Isocyanides as Acceptor Groups in MHAT Reactions with Unactivated Alkenes

The use of isocyanides as acceptor groups in metal–hydride hydrogen atom transfer (MHAT) coupling reactions with nonactivated alkenes to form heterocycles is described. Monosubstituted alkenes couple and cyclize directly, whereas more substituted alkenes proceed via a two-step, one-pot procedure involving MHAT reductive cyclization followed by a MHAT Minisci coupling upon the addition of acid. To highlight the utility of the methodology, a diverse variety of substituted heterocycles such as phenanthridines, indoles, and isoquinolines were prepared.