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

被引：137

作者：

Rafiee, Mohammad ^{[1
]}

Konz, Zachary M. ^{[1
]}

Graaf, Matthew D. ^{[2
]}

Koolman, Hannes F. ^{[3
,4
]}

Stahl, Shannon S. ^{[1
]}

机构：

[1] Univ Wisconsin, Dept Chem, 1101 Univ Ave, Madison, WI 53706 USA

[2] AbbVie, Proc R&D, 1401 Sheridan Rd, N Chicago, IL 60064 USA

[3] AbbVie, Discovery Chem & Technol, 1 North Waukegan Rd, N Chicago, IL 60064 USA

[4] Boehringer Ingelheim Pharma GmbH & Co KG, Med Chem, Birkendorfer Str 65, D-88397 Biberach, Germany

来源：

ACS CATALYSIS | 2018年 / 8卷 / 07期

关键词：

alcohols; aldehydes; carboxylic acids; oxidation; electrocatalysis; electrochemistry; nitroxyl; aminoxyl; TEMPO-MEDIATED OXIDATION; ELECTROCATALYTIC OXIDATION; ELECTROORGANIC SYNTHESIS; SELECTIVE OXIDATION; SECONDARY ALCOHOLS; DERIVATIVES; BENZALDEHYDES; LEVETIRACETAM; EXPLOITATION; MECHANISM;

D O I：

10.1021/acscatal.8b01640

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

An electrocatalytic method has been developed to oxidize primary alcohols and aldehydes to the corresponding carboxylic acids using 4-acetamido-2,2,6,6-tetramethyl-piperidin-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.

引用

页码：6738 / 6744

页数：13

共 57 条

[1]

ANELLI PL, 1987, J ORG CHEM, V52, P2559

[2]

Backvall J.-E., 2010, MODERN OXIDATION MET, V2nd, P147, DOI DOI 10.1002/9783527632039.CH5

[3] Cooperative electrocatalytic alcohol oxidation with electron-proton-transfer mediators [J].

Badalyan, Artavazd ;

Stahl, Shannon S. .

NATURE, 2016, 535 (7612) :406-410

[4] OXIDATION OF ALPHA,BETA-UNSATURATED ALDEHYDES [J].

BAL, BS ;

CHILDERS, WE ;

PINNICK, HW .

TETRAHEDRON, 1981, 37 (11) :2091-2096

[5]

Balaraman E, 2013, NAT CHEM, V5, P122, DOI [10.1038/NCHEM.1536, 10.1038/nchem.1536]

[6] Selective TEMPO-catalyzed chemicals vs. electrochemical oxidation of carbohydrate derivatives [J].

Barbier, Maximilien ;

Breton, Tony ;

Servat, Karine ;

Grand, Eric ;

Kokoh, Boniface ;

Kovensky, Jose .

JOURNAL OF CARBOHYDRATE CHEMISTRY, 2006, 25 (2-3) :253-266

[7]

Bobbitt J.M., 2010, ORG REACT, V74, P103, DOI [10.1002/0471264180.or074.02, DOI 10.1002/0471264180.OR074.02]

[8] A synthesis of levetiracetam based on (S)-N-phenylpantolactam as a chiral auxiliary [J].

Boschi, F ;

Camps, P ;

Comes-Franchini, M ;

Muñoz-Torrero, D ;

Ricci, A ;

Sánchez, L .

TETRAHEDRON-ASYMMETRY, 2005, 16 (22) :3739-3745

[9] Regio- and stereoselective synthesis of the major metabolite of quercetin, quercetin-3-O-β-D-glucuronide [J].

Bouktaib, M ;

Atmani, A ;

Rolando, C .

TETRAHEDRON LETTERS, 2002, 43 (35) :6263-6266

[10]

Brückner C, 2010, STABLE RADICALS: FUNDAMENTALS AND APPLIED ASPECTS OF ODD-ELECTRON COMPOUNDS, P433

← 1 2 3 4 5 6 →