Application of the polybromo ketone-iron carbonyl reaction to natural product synthesis is summarized. The general synthesis of tropane alkaloids has been achieved via the reductive [3+ 4] cyclocoupling of sym-tetrabromoacetone with N-methoxycarbonylpyrrole as the key step. Ready availability of 8-oxabicyclo [3.2. 1] oct-6-en-3-one from the tetrabromoacetone and furan has opened a new, efficient entry to natural C-nucleosides ...