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Electrochemical Oxidation of Alcohols and Aldehydes to Carboxylic Acids Catalyzed by 4-Acetamido-TEMPO: An Alternative to “Anelli” and “Pinnick” Oxidations

Journal Article · · ACS Catalysis
 [1];  [2];  [3];  [4];  [2]
  1. Univ. of Wisconsin, Madison, WI (United States). Dept. of Chemistry; University of Wisconsin-Madison
  2. Univ. of Wisconsin, Madison, WI (United States). Dept. of Chemistry
  3. AbbVie Inc., Chicago, IL (United States). Process Research and Development
  4. AbbVie Inc., Chicago, IL (United States). Discovery Chemistry and Technology; Boehringer Ingelheim International GmbH, Biberach an der Riss (Germany). Medicinal Chemistry
+ Show Author Affiliations
Here, an electrocatalytic method has been developed to oxidize primary alcohols and aldehydes to the corresponding carboxylic acids using 4-acetamido-2,2,6,6-tetramethylpiperidin-1-oxyl (ACT) as a mediator. The method successfully converts benzylic, aliphatic, heterocyclic, and other heteroatom-containing substrates to the corresponding carboxylic acids in aqueous solution at room temperature. The mild conditions enable retention of stereochemistry adjacent to the site of oxidation, as demonstrated in a 40 g-scale synthesis of a precursor to levetiracetam, a medication used to treat epilepsy.
Research Organization:
Univ. of Wisconsin, Madison, WI (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23)
Contributing Organization:
IKA, Staufen im Breisgau (Germany)
Grant/Contract Number:
FC02-07ER64494
OSTI ID:
1471689
Journal Information:
ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 7 Vol. 8; ISSN 2155-5435
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Cited By (8)

Electrochemistry Broadens the Scope of Flavin Photocatalysis: Photoelectrocatalytic Oxidation of Unactivated Alcohols journal November 2019
Electrochemistry Broadens the Scope of Flavin Photocatalysis: Photoelectrocatalytic Oxidation of Unactivated Alcohols journal November 2019
Metabolism Mimicry: An Electrosynthetic Method for the Selective Deethylation of Tertiary Benzamides journal March 2019
Efficient Oxidation of Benzylic and Aliphatic Alcohols Using a Bioinspired Cross-Bridged Cyclam Manganese Complex with H 2 O 2: Efficient Oxidation of Benzylic and Aliphatic Alcohols Using a Bioinspired Cross-Bridged Cyclam Manganese Complex with H 2 O 2 journal November 2018
Electrochemical oxidation synergizing with Brønsted-acid catalysis leads to [4 + 2] annulation for the synthesis of pyrazines journal January 2019
Direct anodic (thio)acetalization of aldehydes with alcohols (thiols) under neutral conditions, and computational insight into the electrochemical formation of the acetals journal January 2019
Competition of Electrocatalytic Activity and Oxidative Ring Cleavage of Unstable Triazolinediones: The Substituent Effect journal January 2019
Biomimetic Cu/Nitroxyl Catalyst Systems for Selective Alcohol Oxidation journal April 2019

Figures / Tables (10)

Scheme 1(p. 3)figure Scheme 1
Figure 1(p. 5)figure Figure 1
Figure 2(p. 7)figure Figure 2
Figure 3(p. 7)figure Figure 3
Scheme 2(p. 8)figure Scheme 2
Figure 4(p. 9)figure Figure 4
Table 1(p. 10)table Table 1
Figure 5(p. 11)figure Figure 5
Figure 6(p. 12)figure Figure 6
Table 2(p. 14)table Table 2

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
59 BASIC BIOLOGICAL SCIENCES
alcohols
aldehydes
aminoxyl
carboxylic acids
electrocatalysis
electrochemistry
nitroxyl
oxidation