A Radical Approach to Anionic Chemistry: Synthesis of Ketones, Alcohols, and Amines Ni, Shengyang Muñoz Padial, Natalia We would like to thank Enamine Ltd for providing samples of several acids. We are grateful to Dr. Dee- Hua Huang and Dr. Laura Pasternack (Scripps Research) for assistance with nuclear magnetic resonance (NMR) spectroscopy and Mr. Andrew Badwal (Pfizer) for high throughput purification. We also thank Stephen Harwood (Scripps Research) for helpful advice and David Hill and Prof. Donna Blackmond (both Scripps Research) for assistance with the mechanistic studies. Historically accessed through two-electron, anionic chemistry, ketones, alcohols, and amines are of foundational importance to the practice of organic synthesis. After placing this work in proper historical context, this Article reports the development, full scope, and a mechanistic picture for a strikingly different way of forging such functional groups. Thus, carboxylic acids, once converted to redox-active esters (RAEs) can be utilized as formally nucleophilic coupling partners with other carboxylic derivatives (to produce ketones), imines (to produce benzylic amines), or aldehydes (to produce alcohols). The reactions are uniformly mild, operationally simple, and, in the case of ketone synthesis, broad in scope (including several applications to the simplification of synthetic problems and to parallel synthesis). Finally, an extensive mechanistic study of the ketone synthesis is performed to trace the elementary steps of the catalytic cycle and provide the end-user with a clear and understandable rationale for the selectivity, role of additives, and underlying driving forces involved. 2020-02-27T09:24:58Z 2020-02-27T09:24:58Z 2019 journal article S. Ni, N. M. Padial, C. Kingston, J. C. Vantourout, D. C. Schmitt, J.T. Edwards, M. M. Kruszyk, R. R. Merchant, P. K. Mykhailiuk, B. B. Sanchez, S. Yang, M. A. Perry, G. M. Gallego, J. J. Mousseau, M. R. Collins, R. J. Cherney, P. S. Lebed, J. S. Chen, T. Qin, P. S. Baran. “A Radical Approach to Anionic Chemistry: Synthesis of Ketones, Alcohols, and Amines”. J. Am. Chem. Soc. 2019, 141, 6726–6739. [https://pubs.acs.org/doi/10.1021/jacs.9b02238] http://hdl.handle.net/10481/59869 10.1021/jacs.9b02238 eng http://creativecommons.org/licenses/by-nc-nd/3.0/es/ open access Atribución-NoComercial-SinDerivadas 3.0 España American Chemical Society