ORGN 622

We describe [I] the first example of intramolecular cycloaddition of a TMM diyl to a remotely tethered aldehyde, [II] the effect of a Lewis acid upon the course of TMM chemistry, [III] examples of exclusive intramolecular cycloaddition, competitive cycloaddition and atom transfer-cyclization (ATC), and exclusive ATC, and [IV] a set of predictive guidelines with which to assess whether cycloaddition or ATC will be the preferred path, and when two processes will be competitive. Remarkably, a wide variety of structures can be obtained simply by varying the length of the tether within the diazene investigated. DFT calculations were used to probe the energy surfaces for both atom transfer and cycloaddition. The transition structure for atom transfer involving the captodative system indicates that it occurs earlier along the reaction coordinate than for a system having only one radical stabilizing group. This is consistent with the existence of an exothermic process leading from the initial diyl to captodatively stabilized distonic diyl. Gratifyingly, theory agrees with observation and provides substantial insight into the chemistry.