Controlling Radical Chain Reactions by Unimolecular Chain Transfer. Intramolecular Hydrogen Transfer Reactions of Silicon Hydrides

摘要

The benefits of intramolecularity are commonly used in synthesis to form carbon-carbon bonds by radical cyclizations. These cyclizations are usually conducted by methods (metal hydride, atom transfer) that involve bimolecular chain transfer steps. The full potential of bimolecular radical carbon-carbon bond forming reactions has yet to be realized. We now suggest the logical reversal of the standard modus operandi: bimolecular radical carbon-carbon bond forming reactions should be conducted with intramolecular chain transfer reactions. We term this class of transformations unimolecular chain transfer (UMCT) reactions.