SYNTHETIC METHODS AND REACTIONS .62. TRANSFORMATIONS WITH CHLOROTRIMETHYLSILANE SODIUM IODIDE, A CONVENIENT IN SITU IODOTRIMETHYLSILANE REAGENT

A new, convenient, inexpensive alternative to iodotrimethylsilane reagent is explored. A mixture of chlorotrimethylsilane/sodium iodide in acetonitrile is found to be a better reagent than iodotrimethylsilane for the cleavage of esters, lactones, carbamates, and ethers. Cleavage of esters and lactones (10 examples) occurred somewhat slower with the present system than with iodotrimethylsilane. On the other hand, ethers (7 examples) cleaved much more readily with the present system. A feasible mechanism is proposed for this disparity. Carbamates (6 examples) also underwent facile cleavage to give the corresponding amines. The general applicability of the method has been shown using various types of substrates. The facile conversion of alcohols to iodides using the present method is also reported. Conversion of alcohols to iodides is much faster with chlorotrimethylsilane/sodium iodide than with iodotrimethylsilane, and iodides are formed in excellent yield. © 1979, American Chemical Society. All rights reserved.