A Radical Approach to Anionic Chemistry: Synthesis of Ketones, Alcohols, and Amines

Shengyang Ni, Natalia M. Padial, Cian Kingston, Julien C. Vantourout, Daniel C. Schmitt, Jacob T. Edwards, Monika M. Kruszyk, Rohan R. Merchant, Pavel K. Mykhailiuk, Brittany B. Sanchez, Shouliang Yang, Matthew A. Perry, Gary M. Gallego, James J. Mousseau, Michael R. Collins, Robert J. Cherney, Pavlo S. Lebed, Jason S. Chen, Tian Qin, Phil S. Baran

Research output: Contribution to journalArticle

20 Citations (Scopus)

Abstract

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.

Original languageEnglish (US)
Pages (from-to)6726-6739
Number of pages14
JournalJournal of the American Chemical Society
Volume141
Issue number16
DOIs
StatePublished - Apr 24 2019
Externally publishedYes

Fingerprint

Ketones
Amines
Alcohols
Synthetic Chemistry Techniques
Imines
Carboxylic Acids
Forging
Aldehydes
Carboxylic acids
Functional groups
Oxidation-Reduction
Esters
Electrons
Derivatives

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Ni, S., Padial, N. M., Kingston, C., Vantourout, J. C., Schmitt, D. C., Edwards, J. T., ... Baran, P. S. (2019). A Radical Approach to Anionic Chemistry: Synthesis of Ketones, Alcohols, and Amines. Journal of the American Chemical Society, 141(16), 6726-6739. https://doi.org/10.1021/jacs.9b02238

A Radical Approach to Anionic Chemistry : Synthesis of Ketones, Alcohols, and Amines. / Ni, Shengyang; Padial, Natalia M.; Kingston, Cian; Vantourout, Julien C.; Schmitt, Daniel C.; Edwards, Jacob T.; Kruszyk, Monika M.; Merchant, Rohan R.; Mykhailiuk, Pavel K.; Sanchez, Brittany B.; Yang, Shouliang; Perry, Matthew A.; Gallego, Gary M.; Mousseau, James J.; Collins, Michael R.; Cherney, Robert J.; Lebed, Pavlo S.; Chen, Jason S.; Qin, Tian; Baran, Phil S.

In: Journal of the American Chemical Society, Vol. 141, No. 16, 24.04.2019, p. 6726-6739.

Research output: Contribution to journalArticle

Ni, S, Padial, NM, Kingston, C, Vantourout, JC, Schmitt, DC, Edwards, JT, Kruszyk, MM, Merchant, RR, Mykhailiuk, PK, Sanchez, BB, Yang, S, Perry, MA, Gallego, GM, Mousseau, JJ, Collins, MR, Cherney, RJ, Lebed, PS, Chen, JS, Qin, T & Baran, PS 2019, 'A Radical Approach to Anionic Chemistry: Synthesis of Ketones, Alcohols, and Amines', Journal of the American Chemical Society, vol. 141, no. 16, pp. 6726-6739. https://doi.org/10.1021/jacs.9b02238
Ni S, Padial NM, Kingston C, Vantourout JC, Schmitt DC, Edwards JT et al. A Radical Approach to Anionic Chemistry: Synthesis of Ketones, Alcohols, and Amines. Journal of the American Chemical Society. 2019 Apr 24;141(16):6726-6739. https://doi.org/10.1021/jacs.9b02238
Ni, Shengyang ; Padial, Natalia M. ; Kingston, Cian ; Vantourout, Julien C. ; Schmitt, Daniel C. ; Edwards, Jacob T. ; Kruszyk, Monika M. ; Merchant, Rohan R. ; Mykhailiuk, Pavel K. ; Sanchez, Brittany B. ; Yang, Shouliang ; Perry, Matthew A. ; Gallego, Gary M. ; Mousseau, James J. ; Collins, Michael R. ; Cherney, Robert J. ; Lebed, Pavlo S. ; Chen, Jason S. ; Qin, Tian ; Baran, Phil S. / A Radical Approach to Anionic Chemistry : Synthesis of Ketones, Alcohols, and Amines. In: Journal of the American Chemical Society. 2019 ; Vol. 141, No. 16. pp. 6726-6739.
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