Historically, chiral aminoalcohols are essential building blocks to access chiral morpholines and piperazines, both of which are privileged structures in active pharmaceutical ingredients. Yet, their syntheses are often time-consuming and laborious. For example, morpholine 92 37 and piperazine 94 were previously synthesized through 6 and 10 step routes, respectively (Figure ). Of the sixteen combined steps in those routes, only four assembled key C-C bonds with the remainder being redox fluctuations and PG/FG manipulations. The chemoselective nature of the decarboxylative coupling allows the pivotal ester-containing chiral aminoalcohol 90 to be accessed quickly on gram scale. Then, both morpholine 92 and piperazine 94 can be accessed divergently in 2-3 additional steps. Having demonstrated the utility of diastereoselective decarboxylative arylation, attention shifted to analogous alkylations and acylations to build functionality-rich saturated carbon frameworks (Figure ). A simple hydroxylactam 4, a known precursor for a number of bioactive compounds, was previously prepared via a 6-step synthesis from suitably protected aspartic acid wherein only one step is strategic (HWE, C-C bond forming). In sharp contrast, 4 can be made in 3 steps by stitching together aminoalcohol cassette and inexpensive glutaric acid derived RAE 95 followed by deprotection and cyclization. The power of diastereoselective decarboxylative acylation can be brought to bear on the divergent synthesis of sphingoid bases 2, 99-102 (Figure ). This approach is well-suited to a hypothetical medicinal chemistry program, as all of these compounds can be divergently derived from common intermediate 97, readily prepared by decarboxylative acylation between 10-RAE and palmitic acid. Stereoselective reduction of the ketone by NaBH4 or aminedirected reduction with LiAlH(O t Bu)3 leads to the formation of 2 and 99, respectively.