This supplement to R35 GM131816 is focused on the development of a series of new deaminative cross-couplings and the training of graduate student Bria Garcia, in line with the goals of PA-21- 071. The scientific goals of this supplement are to develop (1) reductive cross-electrophile couplings of alkylpyridinium salts and (hetero)aryl chlorides, and (2) cascade cyclizations of alkylpyridinium salts tethered to alkenes to deliver a range of cyclic products. Both these reactions transform readily available starting materials into valuable motifs found in bioactive molecules. This research will hone Ms. Garcia’s expertise in catalytic method development. It will also greatly enhance her research capabilities by giving her experiences in high-throughput experimentation (HTE), collaborative interactions and insight with medicinal chemists at Pfizer, Inc., and proficiency in developing stereoselective transformations. This supplement proposal also includes a mentoring plan, including participation in UD’s Chemistry-Biology Interface program, multiple courses and workshops, teaching and mentoring experience, and professional networking opportunities, to maximize Ms. Garcia’s training and future success.