Copper is one of the most abundant and less toxic transition metals. Nature takes advantage of the bioavailability and rich redox chemistry of Cu to carry out oxygenase and oxidase organic transformations using O2 (or H2O2) as oxidant. Inspired by the reactivity of these Cu-dependent metalloenzymes, chemists have developed synthetic protocols to functionalize organic molecules under enviormentally benign conditions. Copper also promotes other transformations usually catalyzed by 4d and 5d transition metals (Pd, Pt, Rh, etc.) such as nitrene insertions or C-C and C-heteroatom coupling reactions. In this review, we summarized the most relevant research in which copper promotes or catalyzes the functionalization of organic molecules, including biological catalysis, bioinspired model systems, and organometallic reactivity. The reaction mechanisms by which these processes take place are discussed in detail.
Conflict of interest statement
The authors declare no competing financial interest.
Copper-Catalyzed Aerobic Oxidations of Organic Molecules: Pathways for Two-Electron Oxidation with a Four-Electron Oxidant and a One-Electron Redox-Active Catalyst.Acc Chem Res. 2015 Jun 16;48(6):1756-66. doi: 10.1021/acs.accounts.5b00060. Epub 2015 May 28. Acc Chem Res. 2015. PMID: 26020118
Copper-Catalyzed Oxidative Carbon-Carbon and/or Carbon-Heteroatom Bond Formation with O2 or Internal Oxidants.Acc Chem Res. 2018 May 15;51(5):1092-1105. doi: 10.1021/acs.accounts.7b00611. Epub 2018 Apr 12. Acc Chem Res. 2018. PMID: 29648789
Overcoming the "oxidant problem": strategies to use O2 as the oxidant in organometallic C-H oxidation reactions catalyzed by Pd (and Cu).Acc Chem Res. 2012 Jun 19;45(6):851-63. doi: 10.1021/ar2002045. Epub 2012 Jan 23. Acc Chem Res. 2012. PMID: 22263575 Free PMC article.
Electronic and Steric Tuning of a Prototypical Piano Stool Complex: Rh(III) Catalysis for C-H Functionalization.Acc Chem Res. 2018 Jan 16;51(1):170-180. doi: 10.1021/acs.accounts.7b00444. Epub 2017 Dec 22. Acc Chem Res. 2018. PMID: 29272106 Free PMC article. Review.
Selenium- and tellurium-containing fluorescent molecular probes for the detection of biologically important analytes.Acc Chem Res. 2014 Oct 21;47(10):2985-98. doi: 10.1021/ar500187v. Epub 2014 Sep 23. Acc Chem Res. 2014. PMID: 25248146 Review.
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A merged copper(I/II) cluster isolated from Glaser coupling.Nat Commun. 2019 Oct 24;10(1):4848. doi: 10.1038/s41467-019-12889-w. Nat Commun. 2019. PMID: 31649254 Free PMC article.
Impact of Intramolecular Hydrogen Bonding on the Reactivity of Cupric Superoxide Complexes with O-H and C-H Substrates.Angew Chem Int Ed Engl. 2019 Dec 2;58(49):17572-17576. doi: 10.1002/anie.201908471. Epub 2019 Oct 23. Angew Chem Int Ed Engl. 2019. PMID: 31469942
Directed Hydroxylation of sp2 and sp3 C-H Bonds Using Stoichiometric Amounts of Cu and H2O2.Inorg Chem. 2019 Jun 3;58(11):7584-7592. doi: 10.1021/acs.inorgchem.9b00901. Epub 2019 May 14. Inorg Chem. 2019. PMID: 31084018 Free PMC article.