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 including pscudouridine, pseudocytidinc, and showdomycin. The artificial analogues such as 2-thiopscudouridine, 6-azapseudouridine, pseudoisocytidine, etc., are also obtainable. The oxabicyclic ketones bearing an isopropyl substituent at the appropriate position serve as intermediates for the synthesis of naturally occurring troponoids, nezukone, α-thujaplicin, and hinokitiol (β-thujaplicin). Carbocamphenilone and camphenic acid have been prepared through the [3 + 4] reaction of 1,1,3-tribromo- 3-methylbutan-2-one and cyclopentadiene. The [3+2] cyclocondensation of an α,ǵa-dibromo ketone and a styrene derivative leads to the single-step synthesis of α-cuparenone. 1,3-Dibromo-3,7-dimethyloct-6-en-2- one derived from nerol (or geraniol) undergoes the biogenctic-type double cyclization. The iron carbonylassisted intramolecular [3 + 2] cyclocoupling gives camphor accompanied by other monoterpenic ketones. A mixture of campherenone and epicampherenone has been obtained from related dibromo ketone prepared from farnesols. The hetero [3+2] reaction by use of dibromo ketones and N,N-dimethylcarboxamides, forming 3 (2H)-furanones, is employable for the preparation of muscarine alkaloid derivatives.