Next, we investigated the electronics of the alkene. MHAT from weak field ligand catalysts occurs more slowly with electron deficient alkenes. Therefore, it was interesting to observe that with the amide starting material, 1an, product 2an' was isolated (Scheme 4a). This likely arises from addition of the nucleophilic cyclohexyl radical (from fragmentation of HEH-Cy •+ ) which is polarity matched with the electron-poor olefin, in contrast to the electrophilic Co III -H. The same reaction without cobalt catalyst gave a similar result. However, by switching to the parent Hantzsch Ester and carrying out the reaction at slightly higher temperature, we were able to isolate the product 2an from sequential MHAT and Smiles-rearrangement (Scheme 4b). Finally, we demonstrated that the product from our methodology can be further arylated under photoredox conditions to yield product 3. Scheme 4. Truce-Smiles rearrangement with amide substrate and α-functionalization of amines. without [Co]-1; without a cooling fan.