Efficient Aerobic Oxidation of Organic Molecules by Multistep Electron Transfer

Overview

Journal Angew Chem Int Ed Engl

Specialty Chemistry

Date 2020 Dec 28

PMID 33368909

Citations 12

Authors

Jie Liu

Arnar Gudmundsson

Jan-E Backvall

Affiliations

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Abstract

This Minireview presents recent important homogenous aerobic oxidative reactions which are assisted by electron transfer mediators (ETMs). Compared with direct oxidation by molecular oxygen (O ), the use of a coupled catalyst system with ETMs leads to a lower overall energy barrier via stepwise electron transfer. This cooperative catalytic process significantly facilitates the transport of electrons from the reduced form of the substrate-selective redox catalyst (SSRC ) to O , thereby increasing the efficiency of the aerobic oxidation. In this Minireview, we have summarized the advances accomplished in recent years in transition-metal-catalyzed as well as metal-free aerobic oxidations of organic molecules in the presence of ETMs. In addition, the recent progress of photochemical and electrochemical oxidative functionalization using ETMs and O as the terminal oxidant is also highlighted. Furthermore, the mechanisms of these transformations are showcased.

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References

Cooper J, Luo C, Kameyama R, Van Humbeck J . Combined Iron/Hydroxytriazole Dual Catalytic System for Site Selective Oxidation Adjacent to Azaheterocycles. J Am Chem Soc. 2018; 140(4):1243-1246. DOI: 10.1021/jacs.7b12864. View

Nutting J, Rafiee M, Stahl S . Tetramethylpiperidine N-Oxyl (TEMPO), Phthalimide N-Oxyl (PINO), and Related N-Oxyl Species: Electrochemical Properties and Their Use in Electrocatalytic Reactions. Chem Rev. 2018; 118(9):4834-4885. PMC: 6284524. DOI: 10.1021/acs.chemrev.7b00763. View

Mitsudome T, Mizumoto K, Mizugaki T, Jitsukawa K, Kaneda K . Wacker-type oxidation of internal olefins using a PdCl2/N,N-dimethylacetamide catalyst system under copper-free reaction conditions. Angew Chem Int Ed Engl. 2009; 49(7):1238-40. DOI: 10.1002/anie.200905184. View

Deng Y, Persson A, Backvall J . Palladium-catalyzed oxidative carbocyclizations. Chemistry. 2012; 18(37):11498-523. DOI: 10.1002/chem.201201494. View

Pagliaro M, Campestrini S, Ciriminna R . Ru-based oxidation catalysis. Chem Soc Rev. 2005; 34(10):837-45. DOI: 10.1039/b507094p. View

Samec J, Ell A, Backvall J . Mechanism of hydrogen transfer to imines from a hydroxycyclopentadienyl ruthenium hydride. Support for a stepwise mechanism. Chem Commun (Camb). 2004; (23):2748-9. DOI: 10.1039/b410698a. View

Svoboda J, Schmaderer H, Konig B . Thiourea-enhanced flavin photooxidation of benzyl alcohol. Chemistry. 2007; 14(6):1854-65. DOI: 10.1002/chem.200701319. View

Liu J, Gudmundsson A, Backvall J . Efficient Aerobic Oxidation of Organic Molecules by Multistep Electron Transfer. Angew Chem Int Ed Engl. 2020; 60(29):15686-15704. PMC: 9545650. DOI: 10.1002/anie.202012707. View

Kozack C, Sowin J, Jaworski J, Iosub A, Stahl S . Aerobic Acyloxylation of Allylic C-H Bonds Initiated by a Pd Precatalyst with 4,5-Diazafluoren-9-one as an Ancillary Ligand. ChemSusChem. 2019; 12(13):3003-3007. PMC: 7641472. DOI: 10.1002/cssc.201900727. View

10.

Murray A, Dowley M, Pradaux-Caggiano F, Baldansuren A, Fielding A, Tuna F . Catalytic Amine Oxidation under Ambient Aerobic Conditions: Mimicry of Monoamine Oxidase B. Angew Chem Int Ed Engl. 2015; 54(31):8997-9000. PMC: 4524416. DOI: 10.1002/anie.201503654. View

11.

Wiebe A, Gieshoff T, Mohle S, Rodrigo E, Zirbes M, Waldvogel S . Electrifying Organic Synthesis. Angew Chem Int Ed Engl. 2018; 57(20):5594-5619. PMC: 5969240. DOI: 10.1002/anie.201711060. View

12.

Xie Y, Mo W, Xu D, Shen Z, Sun N, Hu B . Efficient NO equivalent for activation of molecular oxygen and its applications in transition-metal-free catalytic aerobic alcohol oxidation. J Org Chem. 2007; 72(11):4288-91. DOI: 10.1021/jo0705824. View

13.

Deng Y, Backvall J . Palladium-catalyzed oxidative acyloxylation/carbocyclization of allenynes. Angew Chem Int Ed Engl. 2013; 52(11):3217-21. PMC: 3601422. DOI: 10.1002/anie.201208718. View

14.

Wang D, Weinstein A, White P, Stahl S . Ligand-Promoted Palladium-Catalyzed Aerobic Oxidation Reactions. Chem Rev. 2017; 118(5):2636-2679. DOI: 10.1021/acs.chemrev.7b00334. View

15.

Henderson W, Check C, Proust N, Stambuli J . Allylic oxidations of terminal olefins using a palladium thioether catalyst. Org Lett. 2010; 12(4):824-7. DOI: 10.1021/ol902905w. View

16.

Eswaramoorthy M, Nair J, Raj A, Itoh N, Shoji H, Namba T . A one-step conversion of benzene to phenol with a palladium membrane. Science. 2002; 295(5552):105-7. DOI: 10.1126/science.1066527. View

17.

Pattillo C, Strambeanu I, Calleja P, Vermeulen N, Mizuno T, White M . Aerobic Linear Allylic C-H Amination: Overcoming Benzoquinone Inhibition. J Am Chem Soc. 2016; 138(4):1265-72. PMC: 4831720. DOI: 10.1021/jacs.5b11294. View

18.

Piera J, Persson A, Caldentey X, Backvall J . Water as nucleophile in palladium-catalyzed oxidative carbohydroxylation of allene-substituted conjugated dienes. J Am Chem Soc. 2007; 129(46):14120-1. DOI: 10.1021/ja075488j. View

19.

Dijksman A, Arends I, Sheldon R . Cu(II)-nitroxyl radicals as catalytic galactose oxidase mimics. Org Biomol Chem. 2003; 1(18):3232-7. DOI: 10.1039/b305941c. View

20.

Wickens Z, Morandi B, Grubbs R . Aldehyde-selective Wacker-type oxidation of unbiased alkenes enabled by a nitrite co-catalyst. Angew Chem Int Ed Engl. 2013; 52(43):11257-60. DOI: 10.1002/anie.201306756. View