Copper(I)/TEMPO-catalyzed Aerobic Oxidation of Primary Alcohols to Aldehydes with Ambient Air

Overview

Journal Nat Protoc

Specialties Biology
Pathology
Science

Date 2012 May 29

PMID 22635108

Citations 25

Authors

Jessica M Hoover

Janelle E Steves

Shannon S Stahl

Affiliations

Soon will be listed here.

Abstract

This protocol describes a practical laboratory-scale method for aerobic oxidation of primary alcohols to aldehydes, using a chemoselective Cu(I)/TEMPO (TEMPO = 2,2,6,6-tetramethyl-1-piperidinyloxyl) catalyst system. The catalyst is prepared in situ from commercially available reagents, and the reactions are performed in a common organic solvent (acetonitrile) with ambient air as the oxidant. Three different reaction conditions and three procedures for the isolation and purification of the aldehyde product are presented. The oxidations of eight different alcohols, described here, include representative examples of each reaction condition and purification method. Reaction times vary from 20 min to 24 h, depending on the alcohol, whereas the purification methods each take about 2 h. The total time necessary for the complete protocol ranges from 3 to 26 h.

Citing Articles

Selective Reduction of Esters to Access Aldehydes Using Fiddler Crab-Type Boranes.

Dudas A, Gyomore A, Meszaros B, Gondar S, Adamik R, Fegyverneki D J Am Chem Soc. 2024; 147(1):1112-1122.

PMID: 39723648 PMC: 11726553. DOI: 10.1021/jacs.4c14596.

Effects of the ligand linkers on stability of mixed-valence Cu(I)Cu(II) and catalytic aerobic alcohol oxidation activity.

Jehdaramarn A, Chantarojsiri T, Worakul T, Surawatanawong P, Chainok K, Sangtrirutnugul P Sci Rep. 2024; 14(1):15497.

PMID: 38969824 PMC: 11226613. DOI: 10.1038/s41598-024-66227-2.

Room-Temperature Copper-Catalyzed Etherification of Aryl Bromides.

Strauss M, Greaves M, Kim S, Teijaro C, Schmidt M, Scola P Angew Chem Int Ed Engl. 2024; 63(19):e202400333.

PMID: 38359082 PMC: 11045308. DOI: 10.1002/anie.202400333.

Efficient synthesis of fully renewable, furfural-derived building blocks formal Diels-Alder cycloaddition of atypical addends.

Cioc R, Harsevoort E, Lutz M, Bruijnincx P Green Chem. 2023; 25(23):9689-9694.

PMID: 38028818 PMC: 10680129. DOI: 10.1039/d3gc02357e.

Improved Synthesis of the Selected Serine Protease uPA Inhibitor UAMC-00050, a Lead Compound for the Treatment of Dry Eye Disease.

Ceradini D, Cacivkins P, Ramos-Llorca A, Shubin K Org Process Res Dev. 2022; 26(10):2937-2946.

PMID: 36311379 PMC: 9594321. DOI: 10.1021/acs.oprd.2c00244.

References

Gligorich K, Sigman M . Recent advancements and challenges of palladium(II)-catalyzed oxidation reactions with molecular oxygen as the sole oxidant. Chem Commun (Camb). 2009; (26):3854-67. PMC: 2873851. DOI: 10.1039/b902868d. View

Huang L, Jiang H, Qi C, Liu X . Copper-catalyzed intermolecular oxidative [3 + 2] cycloaddition between alkenes and anhydrides: a new synthetic approach to γ-lactones. J Am Chem Soc. 2010; 132(50):17652-4. DOI: 10.1021/ja108073k. View

Taylor R, Reid M, Foot J, Raw S . Tandem oxidation processes using manganese dioxide: discovery, applications, and current studies. Acc Chem Res. 2005; 38(11):851-69. DOI: 10.1021/ar050113t. View

Hodgson D, Bray C, Kindon N . Enamines from terminal epoxides and hindered lithium amides. J Am Chem Soc. 2004; 126(22):6870-1. DOI: 10.1021/ja031770o. View

Kumpulainen E, Koskinen A . Catalytic activity dependency on catalyst components in aerobic copper-TEMPO oxidation. Chemistry. 2009; 15(41):10901-11. DOI: 10.1002/chem.200901245. View

Marko , Giles , Tsukazaki , Brown , Urch . Copper-Catalyzed Oxidation of Alcohols to Aldehydes and Ketones: An Efficient, Aerobic Alternative. Science. 1996; 274(5295):2044-6. DOI: 10.1126/science.274.5295.2044. View

Uyanik M, Ishihara K . Hypervalent iodine-mediated oxidation of alcohols. Chem Commun (Camb). 2009; (16):2086-99. DOI: 10.1039/b823399c. View

Gonzalez-Nunez M, Mello R, Olmos A, Acerete R, Asensio G . Oxidation of alcohols to carbonyl compounds with CrO3.SiO2 in supercritical carbon dioxide. J Org Chem. 2006; 71(3):1039-42. DOI: 10.1021/jo052137j. View

Sheldon R, Arends I, Dijksman A . Green, catalytic oxidations of alcohols. Acc Chem Res. 2002; 35(9):774-81. DOI: 10.1021/ar010075n. View

10.

Stahl S . Palladium oxidase catalysis: selective oxidation of organic chemicals by direct dioxygen-coupled turnover. Angew Chem Int Ed Engl. 2004; 43(26):3400-20. DOI: 10.1002/anie.200300630. View

11.

Mallat T, Baiker A . Oxidation of alcohols with molecular oxygen on solid catalysts. Chem Rev. 2004; 104(6):3037-58. DOI: 10.1021/cr0200116. View

12.

Hoover J, Stahl S . Highly practical copper(I)/TEMPO catalyst system for chemoselective aerobic oxidation of primary alcohols. J Am Chem Soc. 2011; 133(42):16901-10. PMC: 3197761. DOI: 10.1021/ja206230h. View