As an example of the unique retrosynthetic disconnections that enantiospecific Ni-catalyzed radical cross-coupling can enable (Figure ), chiral piperidine 46 was targeted. This molecule was previously prepared using a standard strategy relying on polar-bond analysis, commencing from vinyl-BPin piperidine 43, Suzuki coupling with 1.5 equiv. of Bn-protected pyridine yield). In stark contrast, iodopyridine 42 containing a sensitive triflate at C-2 could be directly coupled to sulfonylhydrazide 11 to deliver the same target after Cbz removal in 35% overall yield from 11 or 21% from the corresponding commercial alcohol 92.2 : 7.8 e.r.. Another example that showcases the simplifying power of this transformation is the preparation of chiral pyrrolidine 51 ($1620/g in racemic form). The prior six-step route (3% overall yield) relies on a chiral auxiliary based conjugate addition onto vinyl-nitro containing pyrazine 48 which proceeds in 1:1 d.r.