Copper-Promoted Functionalization of Organic Molecules: from Biologically Relevant Cu/O Model Systems to Organometallic Transformations

Overview

Journal Chem Rev

Publisher American Chemical Society

Specialty Chemistry

Date 2019 Jan 31

PMID 30698952

Citations 50

Authors

Rachel Trammell

Khashayar Rajabimoghadam

Isaac Garcia-Bosch

Affiliations

Soon will be listed here.

Abstract

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 O (or HO) 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.

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References

ITOH , Taki , Nakao , HOLLAND , Tolman , Que Jr L . Aliphatic Hydroxylation by a Bis(µ-oxo)dicopper(III) Complex. Angew Chem Int Ed Engl. 2000; 39(2):398-400. DOI: 10.1002/(sici)1521-3773(20000117)39:2<398::aid-anie398>3.0.co;2-2. View

Santagostini L, Gullotti M, Monzani E, Casella L, Dillinger R, Tuczek F . Reversible dioxygen binding and phenol oxygenation in a tyrosinase model system. Chemistry. 2000; 6(3):519-22. DOI: 10.1002/(sici)1521-3765(20000204)6:3<519::aid-chem519>3.0.co;2-i. View

Ohta T, Tachiyama T, Yoshizawa K, Yamabe T, Uchida T, Kitagawa T . Synthesis, structure, and H2O2-dependent catalytic functions of disulfide-bridged dicopper(I) and related thioether-copper(I) and thioether-copper(II) complexes. Inorg Chem. 2001; 39(19):4358-69. DOI: 10.1021/ic000018a. View

Li X, Yang J, Kozlowski M . Enantioselective oxidative biaryl coupling reactions catalyzed by 1,5-diazadecalin metal complexes. Org Lett. 2001; 3(8):1137-40. DOI: 10.1021/ol015595x. View

Taki M, Itoh S, Fukuzumi S . C-H bond activation of external substrates with a bis(mu-oxo)dicopper(III) complex. J Am Chem Soc. 2001; 123(25):6203-4. DOI: 10.1021/ja015721s. View

Itoh S, Kumei H, Taki M, Nagatomo S, Kitagawa T, Fukuzumi S . Oxygenation of phenols to catechols by a (mu-eta 2:eta 2-peroxo)dicopper(II) complex: mechanistic insight into the phenolase activity of tyrosinase. J Am Chem Soc. 2001; 123(27):6708-9. DOI: 10.1021/ja015702i. View

Burkitt M . A critical overview of the chemistry of copper-dependent low density lipoprotein oxidation: roles of lipid hydroperoxides, alpha-tocopherol, thiols, and ceruloplasmin. Arch Biochem Biophys. 2001; 394(1):117-35. DOI: 10.1006/abbi.2001.2509. View

Klinman J . Mechanisms Whereby Mononuclear Copper Proteins Functionalize Organic Substrates. Chem Rev. 1996; 96(7):2541-2562. DOI: 10.1021/cr950047g. View

Liang H, Zhang C, Henson M, Sommer R, Hatwell K, Kaderli S . Contrasting copper-dioxygen chemistry arising from alike tridentate alkyltriamine copper(I) complexes. J Am Chem Soc. 2002; 124(16):4170-1. DOI: 10.1021/ja0125265. View

10.

Ribas X, Jackson D, Donnadieu B, Mahia J, Parella T, Xifra R . Aryl CbondH activation by CuII to form an organometallic aryl-CuIII species: a novel twist on copper disproportionation. Angew Chem Int Ed Engl. 2002; 41(16):2991-4. DOI: 10.1002/1521-3773(20020816)41:16<2991::AID-ANIE2991>3.0.CO;2-6. View

11.

Aboelella N, Lewis E, Reynolds A, Brennessel W, Cramer C, Tolman W . Snapshots of dioxygen activation by copper: the structure of a 1:1 Cu/O(2) adduct and its use in syntheses of asymmetric Bis(mu-oxo) complexes. J Am Chem Soc. 2002; 124(36):10660-1. DOI: 10.1021/ja027164v. View

12.

Battaini G, Monzani E, Perotti A, Para C, Casella L, Santagostini L . A double arene hydroxylation mediated by dicopper(II)-hydroperoxide species. J Am Chem Soc. 2003; 125(14):4185-98. DOI: 10.1021/ja0280776. View

13.

Whittaker J . Free radical catalysis by galactose oxidase. Chem Rev. 2003; 103(6):2347-63. DOI: 10.1021/cr020425z. View

14.

Vedernikov A, Caulton K . Angular ligand constraint yields an improved olefin aziridination catalyst. Org Lett. 2003; 5(15):2591-4. DOI: 10.1021/ol034681p. View

15.

Schonecker B, Zheldakova T, Liu Y, Kotteritzsch M, Gunther W, Gorls H . Biomimetic hydroxylation of nonactivated CH2 groups with copper complexes and molecular oxygen. Angew Chem Int Ed Engl. 2003; 42(28):3240-4. DOI: 10.1002/anie.200250815. View

16.

Osako T, Ohkubo K, Taki M, Tachi Y, Fukuzumi S, Itoh S . Oxidation mechanism of phenols by dicopper-dioxygen (Cu(2)/O(2)) complexes. J Am Chem Soc. 2003; 125(36):11027-33. DOI: 10.1021/ja029380+. View

17.

Evans J, Ahn K, Klinman J . Evidence that dioxygen and substrate activation are tightly coupled in dopamine beta-monooxygenase. Implications for the reactive oxygen species. J Biol Chem. 2003; 278(50):49691-8. DOI: 10.1074/jbc.M300797200. View

18.

Diaz-Requejo M, Belderrain T, Nicasio M, Trofimenko S, Perez P . Cyclohexane and benzene amination by catalytic nitrene insertion into C-H bonds with the copper-homoscorpionate catalyst TpBr3CuNCMe. J Am Chem Soc. 2003; 125(40):12078-9. DOI: 10.1021/ja037072l. View

19.

Ley S, Thomas A . Modern synthetic methods for copper-mediated C(aryl)[bond]O, C(aryl)[bond]N, and C(aryl)[bond]S bond formation. Angew Chem Int Ed Engl. 2003; 42(44):5400-49. DOI: 10.1002/anie.200300594. View

20.

Fujii T, Naito A, Yamaguchi S, Wada A, Funahashi Y, Jitsukawa K . Construction of a square-planar hydroperoxo-copper(II) complex inducing a higher catalytic reactivity. Chem Commun (Camb). 2003; (21):2700-1. DOI: 10.1039/b308073k. View