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

Autor:	Ni S; Department of Chemistry , Scripps Research , 10550 North Torrey Pines Road , La Jolla , California 92037 , United States., Padial NM; Department of Chemistry , Scripps Research , 10550 North Torrey Pines Road , La Jolla , California 92037 , United States., Kingston C; Department of Chemistry , Scripps Research , 10550 North Torrey Pines Road , La Jolla , California 92037 , United States., Vantourout JC; Department of Chemistry , Scripps Research , 10550 North Torrey Pines Road , La Jolla , California 92037 , United States., Schmitt DC; Pfizer Medicinal Sciences , Eastern Point Road , Groton , Connecticut 06340 , United States., Edwards JT; Department of Chemistry , Scripps Research , 10550 North Torrey Pines Road , La Jolla , California 92037 , United States., Kruszyk MM; Department of Chemistry , Scripps Research , 10550 North Torrey Pines Road , La Jolla , California 92037 , United States., Merchant RR; Department of Chemistry , Scripps Research , 10550 North Torrey Pines Road , La Jolla , California 92037 , United States., Mykhailiuk PK; Department of Chemistry , Scripps Research , 10550 North Torrey Pines Road , La Jolla , California 92037 , United States.; Enamine Ltd. , Chervonotkatska 78 , 02094 Kyiv , Ukraine.; Chemistry Department , Taras Shevchenko National University of Kyiv , Volodymyrska 64 , 01601 Kyiv , Ukraine., Sanchez BB; Automated Synthesis Facility , Scripps Research , 10550 North Torrey Pines Road , La Jolla , California 92037 , United States., Yang S; Department of Chemistry , La Jolla Laboratories , Pfizer 10770 Science Center Drive , San Diego , California 92121 , United States., Perry MA; Pfizer Medicinal Sciences , Eastern Point Road , Groton , Connecticut 06340 , United States., Gallego GM; Department of Chemistry , La Jolla Laboratories , Pfizer 10770 Science Center Drive , San Diego , California 92121 , United States., Mousseau JJ; Pfizer Medicinal Sciences , Eastern Point Road , Groton , Connecticut 06340 , United States., Collins MR; Department of Chemistry , La Jolla Laboratories , Pfizer 10770 Science Center Drive , San Diego , California 92121 , United States., Cherney RJ; Research & Development , Bristol-Myers Squibb Company , Rt. 206 & Province Line Road , Princeton , New Jersey 08543 , United States., Lebed PS; Enamine Ltd. , Chervonotkatska 78 , 02094 Kyiv , Ukraine.; ChemBioCenter , Taras Shevchenko National University of Kyiv , Volodymyrska 64 , 01601 Kyiv , Ukraine., Chen JS; Automated Synthesis Facility , Scripps Research , 10550 North Torrey Pines Road , La Jolla , California 92037 , United States., Qin T; Department of Chemistry , Scripps Research , 10550 North Torrey Pines Road , La Jolla , California 92037 , United States., Baran PS; Department of Chemistry , Scripps Research , 10550 North Torrey Pines Road , La Jolla , California 92037 , United States.
Jazyk:	angličtina
Zdroj:	Journal of the American Chemical Society [J Am Chem Soc] 2019 Apr 24; Vol. 141 (16), pp. 6726-6739. Date of Electronic Publication: 2019 Apr 16.
DOI:	10.1021/jacs.9b02238
Abstrakt:	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.
Databáze:	MEDLINE
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