further elaborated into a variety of compounds of potential biological interest.