The catalytic intramolecular Wittig reactions of carbonyl-containing bromides are reported. The R3PO byproducts participate in the catalytic cycle; therefore, the Wittig reaction can be accomplished with only a catalytic amount of organophosphorus reagent. The reaction has also been applied to the efficient and selective synthesis of isoquinolin-1(2H)-ones, indoles, 2,3-dihydro-1H-2-benzazepin-1-ones, benzofurans, and 1,2-dihydroquinolines with a catalytic amount of phosphine oxide (0.1 equiv.) and a tetramethyldisiloxane/titanium isopropoxide ...