A bioinspired repair process allows to expand the synthetic scope of radical reactions.

The organocatalytic [2,3]‐Wittig rearrangement of allyloxyketones was investigated. Extensive screening of chiral amine organocatalysts showed that small pyrrolidine‐based catalysts or simple phenylethylamine with the primary amino group were the most effective ones. Interestingly, CF3‐derived pyrrolidine affords the rearrangement product with an opposite absolute configuration to the product obtained by using the corresponding non‐fluorinated proline derived catalysts. Mechanistic and computational investigations were also performed.

A simple procedure for the conversion of tertiary lactams to 2-monoalkylated cyclic amines is described. The reaction sequence involves conversion of a lactam to a thioiminium ion followed by reaction with an organocopper (RCu) reagent and final reduction with triacetoxyborohydride. The reaction is high yielding and shows an excellent functional group tolerance. Its utility is demonstrated by a rapid synthesis of indolizidine 167B. The excellent chemoselectivity of the process, where only monoalkylation products are formed, is rationalized by a mechanism involving the formation of a transient enamine.