With robust biocatalytic access to the key hydroxylated piperidines in hand, their downstream modular functionalization was explored using radical cross-coupling methods. Thus, a set of 2substituted-3-hydroxypiperidine containing molecules were selected (Figure ) as this structural class is present in a variety of natural products and bioactive compounds. N-Boc-3-hydroxy-2phenylpiperidine 19 was utilized as a key intermediate in the synthesis of neurokinin NK1 receptor antagonists, such as (+)-L-733,060 and (+)-CP-99,994. These lead compounds are known to exhibit a variety of biological activities, including neurogenic inflammation, pain transmission and regulation of the immune response. They have been implicated in a variety of disorders such as migraine, rheumatoid arthritis, and pain. The main synthetic strategy employed involves the use of chiral pool derived intermediates or chiral auxiliaries to achieve diastereoselective synthesis of the 1,2-amino alcohol fragment using polar-bond disconnections, followed by ring-closure. Among the >10 routes reported (see Supporting Information for summary), most suffer from a lack of diastereoselectivity, lengthy routes (7-17 steps), cryogenic temperatures, and expensive transition metals. In contrast, hydroxypiperidine 14 can simply engage in chemoselective Nielectrocatalytic decarboxylative cross coupling with iodobenzene to afford 19 directly (48% isolated yield, single diastereomer). If a medicinal chemist chose to explore the structure-activity relationship (SAR) of the arene moiety this could now be easily accomplished rather than starting from scratch.